Title of Invention

"METHOD OF PURIFYING FISCHER-TROPSCH DERIVED WASTE WATER"

Abstract

A process for the production of highly purified water 32 from Fischer-Tropsch reaction water 12, which process includes at least the steps of a primary treatment stage comprising biological treatment 14 for removing at least a fraction of dissolved organic carbon from the fischer-Tropsch reaction water 12 to produce a primary water-enriched stream 16, a secondary treatment stage comprising solid-liquid separation 24 for removing at least some solids from at least a portion of the primary water-enriched stream 16 to produce a secondary water-enriched streat 28 and a tertiary treatment stage comprising a dissolved salt and organic removal step 30 for removing at least some dissolved salts and organic constituents from at least a portion of the secondary water-enriched stream 28.

Full Text

METHOD OF PURIFYING FISCHER-TROPSCH DERIVED WATER Field of the Invention This invention relates to the purification of water produced during Fischer-Tropsch synthesis for which synthesis a variety of carbonaceous materials are used as feedstock. Background to the Invention The applicant is aware of processes for the synthesis of water from a carbonaceous feedstock, such as natural gas and coal, which processes also produce hydrocarbons. One such process is the Fischer-Tropsch process of which the largest product is water and, to a lesser extent, hydrocarbons including olefins, paraffins, waxes, and oxygenates. There are numerous references to this process such as, for example on pages 265 to 278 of Technology of the Fischer-Tropsch process" by Mark Dry, Catal. Rev. Sci.Eng., Volume 23 (1&2), 1981. The products from the Fischer-Tropsch process may be processed further, for example by hydroprocessing, to produce products including synthetic crude oil, olefins, solvents, lubricating, industrial or medicinal oil, waxy hydrocarbons, nitrogen and oxygen containing compounds, motor gasoline, diesel fuel, jet fuel and kerosene. Lubricating oil includes automotive, jet, turbine and metal working oils. Industrial oil includes well drilling fluids, agricultural oils and heat transfer fluids. In certain areas where carbonaceous feedstocks are to be found, water is in short supply and a relatively costly commodity. Also, environmental concerns prevent the dumping of polluted water derived from the Fischer-Tropsch process into natural water ways and the sea thereby presenting a case for the production and recovery of useable water at the source of the carbonaceous feedstocks. The carbonaceous feedstocks typically include coal and natural gas that are converted to hydrocarbons, water and carbon dioxide during Fischer-Tropsch synthesis. Naturally, other carbonaceous feedstocks such as, for example, methane hydrates found in marine deposits can also be used. Before the water produced during the Fischer-Tropsch process is purified in accordance with the present invention, it is typically subjected to preliminary separation aimed at isolating a water-enriched stream from the Fischer-Tropsch products. The preliminary separation process includes condensing the gaseous product from the Fischer-Tropsch reactor and separating it in a typical three-phase separator. The three streams exiting the separator are: a tail gas, a hydrocarbon condensate including mainly hydrocarbons in the C5 to C20 range and a reaction water stream containing dissolved oxygenated hydrocarbons and suspended hydrocarbons. The reaction water stream is then separated using a coalescer that separates the reaction water stream into a hydrocarbon suspension and a water-rich stream. The coalescer is capable of removing hydrocarbons from the reaction water stream to a concentration of between 10 ppm and 1000 ppm, typically 50 ppm. The water-enriched stream thus obtained forms the feedstock for the method according to the present invention and will be denoted in this specification by the term "Fischer-Tropsch reaction water". The composition of the water-enriched stream or reaction water is largely dependent on the metal used in the Fischer-Tropsch catalyst and the reaction conditions (e.g. temperature, pressure) employed. The Fischer-Tropsch reaction water can contain oxygenated hydrocarbons including aliphatic, aromatic and cyclic alcohols, aldehydes, ketones and acids, and to a lesser extent aliphatic, aromatic and cyclic hydrocarbons such as olefins and paraffins. The Fischer-Tropsch reaction water may also contain small quantities of inorganic compounds including metals from the Fischer-Tropsch reactor, as well as nitrogen and sulphur containing species that originate from the feedstock. The influence of the type of Fischer-Tropsch synthesis used on the quality of Fischer-Tropsch reaction water is illustrated in typical organic analysis (Table 1) of Fischer-Tropsch reaction water generated from three different synthesis operating modes, namely: (Formula Removed) Table 1: Typical Organic Composition of Fischer-Tropsch reaction water from Different Fischer-Tropsch Synthesis Operating Modes (Table Removed) It is evident from the typical analyses of Fischer-Tropsch reaction waters of different origin (Table 1) that these waters, in particular HT Fischer-Tropsch reaction water, contain relatively high concentrations of organic compounds, and direct application or disposal of these waters is generally not feasible without further treatment to remove undesirable constituents. The degree of treatment of the Fischer-Tropsch reaction water depends largely on the intended application, and it is possible to produce a wide range of water qualities ranging from boiler feed water to partially treated water which may be suitable for discharge to the environment. It is also possible to co-treat Fischer-Tropsch reaction water with other typical process waste water as well as rain water. The water purification processes described in this invention may, after making minor adaptations, also be used for the processing of aqueous streams derived from generic synthesis gas conversion processes using metallic catalysts similar to the catalysts used during Fischer-Tropsch synthesis. Summary of the invention According to a first aspect of the invention there is provided a process for the production of purified water from Fischer Tropsch reaction water, which process includes at least the steps of> a) a primary treatment stage comprising an equilibrium staged separation process having at least one stage for removing at least a fraction of non- acid oxygenated hydrocarbons from the Fischer Tropsch reaction water to produce a primary water-enriched stream; and b) a secondary treatment stage comprising at least one membrane separation process for removing at least some suspended solids and acidic oxygenated hydrocarbons from at least a portion of the primary water-enriched stream. The term "purified water" is to be interpreted as meaning an aqueous stream having a COD of between 20 and 500 mg/l, a pH of between 6,0 and 9,0, a suspended solids content of less than 250 mg/l and a total dissolved solids content of less than 600 mg/l. The non-acid oxygenated hydrocarbons are typically selected from the group including: alcohols, aldehydes and ketones, more specifically from the group including: acetaldehyde, propionaldehyde, butyraldehyde, acetone, methyl propyl ketone, methanol, ethanol, propanol, butanol, pentanol, hexanol, and heptanol. The suspended solids are typically catalyst particles. The acidic oxygenated hydrocarbons are typically selected from the group including: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid and octanoic acid. A number of equilibrium staged separation processes are suitable for use in the primary treatment stage. Such processes may include conventional distillation processes typically used in the refining and petrochemical industry as well as solvent extraction using either conventional liquid solvents or liquefied gases. When distillation is used as the primary treatment stage, the bulk of the non-acid oxygenated hydrocarbons contained in the Fischer Tropsch reaction water are removed, leaving predominantly mono-carboxylic acids (e.g. acetic acid, propionic acid) and optionally trace quantities of non-acid compounds. As a result of the presence of organic acids, FischerTropsch reaction water that has undergone primary treatment is known as Fischer Tropsch acid water {primary water-enriched stream). The overheads from distillation may be recovered and worked-up to products, or may be used for fuel or as an energy source. The primary treatment stage may further include a liquid-liquid separation process such as, for example, liquid-liquid extraction, in which the primary water-enriched stream is separated into an acid-enriched and a primary water-enriched stream. The acid-enriched stream may be treated further to recover the acids contained in it. The primary treatment stage may include degassing of the Fischer Tropsch reaction water before further processing to remove compounds having a very low boiling point and dissolved gases. Typically, Fischer Tropsch reaction water originating from HTFT iron catalyst processes which water has undergone primary treatment has limited application due to the relatively high concentrations (> 1 % by mass) of organic acids remaining in the Fischer Tropsch acid water, and further treatment of the water is required. In contrast, Fischer Tropsch reaction water originating from cobalt-based LTFT processes which water has undergone primary treatment contains significantly lower organic acid concentrations ( A number of membrane separation processes are suitable for use in the secondary treatment stage, depending on which constituent is to be removed. The membrane processes used in the secondary treatment stage are typically selected from the group including: micro-filtration, ultra-filtration, reverse osmosis and pervaporation. The secondary treatment stage may include a solid-liquid separation step in which microfiltration and/ or ultrafiltration is used for the removal of at least a fraction of the suspended solids from the primary water-enriched stream. Microfiltration typically includes using capillary polypropylene membranes with a nominal cut-off of 0,2 micrometer or molecular cut-off (MWCO) of 90 000 for removal of catalyst particles at typical pressures of 1 000 kPa, pH at 4 to 7 and temperatures of less than 40°C. Ultra-filtration typically includes using tubular poly-ether sulphone membranes with typically cut-off points of between 10 000 and 40 000 for removal of catalyst particles and suspended oils at typical pressures of less than 2 000 kPa, pH of between 4 and 7 and temperatures of less than 40°C. The secondary treatment stage may further include one or more liquid-liquid separation steps in which reverse osmosis and/or pervaporation is used to remove at least a fraction of the organic compounds in the primary water-enriched stream. Reverse osmosis may be implemented using either a spiral or a tubular configuration and pervaporation is typically applied using membrane distillation. Reverse osmosis typically includes using spiral wound poly-amide membranes with point rejection of better than 99,6 % (typically sea-water membranes) or poly-ether composite membranes with a point rejection of better than 99,6 % for removal of organic substances at typical pressures of less than 60 bar, pH of 4 to 7 and temperatures of less than 40°C. Pervaporation typically includes using flat sheet, chemically cross linked polyvinyl alcohol membranes or a polymer blend of poly-vinyl alcohol and poly-acrylic acid membranes for removal of organics which do not form azeotropes and at typical pressures of less than 4 mm Hg, pH of ca 7 and temperatures of between 30 and 70°C. The pH of the primary water-enriched stream may be adjusted prior to organic removal thereby to convert organic acids into organic salts. Since organic salts are rejected by membranes more readily'than organic acids are, pH adjustment in effect maximizes and economizes the removal of organic constituents. The liquid-liquid separation step results in the production of stream of purified water and a stream enriched with organic constituents. The organic constituents are typically fatty acids. The purified water may be subjected to a further liquid-liquid separation step (or steps) as described above to further reduce the amount of organic constituents contained therein. Applications for the purified water produced by the method described above may include its use as cooling water, make up, and irrigation water. The purified water typically has the following characteristics: (Table Removed) According to a second aspect of the invention there is provided a process for the production of highly purified water from Fischer Tropsch reaction water, which process includes at least the steps of:- a) a primary treatment stage comprising an equilibrium staged separation process having at least one stage for removing at least a fraction of non- acid oxygenated hydrocarbons from the Fischer Tropsch reaction water to produce a primary water-enriched stream; b) a secondary treatment stage comprising at least one membrane separation process for removing at least some suspended solids and acidic oxygenated hydrocarbons from at least a portion of the primary water- enriched stream to produce a secondary water-enriched stream; and c) a tertiary treatment stage comprising a dissolved salt and organic removal stage for removing at least some dissolved salts and organic constituents from at least a portion of the secondary water-enriched stream. The term "highly purified water" is to be interpreted as meaning an aqueous stream having a COD of less than 50 mg/l, a pH of between 6,0 and 9,0, a suspended solids content of less than 50 mg/l and a total dissolved solids content of less than 100 mg/l. The non-acid oxygenated hydrocarbons are typically selected from the group including; alcohols, aldehydes and ketones, more specifically from the group including: acetaldehyde, propionaldehyde, butyraldehyde, acetone, methyl propyl ketone, methanol, ethanol, propanol, butanol, pentanol, hexanol and heptanol. The suspended solids are typically catalyst particles. The acidic oxygenated hydrocarbons are typically selected from the group including: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid and octanoic acid. The dissolved salts removed during the tertiary stage are typically selected from the group including: calcium and sodium salts as well as traces of magnesium, iron and other salts. The organic constituents removed during the tertiary treatments stage are typically selected from the group comprising: acetaldehyde, propionakJehyde, butyraldehyde, acetone, methyl propyl ketone, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, formic acid, acetic acid, propionic acid, butyric acid, and valeric acid. A number of equilibrium staged separation processes are suitable for use in the primary treatment stage. Such processes may include conventional distillation processes typically used in the refining and petrochemical industry as well as solvent extraction using either conventional liquid solvents or liquefied gases. When distillation is used as the primary treatment stage, the bulk of the non-acid oxygenated hydrocarbons contained in the Fischer Tropsch reaction water are removed, leaving predominantly mono-carboxylic acids (e.g. acetic acid, propionic acid) and optionally trace quantities of non-acid compounds. As a result of the presence of organic acids, Fischer-Tropsch reaction water that has undergone primary treatment is known as Fischer Tropsch acid water (primary water-enriched stream). The overheads from distillation may be recovered and worked-up to products, or may be used for fuel or as an energy source. The primary treatment stage may further include a liquid-liquid separation process such as, for example, liquid-liquid extraction, in which the primary water-enriched stream is separated into an acid-enriched and a primary water-enriched stream. The acid-enriched stream may be treated further to recover the acids contained in it. The primary treatment stage may include degassing of the Fischer Tropsch reaction water before further processing to remove compounds having a very low boiling point and dissolved gases. Typically, Fischer-Tropsch reaction water originating from HTFT iron catalyst processes which water has undergone primary treatment has limited application due to the relatively high concentrations (> 1 % by mass) of organic acids remaining in the FT acid water and further treatment of the water is required. In contrast, Fischer-Tropsch reaction water originating from cobalt-based LTFT processes which water has undergone primary treatment contains significantly lower organic acid concentrations ( A number of membrane separation processes are suitable for use in the secondary treatment stage, depending on which constituent is to be removed. The membrane processes used in the secondary treatment stage are typically selected from the group including: micro-filtration, ultra-filtration, reverse osmosis and pervaporation. The secondary treatment stage may include a solid-liquid separation step in which microfiltration and/ or ultrafiltration is used for the removal of at least a fraction of the suspended solids from the primary water-enriched stream. Micro-filtration typically includes using capillary polypropylene membranes with a nominal cut-off of 0,2 micrometer or molecular cut-off (MWCO) of 90 000 for removal of catalyst particles at typical pressures of 1 000 kPa, pH at 4 to 7 and temperatures of less than 40°c. Ultra-filtration typically includes using tubular poly-ether sulphone membranes with typically cut-off points of between 10 000 and 40 000 for removal of catalyst particles and suspended oils at typical pressures of less than 2 000 kPa, pH of between 4 and 7 and temperatures of less than 40°C. The secondary treatment stage may further include one or more liquid-liquid separation steps in which reverse osmosis and/ or pervaporation is used to remove at least a fraction of the organic compounds in the primary water-enriched stream. Reverse osmosis may be implemented using either a spiral or a tubular configuration and pervaporation is typically applied using membrane distillation. Reverse osmosis typically includes using spiral wound poly-amide membranes with point rejection of better than 99,6 % (typically sea-water membranes) or poly-ether composite membranes with a point rejection of better than 99,6 % for removal of organic substances at typical pressures of less than 60 bar, pH between 4 and 7 and temperatures of less than 40°C. Pervaporation typically includes using flat sheet, chemically cross linked polyvinyl alcohol membranes or a polymer blend of poly-vinyl alcohol and poly-acrylic acid membranes for removal of organics which do not form azeotropes and at typical pressures of less than 4 mm Hg, pH of ca 7 and temperatures of between 30and70°C. The pH of the primary water-enriched stream may be adjusted prior to organic removal thereby to convert organic acids into organic salts. Since organic salts are rejected by membranes more readily than organic acids are, pH adjustment in effect maximizes and economizes the removal of organic constituents. The liquid-liquid separation step results in the production of a stream of purified water and a stream enriched with organic constituents. The organic constituents are typically fatty acids. The purified water may be subjected to a further liquid-liquid separation step (or steps) as described above to further reduce the amount of organic constituents contained therein. The tertiary treatment stage may include one or more of the following separation methods for the removal of salts from the secondary water-enriched stream: ion exchange and high rejection reverse osmosis. The tertiary treatment stage may further include one or more of the following separation methods for the removal of organic constituents from the secondary water-enriched stream: use of activated carbon, organic scavenger resins, and chemical oxidation (e.g. ozone and hydrogen peroxides with our without a catalyst or ultraviolet light generated free radicals) Applications for the highly purified water produced by the method described above may include its use as drinking water and boiler feed water. The highly purified water typically has the following characteristics: (Table Removed) Detailed Description of the invention The invention will now be described by way of the following non-limiting example with reference to the accompanying drawing. Figure 1 shows a schematic flow diagram of a process for the production of purified water and/ or highly purified water from Fischer Tropsch reaction water in accordance with the present invention. In the drawing, reference numeral 10 generally indicates a process for the production of purified water and/ or highly purified water in accordance with the present invention. Example: Treatment of Fischer Tropsch reaction water from an iron catalyst HTFT process After separation of by-products, a water-enriched stream from an HTFT process was degassed at atmospheric pressure in an open vessel. Free hydrocarbons in the water-enriched stream were reduced to 0.01 % (by mass) using a coalescer. Primary treatment of the thus obtained FT reaction water was undertaken using distillation and the compositions of the Fischer Tropsch reaction water and a primary water-enriched stream are given in Table 2. Table 2: Composition of HTFT reaction water and Fischer Tropsch acid water (primary water-enriched stream) ie bottoms after primary distillation. (Table Removed) Primary treatment of the HTFT reaction water 12 was effected using distillation 14 which yielded an acidic bottom or primary water-enriched stream 16 and a stream 18 enriched with non-acid oxygenated hydrocarbons. Analysis of the primary water-enriched stream 16 from the distillation column 14 is detailed in Table 2 above. It is evident from this analysis that a large fraction of non-acid components was removed from the Fischer Tropsch reaction water stream 12 during primary distillation 14 leaving an organic acid enriched stream 16 containing 1.25 % (by mass) organic acids consisting predominantly of acetic acid. The measured COD of this stream 16 was in the order of 16000 mg O2/I. For further treatment of the FT acid water stream 16, two alternatives were investigated. In alternative 1, a fraction 20 of the Fischer Tropsch acid water (primary water-enriched stream 16), was treated in an Acid Extraction plant 22 where about 50 % of the organic acids present in stream 20 were extracted using methyl-tertiary-buthyl ether (MTBE) producing an acid rich stream 23 and a water enriched stream 24 known as the acid extraction raffinate. The acid enriched stream 23 could be reworked in the upstream facilities while the raffinate 24 from the extraction plant 22 containing about 0,5 % by mass organic acids, was then cooled and sent to a secondary treatment stage comprising membrane separation processes 28. The membrane separation processes consisted of multi-stage spiral reverse osmosis (SRO) units using high rejection poly-amide membranes. Membrane flux was on average 45 LMH (l/m2.h) whilst the water recovery was 90% on average. Purified water 34 with an average carboxylic acid concentration of 0.05 % by mass was produced as well as a concentrated acids stream 40 containing about 6 % by mass carboxylic acids. The latter could be reworked in the upstream facilities while tertiary treatment 36 could be applied to the purified water 34. The tertiary treatment stage 36 comprised a polishing step using activated carbon (AC) for removal of the final traces of COD. Activated carbon treatment could effectively reduce the carboxylic acid concentration of stream 16 to 30 mg/l in the highly purified water stream 38 making this water stream 38 suitable to substitute raw water intake. In alternative 2, stream 16 was cooled prior to ultra-filtration (UF) 26 (using poly-ether-sulphone membranes) during which mainly fine catalyst particles 30 were removed. UF achieved effective removal of catalyst particles from stream 16 producing a substantially solids-free stream 32. Membrane flux was on average 80 l/m2.h and the silt density index (SDI) of the product stream 32 was consistently less than 3. Water recovery was consistently above 90%. The resulting stream 32 was then subjected to multi-stage spiral reverse osmosis (SRO) treatment 33 using high rejection poly-amide membranes which treatment 33 yielded a stream of purified water 35. The stream of purified water 35 produced during SRO treatment 33 contained on average 0,09 % by mass carboxylic acids. An acid-enriched stream 37 produced during SRO contained about 6 % carboxylic acids. Membrane flux was on average 40 LMH and the water recovery was on average 80 %. The acid-enriched stream 37 could be reworked in upstream facilities to recover its acid constituents as product. The purified water stream 35 was then sent to a tertiary treatment stage comprising a polishing step 39 using activated carbon (AC) for removal of the final traces of COD which step yielded a stream of highly purified water 41. Activated carbon treatment could effectively reduce the carboxylic acid concentration to 30 mg/l in the highly purified water stream 41 making this water stream 41 suitable to substitute raw water intake. Depending on the final intended use of the purified 34,35 or highly purified water 38, 41, the minimum water quality requirements are as set out in Table 3 below and the operating conditions of the equipment used in the method as well as suitable treatment options can be selected accordingly. Table 3: Water Quality - Typical Requirements (Table Removed) It is to be appreciated that the invention is not limited to any specific embodiment or configuration as hereinbefore generally described or illustrated, for example, rain water or water enriched streams from processes other than Fischer Tropsch synthesis may be purified according to the method described above. We Claim: 1. A process for the production of purified water from Fischer-Tropsch reaction water containing oxygenated hydrocarbons, aliphatic, aromatic and cyclic hydrocarbons and inorganic compounds, wherein the purified water is an aqueous stream having a COD of between 20 and 500 mg/1, a pH of between 6,0 and 9,0, a suspended solids content of less than 250 mg/1 and a total dissolved solids content of less than 600 mg/1, and wherein the process comprises at least the steps of:- a) a primary treatment stage comprising distillation or liquid-liquid extraction for removing at least a fraction of non-acid oxygenated hydrocarbons from the Fischer-Tropsch reaction water to produce a primary water-enriched stream; and b) a secondary treatment stage comprising at least one membrane separation process for removing at least some suspended solids and acidic oxygenated hydrocarbons from at least a portion of the primary water-enriched stream. 2. The process as claimed in claim 1, wherein the non-acid oxygenated hydrocarbons are selected from the group comprising: alcohols, aldehydes, and ketones. 3. The process as claimed in claim 1 or claim 2, wherein the acidic oxygenated hydrocarbons are selected from the group comprising: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid heptanoic acid, and octanoic acid. 4. The process as claimed in any one of the preceding claims, wherein the primary treatment stage comprises degassing of the Fischer-Tropsch reaction water before further processing in the primary treatment stage to remove compounds having a very low boiling point and dissolved gases from the Fischer-Tropsch reaction water. 5. The process as claimed in any one of claims 1 to 4, wherein the liquid-liquid extraction separates the primary water-enriched stream into an acid-enriched and a primary water-enriched stream. 6. The process as claimed in claim 5, wherein the acid-enriched stream is treated further to recover the acids contained in it. 7. The process as claimed in any one of the preceding claims, wherein the membrane processes used in the secondary treatment stage are selected from the group comprising: micro-filtration, ultra-filtration, reverse osmosis, and pervaporation. 8. The process as claimed in claim 7, wherein micro-filtration comprises the use of a capillary polypropylene membrane with a nominal cut-off of 0,2 micrometer or molecular cut-off (MWCO) of 90 000 at a pressure of 1 000 kPa, a pH of between 4 to 7 and a temperature of less than 40°C. 9. The process as claimed in claim 7, wherein ultra-filtration comprises the use of a tubular poly-ether sulphone membrane with a cut-off point of between 10 000 and 40 000 at a pressure of less than 2 000 kPa, a pH of between 4 and 7 and a temperature of less than 40°C. 10. The process as claimed in claim 7, wherein reverse osmosis is achieved by use of either of a spiral and a tubular configuration. 11. The process as claimed in claim 7, wherein a spiral wound poly-amide membrane with a point rejection of better than 99,6 % is used to achieve reverse osmosis. 12. The process as claimed in claim 7, wherein a poly-ether composite membrane with a point rejection of better than 99,6 % at a pressure of less than 60 bar, a pH of between 4 and 7 and a temperature of less than 40°C is used to achieve reverse osmosis. 13. The process as claimed in claim 7, wherein pervaporation is applied using membrane distillation. 14. The process as claimed in claim 7, wherein pervaporation is achieved using one or both of a flat sheet, chemically cross linked poly-vinyl alcohol membrane and a polymer blend of poly-vinyl alcohol and poly-acrylic acid membrane for removal of organics which do not form azeotropes at a pressures of less than 4 mm Hg, a pH of about 7 and a temperature of between 30°C and 70°C. 15. The process as claimed in any one of the preceding claims wherein the pH of the primary water-enriched stream is adjusted prior to step b) thereby to convert organic acids into organic salts.

Documents:

4159-delnp-2004-Abstract-(11-05-2012).pdf

4159-DELNP-2004-Abstract-(20-07-2011).pdf

4159-delnp-2004-abstract.pdf

4159-delnp-2004-Claims-(11-05-2012).pdf

4159-DELNP-2004-Claims-(20-07-2011).pdf

4159-delnp-2004-claims.pdf

4159-delnp-2004-Correspondence Others-(11-05-2012).pdf

4159-DELNP-2004-Correspondence Others-(20-07-2011).pdf

4159-delnp-2004-correspondence-others.pdf

4159-delnp-2004-description (complete).pdf

4159-DELNP-2004-Drawings-(20-07-2011).pdf

4159-delnp-2004-drawings.pdf

4159-delnp-2004-Form-1-(11-05-2012).pdf

4159-delnp-2004-form-1.pdf

4159-delnp-2004-form-18.pdf

4159-delnp-2004-Form-2-(11-05-2012).pdf

4159-DELNP-2004-Form-2-(20-07-2011).pdf

4159-delnp-2004-form-2.pdf

4159-delnp-2004-form-26.pdf

4159-delnp-2004-form-3.pdf

4159-delnp-2004-form-5.pdf

4159-delnp-2004-pct-210.pdf

4159-delnp-2004-pct-408.pdf

4159-delnp-2004-pct-409.pdf

4159-DELNP-2004-Petition-137-(20-07-2011)-1.pdf

4159-DELNP-2004-Petition-137-(20-07-2011).pdf