fracking

Hydraulic Fracturing for Mining Natural Gas

aka, Fracking

Part 1 Part 2 Part 3 Part 4

Already, technological advancements like hydraulic fracturing have allowed development of previously uneconomic natural gas and oil deposits. In fact, since 2008, U.S. oil and natural gas production has increased each year. In 2011, U.S. crude oil production reached its highest level in 8 years, and U.S. natural gas production grew in 2011 as well the largest year-over-year volumetric increase in history easily eclipsing the previous all-time production record set in 1973. Overall, oil imports have been falling since 2005, and oil import dependence declined from 57 percent in 2008 to 45 percent in 2011 the lowest level since 1995.

From the US Department of the Interior

Discovery now ?....

natural gas part of the energy mix hydraulic fracturing (or fracking) uses a fluid to create cracks in sedimentary rock and a proppant (small solid) to hold open the crack

Hey professor, what is natural gas ? and since it is natural, can I get it at Whole Foods?

Methane plus small amounts of higher hydrocarbons (primarily ethane). In traditional mining operations It is found associated with other hydrocarbon fuel.

Depending on where you are you may have easy access to refined natural gas

Mostly methane with some ethane and higher hydrocarbons

remember each carbon has 4 valence electrons

and therefore has four bonds

Key Personnel Involved in the Issue

Landowners Concerned citizens Process Engineers Fuel and Energy Specialists Environmental/Energy Auditors Local and Federal Officials Involved with Natural Gas Recovery and Processing Water Quality Engineers and Municipal Officers News Media (Print, TV, Radio, Internet) Covering Natural

Gas Issues Managers at Natural Gas Companies Popular media stars and sons of slain rock stars

Seminar Outcomes for Parts 1 and 2

global energy picture/position of natural gas options for mining natural gas environmental issues concerning hydraulic

fracturing

economic and safety issues existing and potential legislation

Prof. Gennaro J. Maffia

Jerry

Often called a fracking engineer; or words to that effect

Jerry Maffia who is this guy?

1. Professor of Chemical Engineering Manhattan College 2. Manager of Technology Development ARCO a. Petrochemical & Refining b. Start-up & Technical Services

Jerry Maffia some projects

Energy Related Projects a. Alaskan Pipeline and Remote Gas b. Fuel Oxygenates c. Biofuels/Bioseparations d. Energy Integration e. Novel Separations f. Manufacture of Proppants

Jerry Maffia recent locales Project Visits Dubai Abu Dhabi Dhahran Singapore Pingdingshan Dresden Limoges Prague Dublin Chisinau Oxford Plymouth many NA sites

Student Researchers they do all the work

and so on.............

Drexel University Senior Project Team Using CO2 as a Fracking Fluid

Amanda, Amanda

The FracKINGS Design Group

Morgan, Jimmy, Amanda, Amanda

Mining

Methodology....

hydraulic fracturing .how? drill a vertical well extend the drilling horizontally case the well perforate the casing pump in high pressure water and sand to fracture the shale at the perforations recover/dispose of the water cap the well bore send gas to treatment treated gas to interstate pipeline system

What is all the fuss about .........

Hey

Jerr

y w

hat

s th

e st

ory?

SOME HEADLINES.........

Regulations and Current Policy

May 2012 News

Safe Drinking Water Act Several statutes may be leveraged to protect water quality, but EPA's central authority to protect drinking water is drawn from the Safe Drinking Water Act (SDWA). The protection of USDWs is focused in the Underground Injection Control (UIC) program, which regulates the subsurface emplacement of fluid. Congress provided for exclusions to UIC authority (SDWA 1421(d)), however, with the most recent language added via the Energy Policy Act of 2005:

May 2012 News

"The term 'underground injection' (A) means the subsurface emplacement of fluids by well injection; and (B) excludes (i) the underground injection of natural gas for purposes of storage; and (ii) the underground injection of fluids or propping agents (other than diesel fuels) pursuant to hydraulic fracturing operations related to oil, gas, or geothermal production activities." While the SDWA specifically excludes hydraulic fracturing from UIC regulation under SDWA 1421 (d)(1), the use of diesel fuel during hydraulic fracturing is still regulated by the UIC program.

May 2012 News

State oil and gas agencies may have additional regulations for hydraulic fracturing. In addition, states or EPA have authority under the Clean Water Act to regulate discharge of produced waters from hydraulic fracturing operations. Clean Water Act

Disposal of flowback into surface waters of the United States is regulated by the National Pollutant Discharge Elimination System (NPDES) permit program. The Clean Water Act authorizes the NPDES program.

Economic Impact

A World Scale Petrochemical Plant In Pittsburgh

.....are you crazy professor?

Maybe, but ...............

Fracturing now ?....

natural gas part of the energy mix Hydraulic fracturing uses water Dry Frac uses CO2 Gas Frac uses LPG

GasFrac Inc., Calgary, Alberta

Boom in Cotulla, Texas

The economic transformation is the result of a new drilling method, hydraulic fracturing, combined with horizontal drilling, that allows companies to extract oil and gas from impermeable layers of shale.

Selected Headlines follow many differing opinions; often frustrating

Development of Collagen-Based Hydraulic Fracturing Fluid and Study of

Proppant Settling Characteristics

Manhattan College Riverdale, New York

Ramiro Magboo, Student

Charity Njau, Student Dr. Gennaro Maffia, Professor

The Twenty-Seventh International Conference on Solid Waste Technology and Management

Session 8B, Research Advances 2

March 14, 2012

Outline

Objective

Hydraulic Fracturing & Fluid

Natural gas

Experimental Procedures

Results

Conclusion

Collagen and Its Preparation

Environmental Risk

56 56

Collagen fiber formation

From Shanu Shahs Thesis

collagen molecule is a triple helix of amino acid chains molecules bundle into fibrils fibrils produce fibers fibers cluster to fiber bundles

STARTING MATERIAL, OFTEN WASTE

Crude Corium

Manufacturing Process

Type I

Bovine Hide

Collagen

(corium)

Raw Material

Ball milling Dispersing Freezing Freeze Drying Sterilizing Cross-linking

Sonication

US patent 6,660,829 (12/2003)

Product 1

Product 2 Product 3 Product 4

50 - 100 nm diameter

Bovine Fibrils

from Donna Stauffers Thesis; taken with Dr. Peter Cooke at USDA

Dispersing Collagen Nanofibrils blend organic acid DI water milled collagen to make: C/A/W/X the stock solution where C = 0.1 - 0.75 % collagen A = 5 % acetic acid W = 94.25 - 94.9 % water X = additives

KEY FACTOR: Surface Area ~ 1/fibril diameter ~ 75 m2/g

FORMULATION OF THE COLLAGEN DISPERSION

Standard Dispersion 0.75/5/94.25/X:C/A/W/X

Unique Properties of Fibrils

Placing collagen fibrils in a solution at a pH other than its iso-electric point will induce a surface charge (or chemical potential). The fibrils respond by dispersing and retaining water between them.

+ +

+ +

+

+ Fibrils with a diameter of 10-70 nm can hold up to 500x their mass in water in the vicinity of the charged surface.

20/1 dilution; inverted 3500 rpm, 45 mins, 4 C

Non-viscous phase

Viscous phase

Collagen fibrils hold hundreds of times their mass in water in the vicinity of their charged surface

050

100150200250300

3 4 5 6

pH

Swel

ling

Rat

io

Swelling ratio is the mass of water plus collagen divided by the mass of collagen solids held in a viscous plug at the bottom of a centrifuge tube.

NG Sourcing

methane and associated light hydrocarbons recovered from natural gas fields extracted during petroleum processing biogas

What has been done with NG....

unwanted byproduct no market non-transportable consequently gas was vented or flared now often reinjected interstate pipelines (US)

Controversial.... Por qu

Environmental, Health, and Safety (EHS) concerns contamination of drinking water with natural and synthetic toxins uncontrolled release of gas

What is fuel?

Fuel - solid, liquid or gas oxidized to produce energy

Biofuel - recently dead biological material Fossil Fuel - dead biological material

Force, Pressure, Work, Energy, Power

Force: Newton, (kg)(m)(s-2) Pressure: Pascal, (N)(m-2) Work: Joule, (N)(m) Energy: Joule, (N)(m) Power: Watt, (J)(s-1)

Example: a 60 W light bulb expends 216 kJ

every hour of use and costs the consumer about 1 cent (US)

Key Units of Energy

Energy 1 BTU = 1055 J 1 BTU = 1.055 kJ 1 kWh = 3600 kJ = 3412 BTU 1 scf natural gas = 1000 BTU 1 TCF = 1 quad (BTU basis) 100 quads = typical annual US consumption of energy

Energy in Colloquial Terms kWh = 1 kJ/s of power expended for 1 h Typical Power Company Cost ~ $0.165/kWh 293 kWh = mm BTU

2010 Energy Prices per Million BTU Powder River Basin Coal $0.56 Northern Appalachia Coal $2.08 Natural gas $5.67 Ethanol subsidy $5.92 Petroleum $13.56 Propane $13.92 #2 Heating Oil $15.33 Jet fuel $16.01 Diesel $16.21 Gasoline $18.16 Wood pellets $18.57 Ethanol $24.74 Electricity $34.03

Sources for Data Petroleum $13.56 (EIA World Average Price for 1/08/2010) Northern Appalachia Coal $2.08 (EIA Average Weekly Spot 2010 Powder River Basin Coal $0.56 (EIA Average Weekly Spot 1/08/10) Propane $13.92 (EIA Mont Belvieu, TX Spot Price for 1/12/2010) Natural gas $5.67 (NYMEX contract for February 2010) #2 Heating Oil $15.33 (EIA New York Harbor Price for 1/12/2010) Gasoline $18.16 (EIA New York Harbor Price for 1/12/2010) Diesel $16.21 (EIA #2 Low Sulfur New York Harbor for 1/08/2010) Jet fuel (EIA New York Harbor for 1/12/2010) Ethanol $24.74 (NYMEX Spot for February 2010) Wood pellets $18.57 (Typical Wood Pellet Price for 1/12/2010) Electricity $34.03 (EIA Average Retail Price to Consumers for 2009)

Energy Equivalents approximate LHVs Petroleum 138,000 BTU/gal Gasoline 115,000 BTU/gal Diesel 131,000 BTU/gal Ethanol 76,000 BTU/gal Heating oil - 138,000 BTU/gal Jet fuel 135,000 BTU/gal Propane 91,500 BTU/gal Northern Appalachia Coal 13,000 BTU/lb Natural Gas 21,000 BTU/lb Wood pellets 7,000 BTU/lb Electricity 3,412 BTU/kWh

Unit Levels SI Prefixes

1 EW exa 103 PW peta 106 TW tera 109 GW giga 1012 MW mega 1015 kW kilo 1018 W ----- 1021 mW milli 1024 W micro

Therefore a 1 GW power plant provides 1 million kW (or 1 million kJ/s); so about 31.5 PJ or 0.0315 EJ per year

Natural Gas - Background

Most natural gas is created by two mechanisms: biogenic thermogenic Biogenic gas is created by methanogenic organisms Deeper in the earth, thermogenic gas is created from buried organic material

20th Century Production of NG (conversions 1 MM CF= ~ 1 B BTU; 20 TCF = ~ 20 quads)

Natural Gas World-Wide Locations N

atural gas extraction by countries in cubic meters per year

Natural Gas Production and Transportation

millions of years old recently methods for obtaining this gas, bringing it to the surface, and putting it to use were developed. ancient times no transportation or utilization of NG to speak of

Ancient Times

Fire coming from the earth, burning the natural gas as it seeped out from underground were the root of much myth and superstition.

Mount Parnassus approximately 1000 B.C - Oracle of Delphi, giving out prophecies she claimed were inspired by the flame.

buy low, sell high

About 500 B.C. that the Chinese formed crude pipelines out of bamboo shoots to transport the gas

First Pipelines

First Use of Natural Gas in the Home (100 AD) The King of Persia decided to take advantage of this "eternal flame." But instead of having the gas piped to his homelike we do todayhe built his royal kitchen near the flame.

Natural gas in the kitchen or vice versa

Last 200 Years A two-inch diameter pipeline was built, running 5 + miles from the well to the village of Titusville, PA The construction of this pipeline proved that natural gas could be brought safely and relatively easily from its underground source to be used for practical purposes.

Another first for Pennsylvania that is, after the Chinese

19th and early 20th Centuries natural gas was - source of light. Without pipeline capacity - couldnt transport - does this sound familiar?

Bunsen Burner In 1885, German Robert Bunsen invented a device that mixed natural gas with air in the right proportions this created a flame that could be safely used for cooking and heating

Recent Times Without any way to transport it effectively, natural gas discovered pre-WWII was usually just allowed to vent into the atmosphere, or burnt, when found alongside coal and oil, or simply left in the ground when found alone. One of the first lengthy pipelines was constructed in 1891. This pipeline was 120 miles long, and carried natural gas from wells in central Indiana to the city of Chicago.

OHCOOCH 2224 22 ++

Post WWII through the 1960s Welding techniques, pipe rolling, and metallurgical advances were developed thus providing for reliable pipelines Chicago became a hub

Today, Chicago remains a hub for NG projects/destinations

Just for fuel??? No way.................... natural gas to heat homes and operate appliances manufacturing and processing plants boilers used to generate electricity.

How About Remote Gas? Hey Jerry how do we get the gas off of the North Slope?

Well ??????

Conversion Hydrates Submarines Balloons Alcohols New pipelines Just leave it there Pump it back

We know how to do pipelines are they the answer?

Seems pretty crowded imagine this in Alberta

US Pipeline System

Is the US the only place how about Europe?

Are Fracking and Pipelines the Answer for Remote Gas?

You betcha!

Worldwide Energy Consumption

CMO = cubic mile of oil 1 CMO = 152 quads = 160 EJ

Natural Gas 0.61 CMO Oil 1.06 Coal 0.81 Other 0.52

Engineers love new units of measure

Energy Consumption Patterns

0

50

100

150

200

250

300

350

400

450

500

1960 1970 1980 1990 2000 2010

year

Qua

drill

ion

kJ

USWorld

Units of quads

Breakdown of US Energy Consumption, at 100 quads % can be used in place of quads or vice versa

0.00%

5.00%

10.00%

15.00%

20.00%

25.00%

30.00%

35.00%

40.00%

45.00%

coal natural gas petroleum nuclear renewable

primary category of fuel consumption

perc

ent (

also

~ n

umbe

r of q

uads

)

DOE: US Current and Projected Energy Usage (%)

0

5

10

15

20

25

30

35

40

45

50

1980 1990 2000 2010 2020 2030

CoalNuclearNatural GasLiquidsBiofuelsRenewables

World Energy Consumption

Fuel type

Power in TW Energy in EJ

Oil 5.6 180

Gas 3.5 110

Coal 3.8 120

Hydroelectric 0.9 30

Nuclear 0.9 30

Geothermal, wind, solar, wood

0.13 4

Total 15 471

as a reference: 174,000 TW (174 PW) incoming solar power

corrosion prevention, avoiding liquid drop out in pipelines, consistency in synthesis and burner performance.

NATURAL GAS SPECIFICATIONS

Chem

ical

Com

posi

tion

of N

atur

al G

as

The

tabl

e ou

tline

s th

e ty

pica

l com

pone

nts

of

nat

ural

gas

on

the

Uni

on G

as s

yste

m

and

the

typi

cal r

ange

s fo

r th

ese

valu

es

(allo

win

g fo

r th

e di

ffere

nt s

ourc

es).

Component Typical Analysis (mole %)

Range (mole %)

Methane 95.2 87.0 - 96.0

Ethane 2.5 1.5 - 5.1

Propane 0.2 0.1 - 1.5

iso - Butane 0.03 0.01 - 0.3

normal - Butane 0.03 0.01 - 0.3

iso - Pentane 0.01 trace - 0.14

normal - Pentane 0.01 trace - 0.04

Hexanes plus 0.01 trace - 0.06

Nitrogen 1.3 0.7 - 5.6

Carbon Dioxide 0.7 0.1 - 1.0

Oxygen 0.02 0.01 - 0.1

Hydrogen trace trace - 0.02

Specific Gravity 0.58 0.57 - 0.62

Gross Heating Value (MJ/m3), dry basis *

37.8 36.0 - 40.2

Raw Gas

The gross heating value is the total heat obtained by complete combustion at constant pressure of a unit volume of gas in air, including the heat released by condensing the water vapor in the combustion products (gas, air, and combustion products taken at standard temperature and pressure).

LHV vs HHV

It is a bright, bright world ........

Power Plant Components

Boiler - Energy In Generator Energy Out Surface Condenser Energy Out BFW Pump Energy In

Efficiency (many definitions) one of the simplest is (usable energy out)/(total energy in)

Natural Gas Uses

Industrial Primary Energy Consumption by Fuel 1970 - 2025 (Quadrillion Btu)

Fossil Fuel Electric Power Generation - inefficient

How much is left?

With or without fracking ?

Natural Gas Reserves Rank Country/Region

Natural gas proven reserves (m)

% of total Date of information

World 190,163,119,460,000 100% 1 January 2010 est.

1 Russia 47,570,000,000,000 25.02% 1 January 2010 est. 2 Iran 29,610,000,000,000 15.57% 1 January 2010 est. 3 Qatar 25,470,000,000,000 13.39% 1 January 2010 est. 4 Turkmenistan 7,504,000,000,000 3.95% 1 January 2010 est. 5 Saudi Arabia 7,461,000,000,000 3.92% 1 January 2010 est. 6 United States 6,928,000,000,000 3.64% 1 January 2010 est.

7 United Arab Emirates 6,071,000,000,000 3.19% 1 January 2010 est.

8 Nigeria 5,246,000,000,000 2.76% 1 January 2010 est. 9 Venezuela 4,983,000,000,000 2.62% 1 January 2010 est. 10 Algeria 4,502,000,000,000 2.37% 1 January 2010 est. 11 Iraq 3,170,000,000,000 1.67% 1 January 2010 est. 12 Australia 3,115,000,000,000 1.64% 1 January 2010 est. 13 China 3,030,000,000,000 1.59% 1 January 2010 est. 14 Indonesia 3,001,000,000,000 1.58% 1 January 2010 est. 15 Kazakhstan 2,407,000,000,000 1.27% 1 January 2010 est. 16 Malaysia 2,350,000,000,000 1.24% 1 January 2010 est. 17 Norway 2,313,000,000,000 1.22% 1 January 2010 est. European Union 2,250,000,000,000 1.18% 1 January 2010 est. 18 Uzbekistan 1,841,000,000,000 0.97% 1 January 2010 est. 19 Kuwait 1,798,000,000,000 0.95% 1 January 2010 est.

20 Canada 1,754,000,000,000 0.92% 1 January 2010 est

To Frack or Not to Frack in the EU

Sourcing

natural gas fields associated with other hydrocarbon fuels also a source of helium

Sourcing

shallow levels (low pressure) forms by anaerobic decay of organics sediments buried deeper and at higher temperatures than those that contain oil generate natural gas decaying organic wastes of solid waste landfills and from wastewater anaerobic digesters

SOURCING .........

"associated" (found in oil fields) "non-associated" (isolated in natural gas fields) coal beds (as coalbed methane)

SOURCING ..........

commercially extracted from oil fields and natural gas fields gas extracted from oil wells is called casing head gas or associated gas natural gas industry is extracting gas from increasingly more challenging resource types: sour gas, tight gas, shale gas, and coal bed methane

Prepping .........

contains significant amounts of ethane, propane, butane, and pentane - heavier hydrocarbons removed for commercial use methane sold as a consumer fuel or chemical plant feedstock non-hydrocarbons such as carbon dioxide, nitrogen, helium, and hydrogen sulfide must be removed

Mining Sophisticated equipment and advanced computer technology have increased the productivity of exploration. Maps of potential deposits now are made using remote-sensing satellites. Seismic prospectinga technique based on measuring the time it takes sound waves to travel through underground formations and return to the surfacehas revolutionized oil and gas exploration. Computers and advanced software analyze seismic data to provide three-dimensional models of subsurface rock formations. Another method of searching for oil and gas is based on collecting and analyzing core samples of rock, clay, and sand in the earth's layers.

Mining

Sophisticated equipment and advanced computer

technology have increased the productivity of

exploration.

Maps of potential deposits now are made using

remote-sensing satellites.

Mining .......

Once the drilling reaches the oil or gas

natural pressure forces the oil or gas up through the drill hole to

the wellhead, where it enters separation and storage tanks

if natural pressure is not great enough to force the oil to the

surface, pumps may be used.

in some cases, water, steam, or gas

may be injected into the oil deposit to improve recovery

Mining .......

while oil refineries may be many thousands of miles away from

the producing fields

gas processing plants typically are near the

fields, so that impuritieswater, sulfur, and natural gas liquids

can be removed before the gas is piped to customers

Gas Well US DOE Website

Like oil production, some natural gas flows freely to wells because the natural pressure of the underground reservoir forces the gas through the reservoir rocks. These types of gas wells require only a ""Christmas tree", or a series of pipes and valves on the surface, to control the flow of gas.

Primary Pumping Techniques US DOE Website

small number of free-flowing gas formations still exist in many U.S. gas fields, however. pumping system will be required to extract the gas present in the underground formation. "horse head" pump (see photo) which rocks up and down to lift a rod in and out of a well bore, bringing gas and oil to the surface.

Darvaza Burning Gas Craters in Turkmenistan In the heart of the Karakum desert the Darvaza Gas Craters are old Soviet natural gas mines from the 1950s that have been set alight. It can be seen at night from miles away The Karakum Desert is home to the Darvaza Gas Craters

Some gas operations are not so elaborate

Gas supplies still tight in Wuhan, Chongqing, and other Chinese cities, a source from China National Petroleum Corporation (CNPC) told The Beijing News that the company's major natural gas mines are all overloaded with production

Hydraulic Fracturing

somewhat new drilling technology high-volume hydraulic fracturing reach natural gas reserves that underlie many states including Pennsylvania


"horizontal hydrofracking" or just "fracking," deep-shale natural gas drilling high-pressure injection of water, sand, and chemicals to release the trapped gas


"horizontal hydrofracking" or just "fracking," deep-shale natural gas drilling high-pressure injection of water, sand, and chemicals to release the trapped gas environmental and health impacts from high-volume hydraulic fracturing in several states have been documented significant number of spills, blowouts, leaking wells, and other accidents and releases of contaminants

Fracking and Proppants

Definition: Fracking: The process of initiating, and subsequently propagating a fracture in a rock layer, employing the pressure of a fluid as the source of energy. The fracturing is done from a wellbore drilled into reservoir rock formations, in order to increase the extraction and ultimate recovery rates of oil and natural gas.


Definition: Proppants: A proppant is a material, such as grains of sand, ceramic, or other particulates, that prevent the fractures from closing when the injection is stopped.

Proppant Fines Proppant fines generation and the resulting migration in the fracture are considered to be one of the major contributors to poor treatment results and well performance. It has been noted by Coulter & Wells1 that just 5% fines can decrease fracture flow capacity by as much as 60%. Hexions advanced grain-to-grain bonding technology reduces proppant fines generation and migration through the proppant pack. The curable resin coating provides additional strength to individual grains, generates uniform stress distribution throughout the pack, and encapsulates any loose fines that may occur.

Hydraulic fractures may be natural or man-made and are extended by internal fluid pressure which opens the fracture and causes it to extend through the rock. Natural hydraulic fractures include volcanic dikes, sills and fracturing by ice as in frost weathering. Man-made fluid-driven fractures are formed at depth in a borehole and extend into targeted formations. The fracture width is typically maintained after the injection by introducing a proppant into the injected fluid.

United States Patent Application

20100221136

Kind Code A1

Maffia; Gennaro J. September 2, 2010

Porous Metallic Structures Abstract In one aspect, there are provided methods for producing porous metallic structures, wherein the methods involve the use of collagen fibrils on the nanometer scale as a "sacrificial" scaffold upon which metal particles are deposited. Also disclosed are structures comprising a porous metallic matrix having favorable strength, porosity, and density characteristics. Structures produced in accordance with the present disclosure are useful for, inter alia, the fabrication of devices such as filters, heat exchangers, sound absorbers, electrochemical cathodes, fuel cells,catalyst supports, fluid treatment units, lightweight structures and biomaterials.

Pseudo 3-D Image

SEM & LM Images

Titanium

Aluminum

Original Sample Using Copper at 600 C

Titanium

Ceramic Proppants

Proppants Suspended in an Aqueous Fracking Fluid

Most natural gas companies note that between

98 and 99 percent of the 5 million gallons of

fluid used to hydraulically fracture a Marcellus

Shale natural gas well consists of water and

sand..... from Wheeling Intelligencer

History, Success and Materials

A typical Marcellus Shale well can be fracked numerous times during its production life.

The wells travel thousands of feet into the earth before turning horizontally to reach gas pockets.

After the wells are drilled and the protective casing put in place, the fracking process begins.


Petroleum services titan the Halliburton Co. pioneered the fracking process in 1947

Halliburton has performed work in both West Virginia and Pennsylvania.


A typical Marcellus Shale well can be fracked numerous times during its production life. The wells travel thousands of feet into the earth before turning horizontally to reach gas pockets. After the wells are drilled and the protective casing put in place, the fracking process begins.

Marcellus Shale Formation


Petroleum services titan the Halliburton Co. pioneered the fracking process in 1947, and company officials note the firm has performed work in both West Virginia and Pennsylvania.

In fact, fracking has been a common occurrence in Wetzel and Tyler counties for years - with no reported incidents of groundwater contamination.


According to Halliburton, 98.47 percent of the material its workers use for fracking consists of water and sand, leaving just 1.53 percent for other materials.

Some of the chemicals found in Halliburton's fluid mixture include formaldehyde, ammonium chloride, acetic anhydride, methanol, hydrochloric acid, and propargyl alcohol.

Process Flow Diagram

Formation Profile

Formation and Gear

Materials

Halliburton notes that the force of the water being pumped into the earth - which can be as high as 10,000 pounds per square inch - creates tiny fissures in the Marcellus Shale formation. The sand portion of the mixture then flows into these fissures and keeps them open. This creates pathways for the previously trapped natural gas to escape. The entire fracking process takes, on average, three to 10 days to complete.The role of chemicals in the fracking process varies.

Chemicals

Chemicals ........

According to Chesapeake Energy, which says its most common fracking solution contains 0.5 percent worth of chemicals, the chemicals and their roles in the process include: hydrochloric acid - found in swimming pool cleaner, and used to help dissolve minerals and crack the rock; ethylene glycol - found in antifreeze, and used to prevent scale deposits in the pipe that lines the well; isopropanol - found in deodorant, and used to increase the viscosity of the fracture fluid; .

Chemicals ..........

glutaraldehyde - found in disinfectant, and used to eliminate bacteria that can create corrosive by-products; petroleum distillate - found in cosmetics, and used to minimize friction; guar gum - found in common household products, and used as a gel to thicken the water and suspend the sand; ammonium persulfate - found in hair coloring, and used to delay the breakdown of guar gum;

Chemicals .......... formamide - found in pharmaceuticals, and used to prevent corrosion of the well casing; borate salts - found in laundry detergent, and used to maintain fluid viscosity under high temperatures; citric acid - found in soda pop, and used to prevent precipitation of metal; potassium chloride - found in medicine and salt substitutes, and used to prevent fluid from interacting with soil; sodium or potassium carbonate - found in laundry detergent, and used to balance acidic substances.

Gas Available from Fracking

Pros and Cons

Ryan Dean, manager of corporate development with Chesapeake Energy, said any well can be problematic if not constructed properly. And, drilling and hydraulic fracturing are not interchangeable terms. Steel and concrete need to isolate the well bore from the surrounding ground water. If done correctly, there is zero chance of contamination. To assure this, Chesapeake Energy tests the water source within 2,500 feet prior to drilling, establishing a baseline standard. Rick Simmons, statewide enforcement manager for ODNR, said Ohio's regulations are much tougher than other states, like Pennsylvania, which has encountered problems.

Pros and Cons

For example, Pennsylvania has allowed its natural gas drillers to flush vast quantities of contaminated wastewater into rivers that supply drinking water, according to the Associated Press. Of the 10.6 million barrels of wastewater that gushed from the wells in the final six months of 2010, at least 65 percent was recycled, a dramatic increase from previous years, when little or no recycling took place. But the records also show that at least 2.8 million barrels of well wastewater were sent to treatment plants that discharge into rivers and streams.

Pros and Cons

However, some 3.6 million barrels were sent to the same plants during the 12-month period that ended on June 30. According to the AP, that means that even with the recycling effort ramping up tremendously, more tainted wastewater is being dumped into rivers now than was the case a year ago. Dean explained that upon construction of his company's closed pit system, all frack water is stored in a steel tank until reused in process, eliminating the need for underground injection wells and wastewater treatment. "Our track record speaks for itself," he added. Okey inquired of Dean about the cause of problems in Pennsylvania with water and sewer located in the proximity of wells..

Pros and Cons Pennsylvania's hilly topography and the lack of pre-drilling testing has been problematic, Dean acknowledged. "Expanding our testing prior to drilling will help with both our peace of mind and the landowners' peace of mind," he added. In fact, in the state of Ohio, Dean said company officials revealed water wells were contaminated before drilling. "Contamination is a public health concern, and pretesting helps to protect us from liabilities," he explained. Due to the increased scrutiny of both the ODNR and the Ohio Environmental Protection Agency, contamination is highly unlikely. Simmons explained, "Well design and construction is critical for the protection of ground water as well as public health and safety. As liquid waste is produced, it is logged, manifested and tracked from cradle to grave. Ohio has 80,000 fracking wells, mostly vertical.

Pros and Cons of Fracking

Mining companies are pushing hard. As the Stark County lease numbers show, the companies have been calling on landowners, offering to pay for the right to extract gas through fracturing. The companies see a new source for natural gas, something they say the country needs. No doubt they also see profits aplenty. But fracking has opponents, who assert that it will harm the environment and may cause health problems. They point to the mining industrys refusal to identify the chemicals in the fluids pumped underground under high pressure.

Novel Materials

Halliburton Chemicals Used in the Marcellus Shale

Regulation of Natural Gas Production and Transportation

The U.S. DOT Office of Pipeline Safety (OPS) administers the national regulatory program to assure the safe and environmentally sound transportation of natural gas, liquefied natural gas and hazardous liquids by pipeline. The Federal Energy Regulatory Commission reviews and authorizes the operation of the interstate natural gas pipelines.

Intrastate pipelines that run within one state and do not cross state boundaries are typically regulated by a state government agency. For example in Texas, the Railroad Commission of Texas[4] regulates pipelines, and in Louisiana, it is the Louisiana Department of Natural Resources.

Questions

1. Natural gas is everywhere

2. Remote locations require pipelines to transport NG

3. What % of the US total energy picture is NG

4. For #3 how many quads is that

5. Fracking is old technology

6. The Oracle of Delphi was fracked

Questions

7. Fracking is only for horizontal wells

8. The amount of shale gas available is not worth the fracking effort

9. Europe is on board with fracking

10. Environmentalists and gas producers in the use agree on all aspects of fracking

PART 2 Fracking Processes and EHS Issues

Quick Review of Part I

What is Natural Gas?

A naturally occurring gas consisting primarily of methane typically with 020% higher hydrocarbons

(primarily ethane).

Where & How?

Historically, natural gas is defined as methane and associated light hydrocarbons that have been recovered from natural gas fields or extracted during petroleum processing.

MIT Study

Hydraulic Fracturing....

Hydraulic fracturing (or fracking) is the process of using a fluid to create cracks in sedimentary rock and a proppant (small solid) to hold open the crack, releasing trapped oil and gas.

Gas Available from Fracking

EHS Issues

Environmental, Health, and Safety (EHS) concerns have developed over the process of fracking leaks and uncontrolled gas release and contamination of drinking water with natural and synthetic toxins

Who Should Attend

Process Engineers Fuel and Energy Specialists Environmental/Energy Auditors Local and Federal Officials Involved with Natural Gas Recovery and Processing Water Quality Engineers and Municipal Officers News Media (Print, TV, Radio, Internet) Covering

Natural Gas Issues Managers at Natural Gas Companies

Brief Biography Course Director

1. Professor of Chemical Engineering 2. Manager of Technology Development a. Petrochemical & Refining b. Start-up & Technical Services 3. Energy Projects a. Alaskan Pipeline and Remote Gas b. Fuel Oxygenates c. Biofuels/Bioseparations d. Energy Integration e. Novel Separations f. Manufacture of Proppants

Student Researchers

Review of the Learning Objectives Understand global energy picture and the importance of

natural gas Understand fracking for mining natural gas List and understand the environmental issues concerning

hydraulic fracturing of sedimentary rock to capture natural gas

Assess the economic and safety issues involving the mining of natural gas

Understand existing and potential legislation regarding hydraulic fracturing

SI and Imperial Units

Energy 1 BTU = 1055 J 1 BTU = 1.055 kJ 1 kWh = 3600 kJ

Energy in Colloquial Terms kWh = 1 kJ/s of power expended for 1 h Cost (based on PECO): $0.165/kWh

Unit Levels SI Prefixes

1 EW exa 103 PW peta 106 TW tera 109 GW giga 1012 MW mega 1015 kW kilo 1018 W ----- 1021 mW milli 1024 W micro

Natural Gas Background

Worldwide Energy Consumption CMO = cubic mile of oil

1 CMO = 152 quads = 160 EJ

Energy Consumption Patterns

0

50

100

150

200

250

300

350

400

450

500

1960 1970 1980 1990 2000 2010

year

Qua

drill

ion

kJ

USWorld

Raw Gas

Refined Gas

Natural Gas Reserves Rank Country/Region

Natural gas proven reserves (m)

% of total Date of information

World 190,163,119,460,000 100% 1 January 2010 est.

1 Russia 47,570,000,000,000 25.02% 1 January 2010 est. 2 Iran 29,610,000,000,000 15.57% 1 January 2010 est. 3 Qatar 25,470,000,000,000 13.39% 1 January 2010 est. 4 Turkmenistan 7,504,000,000,000 3.95% 1 January 2010 est. 5 Saudi Arabia 7,461,000,000,000 3.92% 1 January 2010 est. 6 United States 6,928,000,000,000 3.64% 1 January 2010 est.

7 United Arab Emirates 6,071,000,000,000 3.19% 1 January 2010 est.

8 Nigeria 5,246,000,000,000 2.76% 1 January 2010 est. 9 Venezuela 4,983,000,000,000 2.62% 1 January 2010 est. 10 Algeria 4,502,000,000,000 2.37% 1 January 2010 est. 11 Iraq 3,170,000,000,000 1.67% 1 January 2010 est. 12 Australia 3,115,000,000,000 1.64% 1 January 2010 est. 13 China 3,030,000,000,000 1.59% 1 January 2010 est. 14 Indonesia 3,001,000,000,000 1.58% 1 January 2010 est. 15 Kazakhstan 2,407,000,000,000 1.27% 1 January 2010 est. 16 Malaysia 2,350,000,000,000 1.24% 1 January 2010 est. 17 Norway 2,313,000,000,000 1.22% 1 January 2010 est. European Union 2,250,000,000,000 1.18% 1 January 2010 est. 18 Uzbekistan 1,841,000,000,000 0.97% 1 January 2010 est. 19 Kuwait 1,798,000,000,000 0.95% 1 January 2010 est.

20 Canada 1,754,000,000,000 0.92% 1 January 2010 est

Natural Gas Uses

Projected Energy Mix - EIA

Fracking Processes and EHS Issues 1. Fracking Processes for Natural Gas Recovery

Fracking Processes and EHS Issues 1. Fracking Processes for Natural Gas Recovery BASIC PROCESS FOR GAS RECOVERY

Fracking Processes and EHS Issues

Hydraulic fracturing techniques have been refined through years of development in Texas and Oklahoma. Most recent enhancements have focused on the nature of the frack additives and the propping agents such as fine sand or ceramic material employed in the fracking process.

Fracking Processes and EHS Issues

Well stimulation in the Marcellus Formation in Pennsylvania utilizes computer simulation/modeling to design the fracking process, such as, volumes of fluid and proppant to use, pressure required, and determine the composition of the frackng fluid. These data are coordinated with characteristics unique to the formation, such as depth, temperature and thermal maturity, and the structural characteristics of the shale.

Shale Exploration and Gas Recovery Based on OERB (Oklahoma Oil & Gas Producers)

Drilling via a drillbit to below the aquifer; drilling muds are used to keep the drill bit cool

The drillbit is removed and surface casing installed

Cement is then pumped down the casing , turns back up at the shoe and seals the hole

Drill is then lowered again to break through the plug and continue to about 500 ft above the planned horizontal (lateral) run

Curve begins so that the horizontal section can be drilled

The drillbit is again removed and a Measurement While Drilling motor is lowered into the hole

The curve can take up to 0.25 mile to complete

During the lateral drilling the bit may be removed for servicing

When completed, production casing is placed inside the full length of the well bore

The annulus is then filled with cement in a similar manner as before

Casing the well is very important since this contains the gas and allows for efficient removal to the surface

The drilling rig removed and replaced by a temporary collection device; Christmas Tree

A perforating gun is lowered by wire line into the casing, and a small charge is initiated causing perforations in the shell casing and the surrounding shale. The perforating gun is then removed.

Hydraulic Fracturing is next, since the perforations are very tight and will not allow much gas flow as is

The high pressure fracking fluid causes the shale to fracture

A plug is placed between the perforated and fracked stages

Stage 2 is now perforated and fracked

Multi-stage fracking (MSF) has become the standard for tight gas formations; after all of the stages have been fracked the plugs are drilled out.

After the plugs have been removed the gas flows freely to the surface and is collected to the grid through a permanent wellhead (Christmas Tree)

Halliburton notes that the force of the water being pumped into the earth - which can be as high as 10,000 pounds per square inch - creates tiny fissures in the Marcellus Shale formation. The sand portion of the mixture then flows into these fissures and keeps them open. This creates pathways for the previously trapped natural gas to escape. The entire fracking process takes, on average, three to 10 days to complete. The role of chemicals in the fracking process varies.

Chemicals (~90/9/

Chemicals ........

According to Chesapeake Energy, which says its most common fracking solution contains 0.5 percent worth of chemicals, the chemicals and their roles in the process include: hydrochloric acid - found in swimming pool cleaner, and used to help dissolve minerals and crack the rock; ethylene glycol - found in antifreeze, and used to prevent scale deposits in the pipe that lines the well; isopropanol - found in deodorant, and used to increase the viscosity of the fracture fluid; .

Chemicals ..........

glutaraldehyde - found in disinfectant, and used to eliminate bacteria that can create corrosive by-products; petroleum distillate - found in cosmetics, and used to minimize friction; guar gum - found in common household products, and used as a gel to thicken the water and suspend the sand; ammonium persulfate - found in hair coloring, and used to delay the breakdown of guar gum;

Each interval isolated in a fracking operation, whether a vertical well or a horizontal well, is subject to a specific sequence of fluid additives, each with its own engineered purpose to facilitate the production of gas from the well. Hydraulic fracturing of Marcellus wells in Pennsylvania typically utilizes a water-based fluid known as slickwater frac. Slickwater fracs are predominantly water, pumped at high pressure, with lesser amounts of sand, along with very dilute concentrations of certain additives and chemicals designed to stimulate the formation, enhance the return, or flowback of the slickwater solution following well stimulation, and increase the production of gas from the reservoir.

PA DEP

The particular chemistry of the frack fluid may vary from site to site. Each frack interval in a horizontal well may require up to 500,000 to 1 million gallons of water. Vertical wells use the same solutions but typically require two to three times the volume of a single horizontal frack interval. The total volume of frack fluid needed for a horizontal well will be significantly higher than that needed for a vertical well.

PA DEP

The term slickwater refers to friction-reducing agents, such as potassium chloride, polyacrylamide or other chemicals, added to the water to reduce the pressure needed to pump the fluid in the wellbore. These additives may reduce tubular friction in the wellbore by 50 to 60%.

PA DEP

PA DEP

The sequence of additives in fracikng a particular interval 1. An acid stage, consisting of several thousand gallons of water mixed with a

dilute acid, such as hydrochloric or muriatic acid. This serves to clear cement debris in the wellbore and provide an

open conduit for other frack fluids, by dissolving carbonate minerals and opening fractures near the wellbore. 2. A pad stage, consisting of approximately 100,000 gallons of slickwater without proppant material. The slickwater pad stage fills the wellbore with the slickwater solution (described below), opens the formation and helps to facilitate the flow and placement of proppant material.

PA DEP

3. A prop sequence stage, which may consist of several substages of water combined with proppant material fine mesh sand or ceramic material, intended to keep open, or prop the fractures created and/or enhanced during the fracing operation after the pressure is reduced. This stage may collectively use several hundred thousand gallons of water. Proppant material may vary from a finer particle size to a coarser particle size throughout this sequence. 4. A flushing stage, consisting of a volume of fresh water sufficient to flush the excess proppant from the wellbore.

PA DEP

Other additives commonly used in the fracking solution employed in Marcellus wells include: A dilute acid solution, as described in the first stage, used during the initial frack sequence. This cleans out cement and debris around the perforations to facilitate the subsequent slickwater solutions employed in fracturing the formation; A biocide or disinfectant, used to prevent the growth of bacteria in the well that may interfere with the fracking operation. Biocides typically consist of bromine based solutions or glutaraldehyde.

PA DEP

A scale inhibitor, such as ethylene glycol, used to control the precipitation of certain carbonate and sulfate minerals; Iron control/stabilizing agents such as citric acid or hydrochloric acid, used to inhibit precipitation of iron compounds by keeping them in a soluble form; Friction reducing agents, such as potassium chloride or polyacrylamide-based compounds, used to reduce tubular friction and subsequently reduce the pressure needed to pump fluid into the wellbore.

PA DEP

Corrosion inhibitors, such as N,n-dimethyl formamide, and oxygen scavengers,such as ammonium bisulfite, are used to prevent degradation of the steel well casing. Gelling agents, such as guar gum (a common food additive), may be used in small amounts to thicken the water-based solution to help transport the proppant material. Occasionally, a cross-linking agent will be used to enhance the characteristics and ability of the gelling agent to transport the proppant material. These compounds may contain boric acid or ethylene glycol.

Materials

Halliburton Chemicals Used in the Marcellus Shale

The Eagle Ford Shale is a hydrocarbon producing formation of significant importance due to its capability of producing both gas and more oil than other traditional shale plays. It contains a much higher carbonate shale percentage, upwards to 70% in south Texas, and becomes shallower and the shale content increases as it moves to the northwest. The high percentage of carbonate makes it more brittle and fracable.

The EF shale play trends across Texas from the Mexican border up into East Texas, roughly 50 miles wide and 400 miles long with an average thickness of 250 feet. It is Cretaceous in age resting between the Austin Chalk and the Buda Lime at a depth of approximately 4,000 to 12,000 feet.

Environmental, Health and Safety Issues

Between state differences in the economic importance of natural gas production, political traditions, environmental impacts of drilling activities, and local governmental responses to risk reduction, and entrepreneurial activities are weighed in relation to policymaking initiatives. Colorados regulatory approach offers a greater degree of environmental protection than Texas. Key reforms adopted in 2007-8 can be largely attributed to electoral victories that ensured unified party control over state government and the determined efforts of the pro-environmental governor to make changes in both the regulatory commission and in the substance of natural gas drilling policies.

Critics point to a number of potentially harmful environmental and public health consequences from the continuing use of hydraulic fracturing to extract gas from underground shale formations. Possible contamination of groundwater supplies. reluctance of company officials to disclose trade secrets, some preliminary studies have revealed the use of toxic fracking fluids such as diesel and benzene. In some cases the failure to adequately seal pipes within a wellbore has led to build-up of pressure that results in the release of gas and these drilling fluids into the natural environment (Lustgarten, 2009a). In one case that was subsequently publicized in a pair of documentaries, U.S. EPA officials in Denver investigated citizen complaints from a community in Fremont County, Wyoming and concluded that a quarter of the water wells located near a fracking operation were contaminated.

An additional environmental concern is how to manage produced waters that surface following fracking operations. These waters have absorbed not only fracking fluids such as biocides (used to minimize corrosion of pipes from bacteria) but substantial quantities of naturally occurring salts as well. Companies can deal with wastewater by re-injecting it into the ground, through treatment and release or by recycling fluids for subsequent fracks A recent article about wastewater fracking jobs in Pennsylvania suggested that potentially unsafe concentrations of radioactive contaminants had been detected in produced waters but not reported. According to Urbina (2011), the effluent was then transported by company officials to municipal treatment plants that were not equipped to handle it and was subsequently discharged into rivers not far from water intake plants that supply drinking water to nearby cities.

Further policymakers are also paying attention to the amount of water withdrawn from underground aquifers. Each frack job also requires large quantities of water, an amount that ranges from two to four million gallons. While companies are strongly encouraged to cut water use by recycling fluids whenever possible, the amounts needed to stimulate the release of natural gas from rock formations in water scarce states like Wyoming or Colorado is a matter of concern to state and local officials worried about balancing energy-related demands with those related to municipal consumption and irrigated agriculture.

The location of drilling operations also matters. Groundwater is also more likely to represent a major source of drinking water in more sparsely populated rural areas than in cities. A study of water use in the Barnett Shale play in Texas indicated that fracking operations consumed less water from groundwater than surface sources; however, largely rural Cooke County depends on subsurface withdrawals for 85% of its water supply (Texas Railroad Commission, 2011).

Finally, there are other environmental impacts affecting land use, noise, and air quality. The tranquility of everyday life can be adversely affected by gas-related exploration activities that can include continuous noise and traffic from trucks hauling sand, chemicals, or wastewater through communities. Companies utilize large seismic trucks called thumpers that are deployed to hit (or thump) the ground with considerable force to aid in the identification of subterranean formations with commercially viable gas reserves (Wiseman, 2009).

The activities associated with preparing sites for drilling operations are also associated with another unwanted byproduct air pollution. One of the most productive gas fields in the U.S. located near Pinedale, Wyoming, has not only yielded considerable economic wealth to the area but amounts of ozone pollution that in March, 2011, were measured at 124 parts per billion; i.e., two thirds higher than EPAs maximum daily limit and higher than the worst day reported by Los Angeles in all of 2010 (Associated Press, 2011). In addition, a recent study indicated that increasing amounts of methane (a greenhouse gas) have been released into the atmosphere because of leaks from shale gas wells and from loose pipe fittings attached to gas pipelines (Zeller, 2011).

Interesting Hearing on Fracking in the Upper Delaware River

Basin Near Deposit, NY

http://www.state.nj.us/drbc/XTOEnergy_hearingtranscript060111.pdf

Indicative of the conflicting opinions in a small community

Novel Manufacture of Fracking Fluid and Proppants


Definition: Proppants: A proppant is a material, such as grains of sand, ceramic, or other particulates, that prevent the fractures from closing when the injection is stopped. Man-made fluid-driven fractures are formed at depth in a borehole and extend into targeted formations. The fracture width is typically maintained after the injection by introducing a proppant into the injected fluid.


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LOST PROTEIN TECHNOLOGY For sturdy, low density, porous metals

with applications in construction, prostheses, cell and bone in-growth, catalysis,

proppants

Key Research 2000 - present

Mary Ann Seltzer Microscopy/Milling Joseph Mulato Specific Gravity Control Donna Stauffer Sonication Jacklyn Shea Decorin Binding Megan Winkelman Andy Lastowka Katie Scherpf Crosslinking Simon Werner Oi (Helen) Chu Catalysis Chris Vives Chris Morrison Lost Protein Tara Iracki Process Development Shannon OBrien Filtration

Manufacturing Process

Type I

Bovine Hide

Collagen

(corium)

Raw Material

Ball milling Dispersing Freezing Freeze Drying Sterilizing Cross-linking

Sonication

US patent 6,660,829 (12/2003)

Product 1

Product 2 Product 3 Product 4

Collagen Assembly

tissue, etc.

fiber bundle

fiber

fibril

micro-fibril

triple helix

alpha chains

Mill

ing

and

reco

very

How to Unravel Collagen? Variety of Mechanical Methods (Hammer Mills, Knife Mills, etc.) Ball Milling of Raw Collagen in a Dilute Solution Seems to be the Most Effective

10 g raw BHC 500 mL DI water 7 days

Bovine Fibrils

Standard Dispersion

0.75/5/94.25/X:C/A/W/X where X is the proppant material

Matrices Formulation Casting Freezing Soaking Lyophilization Crosslinking Sintering

Potential Steps Post-Formulation


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Porous Metallic Structures Abstract In one aspect, there are provided methods for producing porous metallic structures, wherein the methods involve the use of collagen fibrils on the nanometer scale as a "sacrificial" scaffold upon which metal particles are deposited. Also disclosed are structures comprising a porous metallic matrix having favorable strength, porosity, and density characteristics. Structures produced in accordance with the present disclosure are useful for, inter alia, the fabrication of devices such as filters, heat exchangers, sound absorbers, electrochemical cathodes, fuel cells, catalyst supports, fluid treatment units, lightweight structures and biomaterials.

C A W X

dispersion plus additives (inerts, drugs)

sponges/ membranes

collagen sponge plus additive

- A,W

- A,W

C

X

additive

-C X

C, collagen/ A, organic acid/ W, DI water/ X, additive

Lost Protein Production Process

Collagen Nanofibrils DIspersion and Metal Powders

Blend Shape and Freeze Below Eutectic

Controlled Reheat and Lyophilize

Sinter

Porous Metal Sphere

1. 2. 3. 4. 5. 6.

Titanium 1200C for 1 hour

Pseudo 3-D Image

Nickel 1200C for 1 hour

Sintering of the nickel beads resulted in very delicate beads which would become powder under the slightest pressure.

Tin 220C for 1 hour

Tin beads were sintered just below the melting point of tin. This was not adequate enough to burn off the collagen scaffold.


Spheroid metal powder is sintered together.

Titanium

Pros and Cons

Ryan Dean, manager of corporate development with Chesapeake Energy, said any well can be problematic if not constructed properly. And, drilling and hydraulic fracturing are not interchangeable terms. Steel and concrete need to isolate the well bore from the surrounding ground water. If done correctly, there is zero chance of contamination. To assure this, Chesapeake Energy tests the water source within 2,500 feet prior to drilling, establishing a baseline standard. Rick Simmons, statewide enforcement manager for ODNR, said Ohio's regulations are much tougher than other states, like Pennsylvania, which has encountered problems.

Pros and Cons

For example, Pennsylvania has allowed its natural gas drillers to flush vast quantities of contaminated wastewater into rivers that supply drinking water, according to the Associated Press. Of the 10.6 million barrels of wastewater that gushed from the wells in the final six months of 2010, at least 65 percent was recycled, a dramatic increase from previous years, when little or no recycling took place. But the records also show that at least 2.8 million barrels of well wastewater were sent to treatment plants that discharge into rivers and streams.

Pros and Cons

However, some 3.6 million barrels were sent to the same plants during the 12-month period that ended on June 30. According to the AP, that means that even with the recycling effort ramping up tremendously, more tainted wastewater is being dumped into rivers now than was the case a year ago. Dean explained that upon construction of his company's closed pit system, all frack water is stored in a steel tank until reused in process, eliminating the need for underground injection wells and wastewater treatment. "Our track record speaks for itself," he added. Okey inquired of Dean about the cause of problems in Pennsylvania with water and sewer located in the proximity of wells..

Pros and Cons Pennsylvania's hilly topography and the lack of pre-drilling testing has been problematic, Dean acknowledged. "Expanding our testing prior to drilling will help with both our peace of mind and the landowners' peace of mind," he added. In fact, in the state of Ohio, Dean said company officials revealed water wells were contaminated before drilling. "Contamination is a public health concern, and pretesting helps to protect us from liabilities," he explained. Due to the increased scrutiny of both the ODNR and the Ohio Environmental Protection Agency, contamination is highly unlikely. Simmons explained, "Well design and construction is critical for the protection of ground water as well as public health and safety. As liquid waste is produced, it is logged, manifested and tracked from cradle to grave. Ohio has 80,000 fracking wells, mostly vertical.

Pros and Cons of Fracking

Mining companies are pushing hard. As the Stark County lease numbers show, the companies have been calling on landowners, offering to pay for the right to extract gas through fracturing. The companies see a new source for natural gas, something they say the country needs. No doubt they also see profits aplenty. But fracking has opponents, who assert that it will harm the environment and may cause health problems. They point to the mining industrys refusal to identify the chemicals in the fluids pumped underground under high pressure.

Novel Materials

Regulation of Natural Gas Production and Transportation

The U.S. DOT Office of Pipeline Safety (OPS) administers the national regulatory program to assure the safe and environmentally sound transportation of natural gas, liquefied natural gas and hazardous liquids by pipeline. The Federal Energy Regulatory Commission reviews and authorizes the operation of the interstate natural gas pipelines.

Intrastate pipelines that run within one state and do not cross state boundaries are typically regulated by a state government agency. For example in Texas, the Railroad Commission of Texas[4] regulates pipelines, and in Louisiana, it is the Louisiana Department of Natural Resources.

The development of unconventional resources such as shale gas is one of the most promising trends in U.S. energy supplies that could have great potential for enhancing our energy independence and reducing carbon emissions. Many experts have called shale gas an energy game changer that could dramatically alter the energy supply picture for North America and potentially the world as other countries are just beginning to determine the extent of their own unconventional resources and are closely watching developments in North America.

Hydraulic fracturing technology that is critical to unlocking the vast tracks of shale gas located throughout the United States has drawn intense criticism from environmentalists and lawmakers concerned about the potential impact of hydraulic fracturing on water supplies and the environment. As a result of numerous health and environmental concerns raised, legislation commonly known as the FRAC Act was introduced in the 111th Congress (2009-2010) calling for greater federal regulation over hydraulic fracturing and disclosure of the chemicals used in hydraulic fracturing operations.

in March 2010, the U.S. Environmental Protection Agency (EPA) announced that it will conduct a comprehensive research study to investigate the potential adverse impacts that hydraulic fracturing may have on water quality and public health. While the FRAC Act did not reach the floor of the 11th Congress, some members of the 112th Congress (2010-2012) have recently expressed their intention to re-introduce the FRAC Act in 2011. Hydraulic fracturing continues to draw criticism from environmentalists and EPAs scrutiny over the industry is intensifying as EPAs study starts to take shape.

How

abo

ut a

mov

ie?

Debunked ..................?

Future

1000 TCF Available Gas 1000 Quads of energy US Consumption ~ 100 Quads per year from all energy

sources EIA indicates NG will remain at ~22% of US energy

supply picture through 2030

The evolution of global gas markets is unclear. A global liquid natural gas market is beneficial to U.S. and global economic interests and, at the same time, advances security interests through diversity of supply and resilience to disruption. The U.S. should pursue policies that encourage the development of such a market, integrate energy issues fully into the conduct of U.S. foreign policy, and promote sharing of know-how for strategic global expansion of unconventional gas production.

Past research, development, demonstration, and deployment (RDD&D) programs supported with public funding have led to significant advances for natural gas supply and use. Public-private partnerships supporting a broad natural gas research, development, and demonstration (RD&D) portfolio should be pursued.

Existing federal laws govern most environmental aspects of shale gas development. The Clean Water Act regulates surface discharges of water associated with shale gas drilling and production, as well as storm water runoff from production sites. The Safe Drinking Water Act regulates the underground injection of fluids from shale gas activities. The Clean Air Act limits air emissions from engines, gas processing equipment, and other sources associated with drilling and production. The National Environmental Policy Act (NEPA) requires that exploration and production on federal lands be thoroughly analyzed for environmental impacts.

Most of these federal laws have provisions for granting "primacy" to the states (I.e., state agencies implement the programs with federal oversight). State agencies not only implement and enforce federal laws; they also have their own sets of state laws to administer. The states have broad powers to regulate, permit, and enforce all shale gas development activities-the drilling and fracture of the well, production operations, management and disposal of wastes, and abandonment and plugging of the well.

State regulation of the environmental practices related to shale gas development, usually with federal oversight, can more effectively address the regional and state-specific character of the activities, compared to onesizefits-all regulation at the federal level. Some of these specific factors include: geology, hydrology, climate, topography, industry characteristics, development history, state legal structures,population density, and local economics. State laws often add additional levels of environmenta lprotection and requirements. Also, several states have their own versions of the federal NEPA law,requiring environmental assessments and reviews at the state level and extending those reviews beyond federal lands to state and private lands.

Questions

1. Fracking is 100% environmetally friendly

2. Local citizens are all in favor of fracking

3. Gasland is a fiction

4. Novel materials may help with fracking

5. Proppants are best when lightweight and

strong

6. Sand is the most commonly used proppant

Questions

7. Smart fluids would help in the fracking process

8. The amount of shale gas available is not worth the fracking effort

9. Most legislation is likely to be local

10. Some states regulate fracking more than others

Mining Natural Gas: Calculations for Fracking Fluids and Proppants

Mining Natural Gas: Hydraulic Fracturing Calculations (Fourth in a 4-part series) January 10, 2012 at 11:00 a.m.12:30 p.m. (ET) 90 Minute Accredited Online Training

Proppants

Pack width determined by Proppant concentration Closure stress Filter-cake and embedment Pack permeability determined by Proppant size and strength Packing and porosity Regained permeability and gel clean -up Non-Darcy and multiphase flow

White Sand (20/40) 2#/ft2

Closure Stress, psi

Internal versus External Pack Widths External pack width determined by proppant density and loading External width affected by embedment Spalling causes an internal width loss Wall filter-cake is an internal width loss

Carbolite @ 2 lb/ft2

Hydraulic fractures may be natural or man-made and are extended by internal fluid pressure which opens the fracture and causes it to extend through the rock. Natural hydraulic fractures include volcanic dikes, sills and fracturing by ice as in frost weathering. Man-made fluid-driven fractures are formed at depth in a borehole and extend into targeted formations. The fracture width is typically maintained after the injection by introducing a proppant into the injected fluid.

Proteins for Fracking

You have got to be kidding Professor?

Protein Based Fracking Fluids and Proppants

Collagen Based Technology

Proppants Collagen dispersion CAWX Lyophilize to give CX Sinter to give X, lightweight and porous

Fluid Collagen dispersion CAW a smart fluid Active viscosity control and swelling ratio via

pH

MARM - 2008


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The Center for Professional Advancement 2011 Do not duplicate

2.00

2.50

3.00

3.50

4.00

4.50

5.00

5.50

6.00

6.50

7.00

3.00 3.50 4.00 4.50 5.00 5.50 6.00

ln R

PM

ln cp

ln RPM vs. ln cp Day 0 Day 1 Day 7

Rheological (Pseudoplastic) Properties of Collagen Dispersion

Collagen fibrils hold hundreds of times their mass in water in the vicinity of their charged surface

0

50100150200250300

3 4 5 6

pH

Swel

ling

Rat

io

Swelling ratio is the mass of water plus collagen divided by the mass of collagen solids held in a viscous plug at the bottom of a centrifuge tube.

SMART FLUID

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ForceForce

ForceForceForce

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20/1 dilution; inverted 3500 rpm, 45 mins, 4 C

Less-viscous phase

Viscous phase

Kathryn Scherpf and Collagen Beads Made with DipN-Dot molds

Standard Dispersion is the Starting Material

Pseudo 3-D Image


Spheroid metal powder is sintered together.

Macroscopic Visual Inspection


From a fluid mechanical perspective, the most important issue is that of the pressure drop required for the liquid or the gas to flow through the column at a specified flow rate. To calculate this quantity we rely on a friction factor correlation attributed to Ergun.

PRESSURE DROP IN PACKED SYSTEMS


Other fluid mechanical issues involve the proper distribution of the fluid across the cross-section, and developing models of the velocity profile in the liquid film around a piece of packing material so that heat/mass transfer calculations can be made. Design of packing materials to achieve uniform distribution of the fluid across the cross-section throughout the column is an important subject as well. Here, we only focus on the pressure drop issue.


The Kozeny-Carman equation (or Carman-Kozeny equation) is a relation used in the field of fluid dynamics to calculate the pressure drop of a fluid flowing through a packed bed of solids. It is named after Josef Kozeny and Philip C. Carman. The equation is only valid for laminar flow


pressure drop total height of the bed superficial or "empty-tower" velocity, viscosity of the fluid porosity of the bed sphericity of the particles in the packed bed diameter of the related spherical particle

This equation holds for flow through packed beds with particle Reynolds numbers up to approximately 1.0, after which point frequent shifting of flow channels in the bed causes considerable kinetic energy losses. This equation can be expressed as "flow is proportional to the pressure drop and inversely proportional to the fluid viscosity", which is known as Darcy's law1.

ERGUN EQUATION

density 1 kg/m3 0.0624 lbs/cf

viscosity 0.05 cP 0.12097866 lbs/ft-h

v superficial 0.5 m/s 1.64 ft/s

particle dia 0.001 m 39.37 mils

length 8 m 26.24 ft

void 0.5

mass velocity 0.5 kg/s-m2

RHS 9.25

dP 74000 Pa 74 kPa

10.73283 psi


ERGUN EQUATION

density viscosity density viscosity v superficial v superficial particle dia particle dia length length void mass velocity RHS dP dP dP

kg/m3 cP lbs/cf lbs/ft-h m/s ft/s m mils m ft kg/s-m2 Pa kPa psi

1 0.05 0.0624 0.12097866 0.5 1.64 0.0005 19.685 100 328 0.5 0.5 16.75 3350000 3350 485.8781

1 0.05 0.0624 0.12097866 0.5 1.64 0.001 39.37 100 328 0.5 0.5 9.25 925000 925 134.1604

1 0.05 0.0624 0.12097866 0.5 1.64 0.0015 59.055 100 328 0.5 0.5 6.75 450000 450 65.26721

1 0.05 0.0624 0.12097866 0.5 1.64 0.002 78.74 100 328 0.5 0.5 5.5 275000 275 39.88552

1 0.05 0.0624 0.12097866 0.5 1.64 0.0025 98.425 100 328 0.5 0.5 4.75 190000 190 27.55727

1 0.05 0.0624 0.12097866 0.5 1.64 0.003 118.11 100 328 0.5 0.5 4.25 141666.7 141.6667 20.54708

1 0.05 0.0624 0.12097866 0.5 1.64 0.0035 137.795 100 328 0.5 0.5 3.892857 111224.5 111.2245 16.1318

1 0.05 0.0624 0.12097866 0.5 1.64 0.004 157.48 100 328 0.5 0.5 3.625 90625 90.625 13.14409

1 0.05 0.0624 0.12097866 0.5 1.64 0.0045 177.165 100 328 0.5 0.5 3.416667 75925.93 75.92593 11.01216

1 0.05 0.0624 0.12097866 0.5 1.64 0.005 196.85 100 328 0.5 0.5 3.25 65000 65 9.427486

1 0.05 0.0624 0.12097866 0.5 1.64 0.0055 216.535 100 328 0.5 0.5 3.113636 56611.57 56.61157 8.210843

1 0.05 0.0624 0.12097866 0.5 1.64 0.006 236.22 100 328 0.5 0.5 3 50000 50 7.251912

1 0.05 0.0624 0.12097866 0.5 1.64 0.0065 255.905 100 328 0.5 0.5 2.903846 44674.56 44.67456 6.479519

1 0.05 0.0624 0.12097866 0.5 1.64 0.007 275.59 100 328 0.5 0.5 2.821429 40306.12 40.30612 5.845929

1 0.05 0.0624 0.12097866 0.5 1.64 0.0075 295.275 100 328 0.5 0.5 2.75 36666.67 36.66667 5.318069

1 0.05 0.0624 0.12097866 0.5 1.64 0.008 314.96 100 328 0.5 0.5 2.6875 33593.75 33.59375 4.872378

1 0.05 0.0624 0.12097866 0.5 1.64 0.0085 334.645 100 328 0.5 0.5 2.632353 30968.86 30.96886 4.491669

1 0.05 0.0624 0.12097866 0.5 1.64 0.009 354.33 100 328 0.5 0.5 2.583333 28703.7 28.7037 4.163135

1 0.05 0.0624 0.12097866 0.5 1.64 0.0095 374.015 100 328 0.5 0.5 2.539474 26731.3 26.7313 3.877061

1 0.05 0.0624 0.12097866 0.5 1.64 0.01 393.7 100 328 0.5 0.5 2.5 25000 25 3.625956


0

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300

400

500

600

0 50 100 150 200 250 300 350 400 450

Dp,

psi

Diameter, mils


1

10

100

1000

1 10 100 1000

Dp,

psi

Diameter, mils

Hydraulic Fracturing for Mining Natural Gasaka, Fracking Slide Number 2Discovery now ?....Slide Number 4Slide Number 5Slide Number 6Slide Number 7Slide Number 8Mostly methane with some ethane and higher hydrocarbonsremember each carbon has 4 valence electronsand therefore has four bondsKey Personnel Involved in the IssueSlide Number 11Slide Number 12Slide Number 13Seminar Outcomes for Parts 1 and 2Slide Number 15Jerry Maffia who is this guy?Jerry Maffia some projectsJerry Maffia recent localesStudent Researchers they do all the workand so on.............Slide Number 21Slide Number 22MiningMethodology....What is all the fuss about .........Slide Number 26Slide Number 27Slide Number 28Slide Number 29SOME HEADLINES.........Regulations and Current PolicyMay 2012 NewsMay 2012 NewsMay 2012 NewsEconomic ImpactA World Scale Petrochemical Plant In Pittsburgh.....are you crazy professor?Maybe, but ...............Slide Number 35Fracturing now ?....GasFrac Inc., Calgary, AlbertaGasFrac Inc., Calgary, AlbertaSlide Number 39Boom in Cotulla, TexasSlide Number 41Selected Headlines followmany differing opinions; often frustratingSlide Number 43Slide Number 44Slide Number 45Slide Number 46Slide Number 47Slide Number 48Slide Number 49Slide Number 50Slide Number 51Development of Collagen-Based Hydraulic Fracturing Fluid and Study of Proppant Settling Characteristics Slide Number 53Slide Number 54Slide Number 55Collagen fiber formationSlide Number 57Manufacturing ProcessSlide Number 59Slide Number 60Slide Number 61Slide Number 62Slide Number 63Unique Properties of FibrilsSlide Number 65Slide Number 66Slide Number 67Slide Number 68Slide Number 69Slide Number 70Slide Number 71Slide Number 72NG SourcingSlide Number 74GWPSlide Number 76What has been done with NG....Controversial.... Por quWhat is fuel?Force, Pressure, Work, Energy, PowerKey Units of EnergySlide Number 82Slide Number 83Slide Number 84Unit Levels SI PrefixesNatural Gas - Background20th Century Production of NG(conversions 1 MM CF= ~ 1 B BTU; 20 TCF = ~ 20 quads)Natural Gas World-Wide LocationsNatural Gas Production and TransportationSlide Number 90First PipelinesNatural gas in the kitchen or vice versaSlide Number 93Slide Number 94Slide Number 95Slide Number 96Slide Number 97Slide Number 98Slide Number 99Slide Number 100How About Remote Gas?Hey Jerry how do we get the gas off of the North Slope?Well ??????We know how to do pipelines are they the answer?Seems pretty crowded imagine this in AlbertaUS Pipeline SystemIs the US the only place how about Europe?Are Fracking and Pipelines the Answer for Remote Gas?Slide Number 107Worldwide Energy ConsumptionCMO = cubic mile of oil1 CMO = 152 quads = 160 EJEnergy Consumption PatternsBreakdown of US Energy Consumption, at 100 quads % can be used in place of quads or vice versaDOE: US Current and Projected Energy Usage (%)World Energy ConsumptionNATURAL GAS SPECIFICATIONSSlide Number 114Raw GasSlide Number 116Slide Number 117Slide Number 118Power Plant ComponentsNatural Gas UsesIndustrial Primary Energy Consumptionby Fuel 1970 - 2025 (Quadrillion Btu)Fossil Fuel Electric Power Generation - inefficientHow much is left?Natural Gas ReservesTo Frack or Not to Frack in the EUSourcingSourcingSOURCING .........SOURCING ..........Prepping .........MiningMiningMining .......Mining .......Gas Well US DOE WebsiteSlide Number 136Primary Pumping Techniques US DOE WebsiteSlide Number 138Slide Number 139Slide Number 140Slide Number 141Hydraulic FracturingHydraulic FracturingHydraulic FracturingHydraulic FracturingFracking and ProppantsFracking and ProppantsSlide Number 148Slide Number 149Slide Number 150Slide Number 151Slide Number 152Slide Number 153Slide Number 154Slide Number 155Ceramic ProppantsProppants Suspended in an Aqueous Fracking FluidHistory, Success and MaterialsHistory, Success and MaterialsSlide Number 160Slide Number 161History, Success and MaterialsMarcellus Shale FormationHistory, Success and MaterialsHistory, Success and MaterialsSlide Number 166Process Flow DiagramFormation ProfileFormation and GearMaterialsSlide Number 171Chemicals ........Chemicals ..........Chemicals ..........Gas Available from FrackingPros and ConsPros and ConsPros and ConsPros and ConsPros and Cons of FrackingNovel MaterialsNovel MaterialsHalliburton Chemicals Used in the Marcellus ShaleRegulation of Natural Gas Production and TransportationQuestionsQuestionsPART 2Fracking Processes and EHS IssuesSlide Number 188Slide Number 189Slide Number 190Where & How?Slide Number 192Slide Number 193Slide Number 194Hydraulic Fracturing....Gas Available from FrackingEHS IssuesWho Should AttendBrief Biography Course DirectorStudent ResearchersStudent ResearchersReview of the Learning ObjectivesSI and Imperial UnitsUnit Levels SI PrefixesNatural GasBackgroundWorldwide Energy ConsumptionCMO = cubic mile of oil1 CMO = 152 quads = 160 EJEnergy Consumption PatternsRaw GasRefined GasNatural Gas ReservesNatural Gas UsesProjected Energy Mix - EIAFracking Processes and EHS IssuesFracking Processes and EHS IssuesFracking Processes and EHS IssuesFracking Processes and EHS IssuesSlide Number 217Slide Number 218Slide Number 219Slide Number 220Slide Number 221Slide Number 222Slide Number 223Slide Number 224Slide Number 225Slide Number 226Slide Number 227Slide Number 228Slide Number 229Slide Number 230Slide Number 231Slide Number 232Slide Number 233Slide Number 234Slide Number 235Slide Number 236Slide Number 237Chemicals ........Chemicals ..........Slide Number 240Slide Number 241Slide Number 242Slide Number 243Slide Number 244Slide Number 245Slide Number 246Slide Number 247MaterialsHalliburton Chemicals Used in the Marcellus ShaleHalliburton Chemicals Used in the Marcellus ShaleSlide Number 251Slide Number 252Slide Number 253Slide Number 254Slide Number 255Slide Number 256Slide Number 257Slide Number 258Slide Number 259Slide Number 260Slide Number 261Interesting Hearing on Fracking in the Upper Delaware River Basin Near Deposit, NYNovel Manufacture ofFracking Fluid and ProppantsFracking and ProppantsSlide Number 265Slide Number 266Key Research 2000 - presentManufacturing ProcessSlide Number 269Sli

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