WO1992000804A1 - Compositions servant au nettoyage de deversements de petrole ou de dechets dangereux - Google Patents

Compositions servant au nettoyage de deversements de petrole ou de dechets dangereux Download PDF

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Publication number
WO1992000804A1
WO1992000804A1 PCT/US1990/004958 US9004958W WO9200804A1 WO 1992000804 A1 WO1992000804 A1 WO 1992000804A1 US 9004958 W US9004958 W US 9004958W WO 9200804 A1 WO9200804 A1 WO 9200804A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
shavings
oil
leather
chrome tan
Prior art date
Application number
PCT/US1990/004958
Other languages
English (en)
Inventor
Franklin A. Paris
Jerry W. Roberson
Original Assignee
Paris Franklin A
Roberson Jerry W
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Paris Franklin A, Roberson Jerry W filed Critical Paris Franklin A
Publication of WO1992000804A1 publication Critical patent/WO1992000804A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/681—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of solid materials for removing an oily layer on water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/32—Materials not provided for elsewhere for absorbing liquids to remove pollution, e.g. oil, gasoline, fat

Definitions

  • This invention relates to compositions for chemical spill cleanup in general, more particularly to compositions which have a high affinity for oils and are suitable for use in the cleanup of oil from water surfaces and land areas.
  • compositions for controlling and removing an oil slick from surface waters leave much to be desired.
  • Various particulate, granular and fibrous materials capable, to some extent of floating and imbibing or absorbing oils, have been spread on water surfaces and the oily material then collected and recovered by a "sweep-up" operation. Examples of such materials are, e.g. hay, straw, textile fibers, sawdust, wood chips, and the like.
  • U.S. Pat. No. 3,739,913 mentions the use of nylon fiber, rayon fiber, polyester fiber, TEFLON shavings, glass fiber, and fiber of cotton or wool.
  • U.S. Pat. No. 4,519,918 teaches forming a hydrophobic oil absorption composition from wood, cotton, and other substances by treating the material with resin, or copolymer. Unfortunately, these materials when used in containing oil spills, or for oil spill cleanup, have proven less effective than desired. Some of these compositions simply are not adequately absorbant to pick up large quantities of oil from the water surface. Others, even when used in substantial amounts, leave an oil sheen on the water surface. Some rapidly become water logged and sink below the surface of the water such that the oily compositions cannot be recovered.
  • compositions absorb oil too slowly, and the oil does not bond to the composition with high affinity. Few, if any, of these compositions are effective as agents for scrubbing exposed rocks, or the soil of an oil contaminated shore. Recent large oil spills throughout the world have demonstrated the present lack of effective technology for the cleanup of oil contaminated water and shores. For these and other reasons, there exists a clear and real need for more effective oil cleanup compositions.
  • compositions which meet the above-mentioned needs and others.
  • a composition comprising chrome tan leather shavings which have good buoyancy and can float on an oil slick water surface for extended periods of time, have high absorbant capability for removing oil from the surface of the water, have retaining and absorbing capacity so that the oil contaminated water surface can De cleaned by sweeping or pick up of the oil contaminated composition from the water surface, and provides an additional advantage by concurrently re-using an industrial waste product.
  • compositions are provided characterized as useful and effective as agents for scrubbing and cleaning oil contaminated soil and rocks, useful to aid in removing oil from a contaminated shore, or other land area, and which may include shavings and particulates from other leather tanning processes such as those resulting from zirconium, alum, formaldehyde, syntan, melamine-formaldehyde, resorcinol- formaldehyde, or dialdehyde processes, as well as the chrome tanning process.
  • the present invention also extends to use of such compositions as a fencing material to surround and cut off an oil emitting source to inhibit, retard, or prevent, further spread of oil to uncontaminated land or water areas.
  • the present invention is directed to novel applications of an industrial waste composition, leather shavings, and methods of using the same to absorb and chemically absorb hazardous chemical spills and in particular oil, from water and land surfaces.
  • This composition can be spread upon the oil contaminated water, or land to absorb the oil.
  • the oil contaminated composition can be spread and then collected and disposed of to leave the water or land surface cleansed of oil.
  • this composition can be spread upon an oil slick floating on the surface of a body of water, and the oil slick covered to absorb the oil.
  • the oil-containing composition can then be swept up or otherwise removed from the surface of the water to effectively remove and cleanse the oil from the surface water.
  • Other embodiments include shavings from other conventional tanning processes such as alum, zirconium, syntans or synthetic tanning processes, resorcinol-formaldehyde tan shavings and dialdehyde tan leather shavings, for example.
  • composition for absorption and cleanup of hazardous chemicals and oil comprises, in the preferred embodiment of the invention, an admixture of chrome tan leather shavings, a by-product of a leather tanning operation.
  • Such shavings may be utilized in any of a wide variety of forms, particulate, compressed, or in combination with any carrier known in the art.
  • the leather tanning industry is divided into two broad categories, light and heavy leathers. Light leathers include shoe upper, lining, glove, handbag, and novelty leather and is made predominantly from light to medium weight cattlehides and from the skins of calf, goat, and sheep(l).
  • Heavy leather tanning is used for products including soles, straps, upholstery, and the like.
  • Light leathers are routinely tanned with basic chromium sulfate referred to as chrome or mineral tanning.
  • Some shoe and novelty leathers are tanned with vegetable tannins. Combinations of these tannages are used in some instances.
  • Waste shavings of such tanned leather are commonly referred to as chrome tan shavings(l-4).
  • the best mode for carrying out the invention comprises the application of such chrome tan shaving composition to hazardous chemical and oil spills.
  • the chrome tan shavings are produced when basic chromium sulfate is used for chrome tanning the leather., Skins from cattle, calf, goats, sheep and the like may be successfully utilized.
  • the chromium sulfate is applied in aqueous solution to such skins which have been "pickled” with sulfuric acid and sodium chloride to a pH of approximately 2.0-2.5. In this pH range the chrome penetrates the skin and is usually applied in a revolving drum.
  • the chrome reacts with the collagen in the skin when the skins are neutralized slowly to a pH of approximately 3.5-4.0. When the hydrothermal stability, shrink temperature, or melting point of the skin is raised to approximately 90-100 degrees C.
  • chrome tan shavings are usually discarded as a waste product of the tanning process(l and 2). Such process could, of course, be utilized to maximize the production of such shavings to manufacture large scale amounts of such shavings for the chemical and oil spill clean up applications of this invention.
  • the main mechanism of chrome tanning is usually considered to be the coordination of chromium to carboxyl groups of collagen followed by the formation of secondary valences with the amino groups present in the skins.
  • the chrome tan shavings according to the invention can be spread ove ⁇ the surface of contaminated water or upon the surface of an oil-contaminated area of land, e.g. a beach or rocks on the shore line, and left there for a sufficient period of time for the composition to absorb the oil from the water or the soil.
  • the oil-contaminated area can then be cleansed of oil by removing the oil-contaminated composition.
  • an effective way of cleansing an oil-contaminated beach e.g. is to spread the chrome tan shavings on top of the oil-contaminated area allow time for the composition to absorb the oil, and then wash the oil soaked composition into the water.
  • the oil soaked chrome tan shavings, which float on the surface of the water, can then be recovered by any conventional method, e.g. by sweeping up the oil-soaked chrome tan shavings from the surface of the water.
  • the chrome tan shavings of the invention may be used in powered, particulate, compressed or loosely associated form.
  • the composition may be derived from the chrome tanning process of skins as a by-product of manufacturing leather and may be used in a dry or moist condition.
  • An especially preferred chrome tan shaving composition has a moisture content of from about 20-70 percent, but may be otherwise.
  • the chrome tan shavings may be used alone or in a combination with various carriers and absorbants, such as wood chips, cotton seed hulls, activated carbon, nylon fiber, fibers of wool or cotton, etc. to effectively cleanse a contaminated area of oil or other hazardous substances.
  • various carriers and absorbants such as wood chips, cotton seed hulls, activated carbon, nylon fiber, fibers of wool or cotton, etc. to effectively cleanse a contaminated area of oil or other hazardous substances.
  • the chrome tan shavings of the invention may be used in a combination with degradative microorganisms, either natural or genetically engineered, to collect, absorb, and then degrade the oil or other hazardous substance.
  • the chrome tan shavings are useful either alone or in combination with such microorganisms serving to collect and absorb the spill and localize the contamination for microbial decomposition.
  • chrome tan shavings of the invention are also useful in combination with any of a wide range of chemical substances useful in the break-down of oil or other hazardous substances.
  • the chrome tan shavings may be used as a carrier for such substances or such substances may be applied to the contaminated shavings after application of the shavings to the spill.
  • chrome tan shavings have been described and characterized as a waste product of the leather tanning industry it is clear that such product could be synthesized by any of a number of chemical synthesis well known in the art.
  • X-ray fluorescence spectroscopy XFR was utilized to determine inorganic matter of a sample of such chrome tan shavings and a qualitative determination at voltages of 14kV at 0.10mA and 30kV at 0.04mA determined qualitatively the presence of sulfur, chlorine, calcium, chromium and iron in such shavings.
  • Fourier transform infra-red (FTIR) spectroscopy was utilized to determine organic matter of a sample of chrome tan shavings.
  • the sample for analysis was extracted with nanograde dichloromethane, the extract evaporated to a dry residue on a freshly resurfaced potassium bromide plate and mounted in and IBM model 32 computer controlled FTIR spectrophotometer and resulted in a spectral analysis showing infra-red adsorption bands including a hydrocarbon and an ester. Absorption bands were located at wave numbers 2924,2855,1745,1462,1377 and 1161. Atomic absorption spectroscopy (AA) was utilized to determine the metal content of a sample of such chrome tan shavings according to the preferred embodiment of the invention.
  • AA Atomic absorption spectroscopy
  • the sample to be analyzed with AA was first digested in 1:10 nitric acid: deionized water, and then filtered to remove remaining solids and diluted to a known volume.
  • the sample extract was analyzed for calcium, chromium and iron resulting in a determination of approximately 860 parts per million(ppm) calcium, 16,000 ppm chromium, and approximately 180 ppm iron.
  • Turbidimetric tests were used to determine the chloride and sulfate anion content of a sample of chrome tan shavings. Approximate determinations showed a chloride concentration at about 1,100 ppm and a sulfate concentration at about 76,000 ppm.
  • the chrome tan shavings of the present invention may be applied using any method known in the art.
  • the shavings are applied to oil or other hazardous material in layers, but may alternatively be used as a fencing material, flashpoint elevator, or otherwise.
  • the chrome tan shavings of this invention absorb the spills almost instantaneously. After the oil or other hazardous material is absorbed by the chrome tan shavings, the contaminated shavings may easily be collected and cleaned up.
  • the chrome tan shavings of this invention are biodegradable, non-toxic and are superb soil conditioners. When soaked in oil or other hazardous material they can be burned or buried, or otherwise disposed.
  • the chrome tan shavings of this invention have been found effective in absorbing various hazardous materials including various grades of hydrocarbons ranging from light and heavy naphthas, e.g. gasoline mid-distillates, e.g. diesel fuel, kerosene, heating oil and the like through high molecular weight hydrocarbons, asphalt residua and the like; including light and heavy petroleum crudes, from conventional and non- conventional sources, coal liquids, shale oils and the like.
  • the chrome tan shavings of this invention have been found highly absorptive in pick up of oil from a water surface, and from a land surface. Furthermore, these shavings remain afloat on a salt water or fresh water surface for long periods, periods greatly in excess of the time periods usually required for sweep up of an oil contaminated or liquid hazardous waste contaminated water. While the above description contains many specificities, these should not be construed as limitations on the scope of the invention, but merely as exemplifications of preferred embodiments thereof. Those skilled in the art will envision many other possible variations are within its scope.
  • chrome tan shavings of this invention have been described using skins of cattle, calf, goat, and sheep, however, it is understood that any skin capable of being tanned into a leather will suffice and may be successfully utilized, as may synthetic versions thereof.
  • the composition of this invention has been described, in the preferred embodiment as chrome tan shavings, a by product of the chrome tanning process in leather production. It is clear, however, that any size particle or shaving may be utilized, as well as solidified masses thereof, either alone or in combination with other useful compositions well known in the art, such as sawdust, cotton seed hulls, or degradative agents such as various chemicals or microorganisms.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Medicinal Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Public Health (AREA)
  • Materials Engineering (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

On décrit des compositions absorbant le pétrole et des déchets dangereux, et comprenant des rognures résultant du tannage des peaux au chrome ou de particules qui sont des sous-produits de l'industrie du tannage des peaux. Des rognures ou ces particules sont utiles seules ou en combinaison avec des produits chimiques et des micro-organismes qui dégradent le pétrole et des déchets dangereux. Les rognures ou les particules peuvent être synthétisées chimiquement ou produites à partir de peaux d'animaux. Divers modes de réalisation comprennent d'autres particules de peaux tannées, comme, par exemple, des rognures résultant d'opérations de tannage des peaux au zirconium, à l'alun, ou au dialdéhyde, utilisées soit seules, soit en combinaison avec des rognures résultant du tannage de peaux au chrome selon la présente invention.
PCT/US1990/004958 1990-07-10 1990-09-05 Compositions servant au nettoyage de deversements de petrole ou de dechets dangereux WO1992000804A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US55150290A 1990-07-10 1990-07-10
US551,502 1990-07-10

Publications (1)

Publication Number Publication Date
WO1992000804A1 true WO1992000804A1 (fr) 1992-01-23

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Application Number Title Priority Date Filing Date
PCT/US1990/004958 WO1992000804A1 (fr) 1990-07-10 1990-09-05 Compositions servant au nettoyage de deversements de petrole ou de dechets dangereux

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AU (1) AU6402990A (fr)
WO (1) WO1992000804A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998010146A1 (fr) * 1996-09-05 1998-03-12 Prolup Absorbenter Ab Materiau absorbant
DE10151922B4 (de) * 2001-10-20 2006-11-16 Bsr Bio Schuh Recycling Gmbh Biotechnische Herstellung eines Ölbindemittels aus lederhaltigen Rohmaterialien

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2164156A (en) * 1936-05-07 1939-06-27 Permutit Co Treatment of water
GB1420394A (en) * 1973-07-05 1976-01-07 Ciba Geigy Ag Composition for removal of organic materials from water
US3959127A (en) * 1973-12-05 1976-05-25 The United States Of America As Represented By The Secretary Of The Navy Biodegradation of oil on water surfaces
SU524561A1 (ru) * 1974-07-19 1976-08-15 Львовский Ордена Ленина Политехнический Институт Сорбент дл очискти поверхности воды от нефт ных загр знений
US4100154A (en) * 1977-04-22 1978-07-11 A. L. Gebhardt Company Process for recovery and separation of nutritious protein hydrolysate and chromium from chrome leather scrap
SU670541A1 (ru) * 1978-02-16 1979-06-30 Центральная научно-исследовательская лаборатория Производственного объединения "Укрнефть" Способ удалени нефти с поверхности воды
US4753917A (en) * 1979-11-26 1988-06-28 Universal Fibers, Inc. Sorbent for oil or other liquid hydrocarbons and method of manufacturing same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2164156A (en) * 1936-05-07 1939-06-27 Permutit Co Treatment of water
GB1420394A (en) * 1973-07-05 1976-01-07 Ciba Geigy Ag Composition for removal of organic materials from water
US3959127A (en) * 1973-12-05 1976-05-25 The United States Of America As Represented By The Secretary Of The Navy Biodegradation of oil on water surfaces
SU524561A1 (ru) * 1974-07-19 1976-08-15 Львовский Ордена Ленина Политехнический Институт Сорбент дл очискти поверхности воды от нефт ных загр знений
US4100154A (en) * 1977-04-22 1978-07-11 A. L. Gebhardt Company Process for recovery and separation of nutritious protein hydrolysate and chromium from chrome leather scrap
SU670541A1 (ru) * 1978-02-16 1979-06-30 Центральная научно-исследовательская лаборатория Производственного объединения "Укрнефть" Способ удалени нефти с поверхности воды
US4753917A (en) * 1979-11-26 1988-06-28 Universal Fibers, Inc. Sorbent for oil or other liquid hydrocarbons and method of manufacturing same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FULLER, HI., "The USe of Floating Absorvents", JOURNAL OF THE INSTITUTE OF PETROLEUM, Vol. 57, Number 553, p. 39, col. 1, para. 6, (January 1971). *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998010146A1 (fr) * 1996-09-05 1998-03-12 Prolup Absorbenter Ab Materiau absorbant
US6326070B1 (en) 1996-09-05 2001-12-04 Virkensdamm Ab Absorption means
DE10151922B4 (de) * 2001-10-20 2006-11-16 Bsr Bio Schuh Recycling Gmbh Biotechnische Herstellung eines Ölbindemittels aus lederhaltigen Rohmaterialien

Also Published As

Publication number Publication date
AU6402990A (en) 1992-02-04

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