United States Patent: 8318625

Anyone who hasn't been in a coma for the past four years or so is likely to be aware of what is known as the "Deepwater Horizon Oil Spill" in the Gulf of Mexico, the infamous 2010 environmental disaster.

An extended summary of it can be accessed via:

Deepwater Horizon oil spill - Wikipedia, the free encyclopedia; "The Deepwater Horizon Horizon oil spill (also referred to as the BP oil spill, the BP oil disaster, the Gulf of Mexico oil spill, and the Macondo blowout) was an oil spill in the Gulf of Mexico on the BP-operated Macondo Prospect, considered the largest accidental marine oil spill in the history of the petroleum industry ... . Following the explosion and sinking of the Deepwater Horizon oil rig, which claimed 11 lives, a sea-floor oil gusher flowed for 87 days, until it was capped on 15 July 2010. The total discharge is estimated at 4.9 million barrels ... . A massive response ensued to protect beaches, wetlands and esturaries from the spreading oil utilizing skimmer ships, floating booms, controlled burns and 1.84 million US gallons of  ... oil dispersant. Due to the months-long spill, along with adverse effects from the response and cleanup activities, extensive damage to marine and wildlife habitats, fishing and tourism industries, and human health problems have continued through 2013. Three years after the spill, tar balls could still be found on the Mississippi coast."

That oil spill is only the most lately infamous of the many that have occurred before and since, of course; and, we use it to highlight the potential importance of a perhaps unlikely material in dealing with, and limiting the damage caused by, such oil spill environmental disasters: Coal Ash.

According to scientists at the University of Central Florida, not only can Coal Ash now help to limit the environmental damage caused by such oil spills, it can help to recover some of the energy content in the spilled petroleum that would otherwise be lost.

As seen in excerpts from the initial and following links in this dispatch to:

"United States Patent 8,318,625 - Functionalized Fly Ash and Oil Scavenging Using the Same

Patent US8318625 - Functionalized fly ash and oil scavenging using the same - Google Patents

Date: November, 2012

Inventors: Sudipta Seal, et. al., Florida

Assignee: University of Central Florida Research Foundation, Inc., Orlando

Abstract: A method of scavenging oil from an oil-water mixture includes providing a plurality of functionalized fly ash particles having functionalized surfaces including reactive groups or reactive materials having hydrophobic groups covalently bound to the reactive groups or reactive materials. The oil-water mixture is contacted with the plurality of functionalized fly ash particles. The plurality of functionalized fly ash particles absorb oil from the oil-water mixture to form oil-laden fly ash particles. The oil-laden fly ash particles can be fed into a combustion process to generate heat from oil absorbed thereon, or absorbed oil from the oil-laden fly ash particles can be separated using a desorption process, and the oil recovered after separating.

Claims: A composition of matter, comprising: at least one functionalized fly ash particle, comprising: a bulk portion and a surface portion having a surface area, (i) O directly bound to said surface portion, and (ii) hydrophobic groups comprising condensation residue from an organic alcohol or organic acid covalently bound to said Oxygen. 

The composition ... wherein said said surface portion includes zeolite, and wherein said hydrophobic groups are covalently bound to said zeolite.

(We've previously discussed "zeolite" minerals and compounds; and, how some of them can actually be derived from Coal Ash. See, for one instance, our report of:

West Virginia Coal Association | Mobil Oil 1978 Coal Conversion with Zeolite Catalyst | Research & Development; concerning both:

"US Patent 4,086,262 - Conversion of Synthesis Gas to Hydrocarbon Mixtures; 1978; Mobil Oil Corporation; Abstract: Contacting a mixture of carbon monoxide and hydrogen with an intimate mixture of a carbon monoxide reduction catalyst, such as a Fischer-Tropsch catalyst or a methanol synthesis catalyst, and an acidic crystalline aluminosilicate (and) wherein said acidic crystalline aluminosilicate is a H-ZSM-5 crystalline zeolite. This invention is concerned with an improved process for converting synthesis gas, i.e., mixtures of gaseous carbon oxides with hydrogen or hydrogen donors, to hydrocarbon mixtures. In one aspect, this invention is particularly concerned with a process for converting synthesis gas to hydrocarbon mixtures rich in aromatic hydrocarbons. In another aspect, this invention is concerned with a process for converting synthesis gas to hydrocarbon mixtures particularly rich in liquefiable petroleum gases such as propane. In still another aspect, this invention is concerned with providing novel catalysts for the conversion of synthesis gas to hydrocarbon mixtures. Processes for the conversion of coal ... to a gaseous mixture consisting essentially of hydrogen and carbon monoxide, or of hydrogen and carbon dioxide, or of hydrogen and carbon monoxide and carbon dioxide, are well known"; and:

"Synthesis of ZSM-5 Zeolite from Fly Ash and Rice Husk Ash; Kasetsart University, Thailand; 2003".)

The composition ... wherein said hydrophobic groups cover 20% to 80% of said surface area.

Background and Field: This Disclosure is related to functionalized fly ash particles and scavenging of oil, such as from oil spills, using the same. An affordable and easily deployable solution to scavenge oil from oil spills is needed. It would also be desirable to recover the oil or the energy value from the oil scavenged from oil spills.

Disclosed embodiments include functionalization of fly ash particles, with fly ash particles being known to be a waste material resulting from combustion of coal in electrical power plants, to absorb oil from an oil-water mixture. Disclosed embodiments allow handling of the oil spill waste in an environmentally friendly "green" manner that avoids adding oil spill waste to landfills, or burning the wastes and adding to air pollution. Disclosed embodiments also can include recovering the oil scavenged from oil spills or the energy value from the oil scavenged. 

The entire chemical surface functionalization method describe herein can in certain embodiments be performed at low temperatures ... and consume a small amount of chemicals. Disclosed embodiments are therefore low cost, and moreover, capable of producing very large quantities of functionalized fly ash material in powder form. 

Fly ash particles can be generally captured from the chimneys of coal-fired power plants, or be obtained from providers that perform such capturing, and is one of two types of ash that jointly are known as coal ash.

As used herein, 'fly ash' refers to the residue from the combustion of powdered or ground coal.

The Inventors have recognized that fly ash particles have low oil sorption capacity due to their relatively low surface area and its formation at very high combustion temperatures leading to a composition having a hydrophilic surface. Simply increasing the surface area of fly ash by a solution-phase treatment can increase its sorption capacity for hydrophilic compounds, but this material is still unsuitable for oil sorption. Hydrophobic surface-functionalization of laboratory-synthesized silica aerogels has been shown to produce a many-fold increase in oil sorption capacity, but these materials are expensive and are thus impractical for large-scale use. 

As discovered by the Inventors, it is possible to tailor the surface properties of fly ash particles by an inexpensive, generally low temperature process that substantially increases the surface area of fly ash or other ceramic powders (e.g., alumino-silicate powders) through adding hydrophobic groups by surface functionalization that greatly increase the capacity for adsorption of hydrophobic oil molecules. In one embodiment, disclosed surface-functionalized fly ash particle powders can be placed in a low-cost oil-permeable mesh packaging material for use in oil clean-up operations following oil spills."

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We won't reproduce all of the technical details of treating Coal Ash to make of it an effective oil absorbent. Basically, it's "functionalized" by being washed with a solution of sodium hydroxide, NaOH, "lye", and then neutralized by being washed with a dilute solution of hydrochloric acid, perhaps with an added organic solvent. All of that is conducted at fairly low temperatures, below the boiling point of water.

There's not a lot more to it, although the inventors go into some detail describing both the process and how the prossed Coal Ash can be packaged and used for oil spill clean-up.

One thing that isn't too-well spelled out is that the absorbed oil can be extracted from the Fly Ash, after the agglomerated Fly Ash, having absorbed the oil, is skimmed, as it more easily is, out of the water. Another option for recovering the energy content might be, of course, to simply dump the oil-containing Ash into Coal headed into a power plant furnace, as noted in a more recent variation of the technology and process:

"United States Patent: 8404609 - Method of Forming Functionalized Fly Ash Particles

Patent US8404609 - Method of forming functionalized fly ash particles - Google Patents

Date: March 26, 2013

Inventors: Sudipta Seal, et. al., Florida

Assignee: University of Central Florida Research Foundation, Inc., Orlando

Abstract: A method of forming functionalized fly ash particles includes contacting a plurality of fly ash particles with a hydroxide compound under conditions to directly bond oxygen (O) onto a surface portion of the plurality of fly ash particles. The plurality of fly ash particles having Oxygen directly bound to their surface portion are reacted with an organic alcohol or an organic acid to covalently bond hydrophobic groups in the form of condensation residue from the organic alcohol or organic acid to the Oxygen to form the plurality of functionalized fly ash particles.

The method ... wherein said reacting comprises reacting said plurality of fly ash particles having said Oxygen directly bound to said surface portion and said organic alcohol in an acid environment, and wherein said hydrophobic groups comprise alkoxide groups (and) wherein a pH during said reacting is between 2 and 4. 

The method ... wherein said reacting comprises reacting said plurality of fly ash particles having said Oxygen directly bound to said surface portion and said organic acid, and wherein said hydrophobic groups comprise carboxylic (RCOO) groups (and) wherein said conditions for said alkali treatment are selected to form a zeolite surface layer on said surface portion, and wherein said hydrophobic groups are covalently bound to said zeolite layer. 

The method ... further comprising filtering and washing said functionalized fly ash particles with an alcohol, and then drying.

(Since "alcohol" is needed in these processes to wash the treated Coal Ash, we might as well take the opportunity to remind you, that, as seen for only two examples in:

West Virginia Coal Association | Princeton Scientists Convert More CO2 to Methanol and Ethanol | Research & Development; concerning: "United States Patent Application 20110114502 - Reducing Carbon Dioxide to Products; May, 2011; Inventors: Emily Barton Cole (and) Andrew Bocarsly, et. al.; (Presumed Assignee: Liquid Light, NJ); Abstract: A method for reducing carbon dioxide to one or more products is disclosed. The method ... wherein said products (of the Carbon Dioxide chemical reduction) comprise one or more of ... ethanol, ... isopropanol, (or) methanol"; and:

West Virginia Coal Association | New Jersey CO2 to High-Energy Alcohol | Research & Development; concerning: "United States Patent Application 20120132538 - Electrochemical Production of Butanol from Carbon Dioxide and Water; May 31, 2012; Inventors: Emily Barton Cole, Andrew Bocarsly, et. al.; (Though not disclosed in this early publication, there is little doubt that the ultimate Assignee of rights will be the company, Liquid Light.);;Abstract: Methods and systems for electrochemical production of butanol are disclosed. A method may include, but is not limited to, steps (A) to (D). Step (A) may introduce water to a first compartment of an electrochemical cell. The first compartment may include an anode. Step (B) may introduce carbon dioxide to a second compartment of the electrochemical cell. The second compartment may include a solution of an electrolyte, a catalyst, and a cathode. Step (C) may apply an electrical potential between the anode and the cathode in the electrochemical cell sufficient for the cathode to reduce the carbon dioxide to a product mixture. Step (D) may separate butanol from the product mixture";

whatever alcohol is most preferred, we can likely synthesize it from Carbon Dioxide.)

The method ... wherein said reacting is performed at a temperature (less than or equal to) 100 C.

Background and Summary: This Disclosure is related to functionalized fly ash particles and scavenging of oil, such as from oil spills, using the same. An affordable and easily deployable solution to scavenge oil from oil spills is needed. It would also be desirable to recover the oil or the energy value from the oil scavenged from oil spills. 

One disclosed embodiment comprises a method of scavenging oil from an oil-water mixture. The method includes providing a plurality of functionalized fly ash particles having functionalized surfaces including a reactive surface portion having oxygen directly bound thereto and hydrophobic groups comprising condensation residue from an organic alcohol or organic acid bound to the oxygen. The oil-water mixture is then contacted with the plurality of functionalized fly ash particles. 

The plurality of functionalized fly ash particles absorb oil from the oil-water mixture to form oil-laden fly ash particles. The oil-laden fly ash particles can be fed into a combustion process to generate heat from oil absorbed on the oil-laden fly ash particles, such as a combustion process that comprises combustion of coal."

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And, that's about it: Coal Ash can be used as an effective agent for cleaning up, and recovering the energy content of, spilled Oil.

Moreover, although its dramatic spills of petroleum in the ocean, as in the Deepwater Horizon disaster documented above, that garner international media attention and notoriety, as seen in:

Floreffe, Pennsylvania Oil Spill | Emergency Management | US EPA; "In January 1988, a four-million gallon oil storage tank owned by Ashland Oil Company, Inc., split apart and collapsed at an Ashland oil storage facility located in Floreffe, Pennsylvania, near the Monongahela River. The split released diesel oil over the tank's containment dikes, across a parking lot on an adjacent property, and into an uncapped storm drain that emptied directly into the river. Within minutes the oil slick moved miles down river, washing over two dam locks and dispersing throughout the width and depth of the river. The oil was carried by the Monongahela River into the Ohio River, temporarily contaminating drinking water sources for an estimated one million people in Pennsylvania, West Virginia, and Ohio, contaminating river ecosystems, killing wildlife, damaging private property, and adversely affecting businesses in the area. Contractors employed by Ashland performed the actual cleanup duties. The contractors used booms, vacuum trucks, and other equipment to retrieve the spilled oil, recovering about 20 percent of the oil that flowed into the river. EPA, in cooperation with other agencies, monitored the cleanup process and river conditions. Personnel set up a river monitoring system to track the spill, as well as a sampling and analysis process to protect water supplies. The Agency also performed follow-up activities such as compliance inspections and a Spill Prevention, Control, and Countermeasure (SPCC) plan inspection. Several important lessons were learned from this spill response. Evaluators of the response recommended that inventories of locally available equipment be prepared to assist emergency responders in quickly locating needed equipment. It was also recommended that to protect public water sources in future emergencies, water suppliers should plan for the availability of contingency water supplies and equipment";

they happen even in places where you might not expect them; and, Coal Ash, as treated by the University of Central Florida's processes of "US Patent 8,404,609 - Method of Forming Functionalized Fly Ash Particles" and "United States Patent 8,318,625 - Functionalized Fly Ash and Oil Scavenging Using the Same", could prove invaluable even in the heart of US Coal Country, to rescue our precious environment and it's inhabitants from the careless ravages of Big Oil.

Yo! Save the Catfish!

Coal Ash can do that!

West Virginia Coal Association - PO Box 3923 - Charleston, WV 25339 | 304-342-4153 | website developed by brickswithoutstraw