Stock material or miscellaneous articles – Hollow or container type article – Nonself-supporting tubular film or bag
Reexamination Certificate
2000-11-02
2002-06-11
Teskin, Fred (Department: 1713)
Stock material or miscellaneous articles
Hollow or container type article
Nonself-supporting tubular film or bag
C428S035700, C428S402000, C428S407000, C423S335000, C423S610000, C423S625000, C252S179000, C521S030000, C521S031000, C521S034000, C525S333300, C525S333400, C525S329400, C525S337000, C525S523000, C525S529000
Reexamination Certificate
active
06403177
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to the extraction of ammonia and amines from aqueous solution using tetraphenylborate salts, in particular sodium tetraphenylborate.
BACKGROUND OF THE INVENTION
Contaminants may enter the environment through discharge of industrial waste into a local water source, thereby imparting damaging and potentially devastating effects to the ecosystems which are dependent on the water source. Various methods have been proposed and implemented to reduce the level of contaminants present in water. However, such methods tend to be complicated and expensive, There is a need for alternative innovative technologies for removal of contaminants from waste water.
U.S. Pat. No. 4,695,387 (Berry et al.) discloses a process for continuous removal of ammonia from waste water using adsorption of ammonium ions to zeolite, and formation of ammonium phosphate from the adsorbed ammonium ions. The method employs a complex separation device having a plurality of chambers through which waste water must circulate. Although ammonium ion concentrations are reduced in waste water using this method, the removal of other nitrogen-containing contaminants from waste water is not addressed.
U.S. Pat. No. 5,641,413 (Momont et al., 1997) teaches removal of nitrogen from waste water having a high chemical oxygen demand. This method involves high temperature, high pressure oxidation and thermal denitrification to convert nitrogen-containing contaminants essentially to nitrogen gas. The process of U.S. Pat. No. 5,433,868 (Fassbender) employs a hydrothermal technique for removal of ammonia from water derived from sewage plant effluent. U.S. Pat. No. 5,407,655 (Sarritzu) discloses a process for recovery of pure (non-aqueous) ammonia from waste water through reaction with carbon dioxide, which also involves thermal decomposition, However, the high temperatures and pressures required in these processes necessitate the use of specialized tanks and equipment and thus tend to be expensive to conduct on a large scale.
U.S. Pat. No. 5,640,840 (Heitkamp et al., 1996) discloses a method for treatment of a liquid waste stream using microbial biodegradation whereby nitrogen-containing organic contaminants are ultimately converted to ammonia and carbon dioxide. The process involves flowing oxygenated waste water through a bed reactor supporting microbes capable of such biodegradation. This method requires the on-site presence of such a reactor, and recovery of purified water from the reactor may be a lengthy process.
Tetraphenylborates, particularly in the form of their alkali metal salts, are useful as counter ion components of cationic polymers in the field of non-linear optics (EP-A2-0 490 385), as polymerization initiators (U.S. Pat. No. 5,124,235), and as hydrophobic anionic functional groups dissolved in a polymeric matrix that is used in the separation of cesium and strontium from nuclear waste (U.S. Pat. No. 5,666,641). No work has heretofore been conducted to incorporate the use of tetraphenylborates in precipitation of ammonium ion or amines from waste water. All patents and publications referred to herein are expressly incorporated by reference.
SUMMARY OF THE INVENTION
An object of the invention is to provide a method of extracting ammonia and organic amines from water in an effective and environmentally acceptable manner.
One aspect of the invention provides a method for treatment of contaminated water to remove a nitrogen-containing species selected from ammonium ion and amines, which comprises contacting the water with sodium tetraphenylborate under acidic conditions, preferably weakly acidic conditions such as a pH value of between 3 and 7, and separating the treated water from the resultant precipitate of a salt of tetraphenylborate and the nitrogen-containing species.
Another aspect of the invention provides a method for treatment of contaminated water to remove a nitrogen-containing species selected from ammonium ion and amines (which hereinafter includes imines and any other species wherein the nitrogen atom will receive a proton), which comprises adjusting the pH value of the water to the acidic range, providing a polymer comprising a polymer backbone having a tetraphenylborate salt immobilized thereon, contacting the water with the polymer to dissociate the tetraphenylborate salt to tetraphenylborate ions and cations, whereby the nitrogen-containing species binds with the tetraphenylborate ions, and separating the treated water from the polymer having the nitrogen-containing species bound thereto. Preferably, the tetraphenylborate salt is a salt of Li
+
, Na
+
, K
+
, H
+
, Ca
+2
or Mg
+2
. More preferably, Na
+
is the cation.
A further aspect of the invention provides a polymer for removing a nitrogen-containing species selected from ammonium ion and amines from contaminated water, which polymer comprises a polymer backbone having a tetraphenylborate salt immobilized thereon in the form of dissociated tetraphenylborate ions and cations.
According to another aspect of the invention, there is provided an article for use in the removal of ammonium ion or amine from contaminated water, which comprises a containment vehicle having associated therewith a quantity of a polymer as defined above. The polymer may be, for example, in the form of cross linked beads or inert particles, e.g. silica, surface treated to be coated with tetraphenylborate groups, and the containment vehicle comprises, for example, a porous bag for the beads, a structure for supporting a bed of the beads, or a bed of sand having the beads entrained therein.
The invention also provides an article which comprises a means for introducing a solid or gaseous contaminated water source containing ammonia or amines, and converting said source to aqueous state.
The term contaminated water should be understood to encompass any water source containing ammonium ion or amine, and the invention is contemplated for use in the removal of ammonium ion or amine from any such water source. Thus, the method may be used, for instance to remove ammonium ion or amine from ground water, non-point run-off water, mine infiltration water, industrial effluent, and any other type of contaminated water or waste water.
In the case where ammonium ions or amines may be air-borne, or found in any other gaseous medium, such compounds may be captured and converted from the gaseous medium to an aqueous medium and removed according to the invention. An example of such an application is in the case of volatile ammonia and amines which arise from animal waste in an environment such as an enclosed chicken barn. Additionally, ammonium ion or amines derived from a solid source, such as animal waste, could be solubilized in water and removed therefrom according to the invention.
The invention may also be used as a pre-concentration method for extracting and concentrating small traces of amines or ammonium ion before analysis therefor. The invention can thus be employed for test methods to quantify amines or ammonium ion. The invention may be used for analysis of street-drug mixtures, most of which are amines, whereby the amine component can be sequestered from an admixture. The invention may also be used for recovery of any amine which can be converted into a quaternary (charged) nitrogen system. Even (CH
3
)
4
N
+
and related species having no N—H bond can be extracted using the method of the invention.
Amines which form insoluble salts with the tetraphenylborate anion and can be removed from aqueous media according to the invention include aliphatic amines such as alkylamines including methylamine, ethylamine, and propylamine, as well as guanidine and biguanidine; diamines of the formula NH
2
(CH
2
)
n
NH
2
where n is an integer, such as ethylene diamine and propylene diamine; aromatic amines such as aniline and benzylamine; heterocyclic amines such as optionally substituted pyridine, pyramidine and pyrazine; polycyclic amines such as tropane and 1,4-diazabicyclo [2.2.2] octane (DABCOH),
Brown G. Ronald
Cameron Elinor M.
Cameron Neil S.
Cameron T. Stanley
Knop Osvald
Dalhousie University
Teskin Fred
Woo Louis
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