WO2012103582A1 - Cellulose phosphate powder product and process for manufacture thereof, and application to removal of contaminants from aqueous solutions - Google Patents

Cellulose phosphate powder product and process for manufacture thereof, and application to removal of contaminants from aqueous solutions Download PDF

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Publication number
WO2012103582A1
WO2012103582A1 PCT/AU2012/000083 AU2012000083W WO2012103582A1 WO 2012103582 A1 WO2012103582 A1 WO 2012103582A1 AU 2012000083 W AU2012000083 W AU 2012000083W WO 2012103582 A1 WO2012103582 A1 WO 2012103582A1
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Prior art keywords
water
removal
aqueous solutions
accordance
water soluble
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PCT/AU2012/000083
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French (fr)
Inventor
Adam Justin Blunn
Original Assignee
Australian Biorefining Pty Ltd
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Priority claimed from AU2011900307A external-priority patent/AU2011900307A0/en
Application filed by Australian Biorefining Pty Ltd filed Critical Australian Biorefining Pty Ltd
Priority to BR112013019640-8A priority Critical patent/BR112013019640A2/en
Priority to US13/983,225 priority patent/US9694343B2/en
Priority to JP2013552063A priority patent/JP6076264B2/en
Priority to SG2013065644A priority patent/SG193010A1/en
Priority to EA201370173A priority patent/EA201370173A1/en
Priority to AU2012212392A priority patent/AU2012212392A1/en
Priority to EP12742299.6A priority patent/EP2670711A4/en
Priority to CA2828777A priority patent/CA2828777A1/en
Priority to CN201280017492.4A priority patent/CN103476710B/en
Publication of WO2012103582A1 publication Critical patent/WO2012103582A1/en

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    • 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
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/14—Powdering or granulating by precipitation from solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/16—Esters of inorganic acids
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • B01J2220/4831—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton having been subjected to further processing, e.g. paper, cellulose pulp
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/103—Arsenic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/106—Selenium compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/206—Manganese or manganese compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/16—Esters of inorganic acids

Definitions

  • This invention relates to a chemical process for synthesising a modified cellulose phosphate powder from biomass sou roes of oetlulose Including, but not limited to, algae, bagasse, and waste paper.
  • This invention further relates to the application of the cellulose phosphate powder for use in removel of various contaminants or chemical species from water. Including but not limited to Mercury, Cadmium, Chromium, Copper, Zinc, Iron, Bismuth, Selenium, Tin, Cobalt, Nickel, Vanadium, Manganese, Uranium, Thorium, Arsenic, Load and Ammonia.
  • This Invention has particular application in near neutral pH aqueous solutions that are contaminated with various water soluble species.
  • Typical species include those containing transition metals, and also other contaminants containing ammonia, arsenic, and selenium. At low concentrations these contaminants are soluble in water and often have toxicological, clinical or environmental impacts. At low concentrations, many contaminants are difficult to separate from water.
  • the existing solutions for removal of trace level contaminants, particularly those utilized in industrial applications include the use of ion exchange resins, activated carbon or alumina, or titanium dioxide, reverse osmosis, chemical precipitation, or biological filtration. Each of these works with only specific contaminants. However none of these options is satisfactory for all contaminants. Further, other limitations of these processes include insufficient removal of particular contaminants, impractical application for large volumes, and high expense. Often a combination of two or more techniques is necessary, and creates process engineering difficulties.
  • the present invention involves creating a modified cellulose based powder by reacting a biomass based celiuloslc raw material with dilute phosphoric acid at elevated temperature.
  • the cellulosic raw material is partially dissolved and then the remaining insoluble raw material is separated from the dilute phosphoric add solution.
  • the clear phosphoric acid solution is then neutralized with subsequent precipitation of the modified cellulose, followed by , separating, washing and removal of excess water prior to use.
  • the resulting product is a sorbent powder.
  • sorbent (Wherever the term "sorbent* is used in this specification, this shall be Interpreted to mean adsorbent However, It is to be understood that the product may also have absorbent properties.)
  • the sorbent product which may be in the form of a powder or a slurry, is particularly useful for removal of low levels of contaminants from water and aqueous solutions. The solid residue resulting from extraction is then inert and non flammable, and the remaining filtrate is discarded, or may be processed for recovery of unreacted phosphoric acid .
  • the method of application includes but is not limited to contacting the sorbent product with the contaminated water or aqueous solution by mixing and then separating either by allowing the product to settle and decanting the supernatant treated water or solution, or by filtering, or some other method of solid liquid separation.
  • sorbent product can be used as an active component in a filter or permeable reactive barrier
  • the synthesis of the sorbent powder is performed by utilizing a ceilulosic feedstock.
  • a ceilulosic feedstock This may include but is not Hmfted to algae, bagasse, and favourably, waste paper.
  • the ceilulosic feedstock is then mixed with dilute phosphoric acid (typically in the concentration range from approximately 2g/ ⁇ up to 40 g/l but may also be In the range 1g/I up to 80g/[), and heated to reaction temperature for at least 2 minutes, but more preferably at least 5 minutes, up to 4 hours.
  • the heating may be performed by conventional means, but may also include alternative heating technologies for water Including microwave heating.
  • the ratio of ceilulosic feedstock to dilute phosphoric acid may typically be between a ratio of 1 part feedstock to 5 parts dilute phosphoric acid, up to 1 part feedstock to 40 parts of dilute phosphoric acid. However, this ratio may also foreseeabiy be in the range of 1 part feedstock to 2 parts dilute phosphoric acid , up to 1 part feedstock to 80 parts of dilute phosphoric acid. This is more of a practical issue rather than a technical limit.
  • the yield of sorbent from feedstock ranges from 4% by weight up to 40% by weight depending upon the feedstock used, the dilute acid concentration and volume, and the temperature and heating time of the synthesis.
  • the remaining solids and the solution are separated by any suitable means. Simple filtering has been shown to be effective.
  • the solid residue consists of insoluble end unreactive ceilulosic -feedstock. This residue is non flammable and, based upon this characteristic, may be useful as a tire retardant and in insulation products.
  • the filtrate or supernatant la neutralized to pH 7 with any suitable neutraizing agent but preferably caustic soda. As the neutralization is performed, a fine precipitate develops in solution which settles easily and filters easily. This precipitate is the object of the process and is recovered by filtering or other suitable solid liquid separation technique. The precipitate is then washed with water to remove any remaining salts, and excess water removed. Accordingly, the product may be a dried powder or may be in the form of a slurry.
  • the application of the sorbent product for treatment of low level water contaminants is performed by simple mixing of the sorbent product with water. Contact and mixing time may typically be between approximately 5 minutes and 2 hours. However, this range may be greater and foreseeably may be between approximately 2 minutes and 24 hours, with dose rate determined by total load of contaminants and capacity of the sorbent for a given contaminant.
  • solid liquid separation is performed by any suitable means including but not limited to tittering, centrifugation, and decanting. Additionally the sorbent can be utilized as a filter bed with the contaminated water passed through the filter bed with removal of various contaminants taking place within the filter bed.
  • the present invention provides an alternative and more cost effective solution for the removal of the abovementioned contaminants from water.
  • the cellulose phosphate product has different physical characteristics and improved performance as water treatment product, particularly for trace contaminants, in addition, the cellulose phosphate of the present invention has a Fourier Transformation Infrared spectrum that shows significant differences from conventional cellulose phosphate esters and ethers.
  • the process described in the present invention utilizes a different method of synthesis to previously taught approaches and otters a number of advantages including greater simplicity, tower risk and production costs. This results In a product with affinity for a range of contaminants (the affinity of which may vary according to the contaminant) without the need for further functionalization.
  • Example 1 3.128 g of waste paper was reacted with 120 mis of 8% w/v phosphoric acid at 104 degrees C for 2hours 43 minutes. The resultant mixture was cooled, separated by filtering end the residue washed and dried. 2.206 g of residue was recovered. The filtrate and washings were neutralized with 40 g/l caustic soda to a pH of 7.0, the resultant precipitated powder was filtered and washed and dried to give a final weight of 0.845 g of sorbent powder. 0.5g of this powder was added to a 1 litre water sample with 24 hours mixing and the resultant change in composition was:
  • Example 2 2.003 g of bagasse was reacted with 100 mis of 8% w/v phosphoric acid at 100 degrees C for 3 hours and 15 minutes. The resultant mixture was cooled separated by filtering and the residue washed and dried. 1.782 g of residue was recovered. The filtrate and washings were neutralized with 40 g/l caustic soda to a pH of 7.0, the resultant precipitated powder was filtered and washed and dried to give a final weight of 0.241 g of sorbent powder.
  • Example 3 1.030 g of dried filamentous algae was reacted with 100 mis of 8% w/v phosphoric acid at 100 degrees C for 3 hours and 15 minutes. The resultant mixture was cooled separated by filtering and the residue washed and- dried. 0.962 g of residue was recovered. The filtrate end washings were neutralized with 40 g/l caustic soda to a pH of 7.0, the resultant precipitated powder was filtered and washed and dried to give a final weight of 0.073 g of sorbent powder.
  • Example 4 1170 g of waste paper was boiled with 23.3 litres of 4.4% w/v phosphoric acid for 2 hours. The resultant mixture was cooled separated by deoanting end then filtering and the residue washed and dried. The filtrate and washings were neutralized with 80 g/l caustic soda to a pH of 6.5, the resultant precipitated powder was filtered and washed and dried to give a final weight of 221 g of sorbent powder. 339 mg of this powder was prepared as a column filter and 100 ml of contaminated water was passed through the filter. The resultant change in water composition was:
  • the invention enables the reduction of a range of trace contaminants from contaminated water sources with near neutral pH. without any toxic or aesthetic reduction In water quality.
  • This invention has particular application in dilute waste water treatment, or environmental water treatment

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Materials Engineering (AREA)
  • Biochemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions comprising reacting one or more biomass based cellulose containing raw materials with dilute phosphoric acid where the reaction mixture containing said cellulose containing materials is heated to a reaction temperature and after completion of the reaction time, separation of the dilute phosphoric acid solution from the remaining insoluble raw material, neutralisation of the solution by means of a suitable neutralising agent resulting in precipitation of the modified cellulose, and then separating, washing and removing excess water from the resultant precipitate.

Description

Cellulose phosphate powder product and process for manufacture thereof, and application to removal of contaminants from aqueous solutions
Field of the Invention
This invention relates to a chemical process for synthesising a modified cellulose phosphate powder from biomass sou roes of oetlulose Including, but not limited to, algae, bagasse, and waste paper.
This invention further relates to the application of the cellulose phosphate powder for use in removel of various contaminants or chemical species from water. Including but not limited to Mercury, Cadmium, Chromium, Copper, Zinc, Iron, Bismuth, Selenium, Tin, Cobalt, Nickel, Vanadium, Manganese, Uranium, Thorium, Arsenic, Load and Ammonia.
Backoround of the Invention
This Invention has particular application in near neutral pH aqueous solutions that are contaminated with various water soluble species. Typical species include those containing transition metals, and also other contaminants containing ammonia, arsenic, and selenium. At low concentrations these contaminants are soluble in water and often have toxicological, clinical or environmental impacts. At low concentrations, many contaminants are difficult to separate from water. The existing solutions for removal of trace level contaminants, particularly those utilized in industrial applications, include the use of ion exchange resins, activated carbon or alumina, or titanium dioxide, reverse osmosis, chemical precipitation, or biological filtration. Each of these works with only specific contaminants. However none of these options is satisfactory for all contaminants. Further, other limitations of these processes include insufficient removal of particular contaminants, impractical application for large volumes, and high expense. Often a combination of two or more techniques is necessary, and creates process engineering difficulties.
Summary of the Invention
The present invention involves creating a modified cellulose based powder by reacting a biomass based celiuloslc raw material with dilute phosphoric acid at elevated temperature. The cellulosic raw material is partially dissolved and then the remaining insoluble raw material is separated from the dilute phosphoric add solution. The clear phosphoric acid solution is then neutralized with subsequent precipitation of the modified cellulose, followed by , separating, washing and removal of excess water prior to use. The resulting product is a sorbent powder. (Wherever the term "sorbent* is used in this specification, this shall be Interpreted to mean adsorbent However, It is to be understood that the product may also have absorbent properties.) The sorbent product, which may be in the form of a powder or a slurry, is particularly useful for removal of low levels of contaminants from water and aqueous solutions. The solid residue resulting from extraction is then inert and non flammable, and the remaining filtrate is discarded, or may be processed for recovery of unreacted phosphoric acid .
As a sorbent for trace contaminants, the method of application includes but is not limited to contacting the sorbent product with the contaminated water or aqueous solution by mixing and then separating either by allowing the product to settle and decanting the supernatant treated water or solution, or by filtering, or some other method of solid liquid separation.
Additionally the sorbent product can be used as an active component in a filter or permeable reactive barrier
Detailed Description of the Preferred Embodiments
The synthesis of the sorbent powder is performed by utilizing a ceilulosic feedstock. This may include but is not Hmfted to algae, bagasse, and favourably, waste paper. The ceilulosic feedstock is then mixed with dilute phosphoric acid (typically in the concentration range from approximately 2g/\ up to 40 g/l but may also be In the range 1g/I up to 80g/[), and heated to reaction temperature for at least 2 minutes, but more preferably at least 5 minutes, up to 4 hours. The heating may be performed by conventional means, but may also include alternative heating technologies for water Including microwave heating. The ratio of ceilulosic feedstock to dilute phosphoric acid may typically be between a ratio of 1 part feedstock to 5 parts dilute phosphoric acid, up to 1 part feedstock to 40 parts of dilute phosphoric acid. However, this ratio may also foreseeabiy be in the range of 1 part feedstock to 2 parts dilute phosphoric acid , up to 1 part feedstock to 80 parts of dilute phosphoric acid. This is more of a practical issue rather than a technical limit. The yield of sorbent from feedstock ranges from 4% by weight up to 40% by weight depending upon the feedstock used, the dilute acid concentration and volume, and the temperature and heating time of the synthesis.
Following reaction of the feedstock with dHute phosphoric acid, the remaining solids and the solution are separated by any suitable means. Simple filtering has been shown to be effective. The solid residue consists of insoluble end unreactive ceilulosic -feedstock. This residue is non flammable and, based upon this characteristic, may be useful as a tire retardant and in insulation products. Subsequent to the initial solid liquid separation, the filtrate or supernatant la neutralized to pH 7 with any suitable neutraizing agent but preferably caustic soda. As the neutralization is performed, a fine precipitate develops in solution which settles easily and filters easily. This precipitate is the object of the process and is recovered by filtering or other suitable solid liquid separation technique. The precipitate is then washed with water to remove any remaining salts, and excess water removed. Accordingly, the product may be a dried powder or may be in the form of a slurry.
The application of the sorbent product for treatment of low level water contaminants is performed by simple mixing of the sorbent product with water. Contact and mixing time may typically be between approximately 5 minutes and 2 hours. However, this range may be greater and foreseeably may be between approximately 2 minutes and 24 hours, with dose rate determined by total load of contaminants and capacity of the sorbent for a given contaminant. Following mixing of the sorbent and the water to be treated, solid liquid separation is performed by any suitable means including but not limited to tittering, centrifugation, and decanting. Additionally the sorbent can be utilized as a filter bed with the contaminated water passed through the filter bed with removal of various contaminants taking place within the filter bed.
The use of cellulose phosphate derivatives has been described in prior art patents DE19850286 <A1); DE19753198 (A1); DE19859746 (A1); US6579977 (B1); US6761272 (51); U82007093664 (At); GB1001603 (A). In these patents all cellulose feedstocks described are prepared via several steps which include caustic pulping, further pulp preparation, and derlvattsatlon with complex and expensive phosphate reagents. In the above prior art documents, derivabsation is performed In organic solvents which increase the safety risks and expense of producing a cellulose phosphate derivative. Further, additional dertvatJeatlon is needed to achieve satisfactory performance for trace contaminant removal and this usually includes but is not limited to addition of amine or nitrogen species to effect an improved functionality of the cellulose derivative.
The present invention provides an alternative and more cost effective solution for the removal of the abovementioned contaminants from water. The cellulose phosphate product has different physical characteristics and improved performance as water treatment product, particularly for trace contaminants, in addition, the cellulose phosphate of the present invention has a Fourier Transformation Infrared spectrum that shows significant differences from conventional cellulose phosphate esters and ethers. The process described in the present invention utilizes a different method of synthesis to previously taught approaches and otters a number of advantages including greater simplicity, tower risk and production costs. This results In a product with affinity for a range of contaminants (the affinity of which may vary according to the contaminant) without the need for further functionalization.
The following examples are provided in order to illustrate the process:
[Example 1: 3.128 g of waste paper was reacted with 120 mis of 8% w/v phosphoric acid at 104 degrees C for 2hours 43 minutes. The resultant mixture was cooled, separated by filtering end the residue washed and dried. 2.206 g of residue was recovered. The filtrate and washings were neutralized with 40 g/l caustic soda to a pH of 7.0, the resultant precipitated powder was filtered and washed and dried to give a final weight of 0.845 g of sorbent powder. 0.5g of this powder was added to a 1 litre water sample with 24 hours mixing and the resultant change in composition was:
Figure imgf000005_0001
Example 2: 2.003 g of bagasse was reacted with 100 mis of 8% w/v phosphoric acid at 100 degrees C for 3 hours and 15 minutes. The resultant mixture was cooled separated by filtering and the residue washed and dried. 1.782 g of residue was recovered. The filtrate and washings were neutralized with 40 g/l caustic soda to a pH of 7.0, the resultant precipitated powder was filtered and washed and dried to give a final weight of 0.241 g of sorbent powder.
Example 3: 1.030 g of dried filamentous algae was reacted with 100 mis of 8% w/v phosphoric acid at 100 degrees C for 3 hours and 15 minutes. The resultant mixture was cooled separated by filtering and the residue washed and- dried. 0.962 g of residue was recovered. The filtrate end washings were neutralized with 40 g/l caustic soda to a pH of 7.0, the resultant precipitated powder was filtered and washed and dried to give a final weight of 0.073 g of sorbent powder.
(Example 4: 1170 g of waste paper was boiled with 23.3 litres of 4.4% w/v phosphoric acid for 2 hours. The resultant mixture was cooled separated by deoanting end then filtering and the residue washed and dried. The filtrate and washings were neutralized with 80 g/l caustic soda to a pH of 6.5, the resultant precipitated powder was filtered and washed and dried to give a final weight of 221 g of sorbent powder. 339 mg of this powder was prepared as a column filter and 100 ml of contaminated water was passed through the filter. The resultant change in water composition was:
Figure imgf000006_0001
The invention enables the reduction of a range of trace contaminants from contaminated water sources with near neutral pH. without any toxic or aesthetic reduction In water quality. This invention has particular application in dilute waste water treatment, or environmental water treatment
Accordingly the Invention has both commercial and environmental advantages. It will of course be realised that while the foregoing has been given by way of illustrative example of this invention, all such and other modifications and variations thereto as would be apparent to persons skilled In the art are deemed to fall within the broad scope and ambit of this invention as Is herein set forth.

Claims

Claims
1. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions comprising reacting one or more biomass based cellulose containing raw materials with dilute phosphoric acid where the reaction mixture containing said cellulose containing materials is heated to a reaction temperature and after completion of the reaction time, separation of the dilute phosphoric acid solution from the remaining insoluble raw material, neutralisation of the solution by means of a suitable neutralising agent resulting in precipitation of the modified cellulose, and then separating, washing and removing excess water from the resultant precipitate.
2. A process tor producing a cellulose based sorbent material comprising reacting one or more biomass based cellulose containing raw materials with dilute phosphoric acid where the reaction mixture containing said cellulose containing materials is heated to a reaction temperature and after completion of the reaction time, separation of the dilute phosphoric acid solution from the remaining insoluble raw material, neutralisation of the solution by means of a suitable neutralising agent resulting in precipitation of the modified cellulose, and then filtering, washing and drying the resultant precipitate.
3. A process for producing a cellulose based sorbent material in accordance with claim 1 or 2 in which the concentration of the phosphoric acid is in the range of approximately lg/1 to 80g/l.
4. A process for producing a cellulose based sorbent material in accordance with daim 1 or 2 in which the concentration of the phosphoric acid is in the range of approximately 2g/l to 40g/l.
5- A process for producing a cellulose based sorbent material in accordance with any one of claims 1 to 4 wherein the reaction mixture is heated to reaction temperature for at least 2 minutes.
6. A process for producing a cellulose based sorbent material in accordance with any one of claims 1 to 4 wherein the reaction mixture is heated to reaction temperature for at least 5 minutes.
7. A process for producing a cellulose based sorbent material in accordance with any one of claims 1 to 4 wherein the reaction mixture is heated to reaction temperature for at least 1 hour.
8. A process for producing a cellulose based sorbent material tn accordance with any one of claims 1 to 4 wherein the reaction mixture is heated to reaction temperature for up to 4 hours.
9. A process for producing a cellulose based sorbent material in accordance with any one of claims 1 to 8 in which the ratio of cellulosic feedstock to dilute phosphoric acid is in the range of part feedstock to 5 parts dilute phosphoric acid up to 1 part feedstock to 40 parts of dilute phosphoric acid.
10. A process for producing a cellulose based sorbent material In accordance with any one of claims 1 to 8 in which the ratio of cellulosic feedstock to dilute phosphoric acid is in the range of part feedstock to 2 parts dilute phosphoric aoid up to 1 part feedstock to 80 parts of dilute phosphoric acid.
11. A process for producing a cellulose based sorbent material in accordance with any one of claims 1 to 10 wherein the neutralisation agent used to neutralize the solution Is caustic soda.
12. A process for producing a cellulose based sorbent material in accordance with any one of claims 1 to 11 wherein the solution is neutralized to approximately pH 7.
13. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions in accordance with any one of claims 1 to 12 wherein at least one contaminant contains Mercury.
14. A process for producing a oellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions in accordance with any one of claims 1 to 12 wherein at least one contaminant contains Cadmium.
15. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions in accordance with any one of claims 1 to 12 wherein at least one contaminant contains Chromium.
16. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions in accordance with any one of claims 1 to 12 wherein at least one contaminant contains Copper.
17. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions in accordance with any one of claims 1 to 12 wherein at least one contaminant contains Zinc.
18. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and otner aqueous solutions in accordance with any one of claims 1 to 12 wherein at least one contaminant contains Iron.
19. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions in accordance with any one of claims 1 to 12 wherein at least one contaminant contains Bismuth.
20. A prooesB for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions in accordance with any one of claims 1 to 12 wherein at least one contaminant contains Selenium.
21. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions in accordance with any one of claims 1 to 12 wherein at least one contaminant contains Tin.
22. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions in accordance with any one of claims 1 to 12 wherein at least one contaminant contains Cobalt
23. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions In accordance with any one of claims 1 to 12 wherein at least one contaminant contains Nickel.
24. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions in accordance with any one of claims 1 to 12 wherein at least one contaminant contains Vanadium.
26. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions in accordance with any one of claims 1 to 12 wherein at least one contaminant contains Manganese.
26. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions in accordance with any one of claims 1 to 12 wherein at least one contaminant contains Uranium.
27. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions In accordance with any one or claims 1 to 12 wherein at least one contaminant contains Thorium.
28. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions in accordance with any one of claims 1 to 12 wherein at least one contaminant contains Arsenic.
29. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions in accordance with any one of claims 1 to 12 wherein at least one contaminant contains Lead.
30. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions in accordance with any one of claims 1 to 12 wherein at least one contaminant contains Ammonia.
31. A process for producing a cellulose based sorbent material for the removal of water soluble contaminants from water and other aqueous solutions substantially as hereinbefore described with reference to the examples.
32. A cellulose based sorbent product manufactured in accordance with the process in any one of claims 1 to 13.
33. A cellulose based sorbent product manufactured in accordance with the process in any one of claims 1 to 13 In which the product is in the form of a powder.
34. A cellulose based sorbent product manufactured in accordance with the process In any one of claims 1 to 13 in which the product Is In the form of a slurry.
35. A method for the removal of water soluble contaminants from water and other aqueous solution by contacting a sorbent product manufactured in accordance with the process in any one of claims 1 to 13 with the contaminated water or aqueous solution by mixing and then separating the product and the treated water or aqueous solution.
36. A method in accordance with claim 17 In which Seperation b effected by allowing the product to settle and decanting the supernatant treated water or aqueous solution.
37. A method in accordance with claim 17 in which separation is effected by filtration
38. A method in accordance with claim 17 in which separation is effected by some other method of solid liquid separation.
39. A method for the removal of water soluble contaminants from water and other aqueous solutions by utilising the sorbent product manufactured In accordance with the process in any one of claims 1 to 13 as an active component In a filter.
40. A method for the removal of water soluble contaminants from water and other aqueous solutions by utilising the sorbent product manufactured In accordance with the process in any one of claims 1 to 13 as an active component in a permeable reactive barrier.
41. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one contaminant contains Mercury.
42. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one contaminant contains Cadmium.
43. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one oontaminant contains Chromium.
44. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one contaminant contains Copper.
45. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one contaminant contains Zinc.
46. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one contaminant contains Iron.
47. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one contaminant contains Bismuth.
48. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one contaminant contains Selenium.
4Θ. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one contaminant contains Tin.
50. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one contaminant contains Cobalt.
51. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one contaminant contains Nickel.
52. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one contaminant contains Vanadium.
53. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one contaminant contains Manganese.
54. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one contaminant contains Uranium.
55. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one contaminant contains Thorium.
56. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one contaminant contains Arsenic.
57. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one contaminant contains Lead.
58. A method for the removal of water soluble contaminants from water and other aqueous solutions wherein at least one contaminant contains Ammonia.
PCT/AU2012/000083 2011-02-01 2012-02-01 Cellulose phosphate powder product and process for manufacture thereof, and application to removal of contaminants from aqueous solutions WO2012103582A1 (en)

Priority Applications (9)

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BR112013019640-8A BR112013019640A2 (en) 2011-02-01 2012-02-01 processes for producing a cellulose-based absorbent material, cellulose-based absorbent products and methods for removing water-soluble contaminants from water and other aqueous solutions
US13/983,225 US9694343B2 (en) 2011-02-01 2012-02-01 Cellulose phosphate powder product and process for manufacture thereof, and application to removal of contaminants from aqueous solutions
JP2013552063A JP6076264B2 (en) 2011-02-01 2012-02-01 Cellulose phosphate powder product, process for producing the same, and use for removing contaminants from aqueous solutions
SG2013065644A SG193010A1 (en) 2011-02-01 2012-02-01 Cellulose phosphate powder product and process for manufacture thereof, and application to removal of contaminants from aqueous solutions
EA201370173A EA201370173A1 (en) 2011-02-01 2012-02-01 PRODUCT FROM POWDER OF PHOSPHATE OF CELLULOSE AND METHOD FOR ITS PREPARATION AND ALSO APPLICATION FOR REMOVAL OF POLLUTANT IMPURITIES FROM AQUEOUS SOLUTIONS
AU2012212392A AU2012212392A1 (en) 2011-02-01 2012-02-01 Cellulose phosphate powder product and process for manufacture thereof, and application to removal of contaminants from aqueous solutions
EP12742299.6A EP2670711A4 (en) 2011-02-01 2012-02-01 Cellulose phosphate powder product and process for manufacture thereof, and application to removal of contaminants from aqueous solutions
CA2828777A CA2828777A1 (en) 2011-02-01 2012-02-01 Cellulose phosphate powder product and process for manufacture thereof, and application to removal of contaminants from aqueous solutions
CN201280017492.4A CN103476710B (en) 2011-02-01 2012-02-01 Cellulose phosphate powder-product and manufacture method thereof and from aqueous solution, remove the application of pollutant

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AU2011900307A AU2011900307A0 (en) 2011-02-01 Cellulose phosphate powder product and process for the manufacture thereof, and application to removal of contaminants from water

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JP (1) JP6076264B2 (en)
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BR (1) BR112013019640A2 (en)
CA (1) CA2828777A1 (en)
CL (1) CL2013002208A1 (en)
EA (1) EA201370173A1 (en)
PE (1) PE20140631A1 (en)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2659296A1 (en) * 2016-09-14 2018-03-14 Universidad De Valladolid MULTILECHE PILOT PROCESS AND PLANT FOR BIOMASS FRACTIONATION (Machine-translation by Google Translate, not legally binding)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111790357A (en) * 2020-07-22 2020-10-20 广东药科大学 Preparation method of modified traditional Chinese medicine residue biomass adsorbent and application of modified traditional Chinese medicine residue biomass adsorbent in treatment of dye wastewater
CN113831795A (en) * 2021-09-26 2021-12-24 齐耐润工业设备（上海）有限公司 Teflon coated metal net and preparation method thereof

Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB899284A (en) * 1957-11-01 1962-06-20 Atomic Energy Authority Uk Improved phosphorylated cellulose and method of obtaining it
GB1001603A (en) 1961-04-10 1965-08-18 Fmc Corp Separation, purification and recovery processes
GB1445754A (en) * 1972-11-20 1976-08-11 Elepon Kakoki Co Method of adsorbing heavy metal ions
JPS58161926A (en) * 1982-03-18 1983-09-26 Sumitomo Chem Co Ltd Method for recovering uranium
CZ21197A3 (en) * 1997-01-22 1997-10-15 Eco Agua Servis Prazak Michal Process for removing dissolved compounds of nickel and other heavy metals from water
DE19753196A1 (en) 1997-12-01 1999-07-08 Eisu Innovative Ges Fuer Techn Production of cellulosic biosorbents, used for removing heavy metals from aqueous solution
DE19850286A1 (en) 1998-10-30 2000-05-04 Eisu Innovative Ges Fuer Techn Production of cellulosic biosorbents, used for removing heavy metals from aqueous solution
DE19859746A1 (en) 1998-12-23 2000-06-29 Georg Haertel Materials, for removing heavy metals and organic pollutants from contaminated water, contain cellulose or starch derivative
JP2002192186A (en) * 2000-12-22 2002-07-10 Fuji Photo Film Co Ltd Heavy metal trapping method and heavy metal recovering method
US6512110B1 (en) 1997-06-10 2003-01-28 Xyrofin Oy Process for the production of xylose from a paper-grade hardwood pulp
US6579977B1 (en) 1997-12-01 2003-06-17 Eisu Innovative Gesellschaft Fur Technik Und Umweltschutz Mbh Biosorbents and process for producing the same
US6761272B1 (en) 1999-05-28 2004-07-13 Helmut Körber Filters consisting of filter paper or paper-type nonwoven material
US20050175758A1 (en) * 2002-04-09 2005-08-11 Helmut Korber Rapid-action agent for preparing cold and hot beverages from drinking water
RU2291113C1 (en) * 2005-07-19 2007-01-10 Учреждение образования "Белорусский государственный технологический университет" Method of purification of waste water from ions of chromium (iii) and (iv)
US20070093654A1 (en) 2003-10-31 2007-04-26 Kowa Co., Ltd. Cellulose II phosphate ester and metal-adsorbing material using the same
RU2334802C2 (en) * 2006-11-17 2008-09-27 ОАО "Соликамский магниевый завод" Method of extraction and concentration of thorium out of spent melt of saline sprinkler filter - process waste of chlorinate treatment of loparit concentrate
CN101508426A (en) * 2009-03-24 2009-08-19 中南大学 Method for separating tellurium from tellurium slag
TW200938494A (en) * 2007-12-17 2009-09-16 Applied Process Technology Inc Removal of selenium in contaminated wastewater streams
TWI320029B (en) * 2004-02-24 2010-02-01 Method for removal of arsenic from water
MX2008012759A (en) * 2008-10-03 2010-04-05 Ct De Investigacion En Materia Filtrating material based on flavonoids for removing fluorine (f), arsenic (as), copper (cu), lead (pb), chromium (cr) and zinc (zn) from water effluents.
GR1006922B (en) * 2009-09-07 2010-07-30 Δημητριος Βασιλειου Βαγενας Biological filter for removing hydrogen sulphide, ammonia, iron and manganese from drinkable water with no use of mechanical aeration
US20100252509A1 (en) * 2009-04-01 2010-10-07 Kipers Kenneth C Filter Medium for Metal-Working Liquids
AU2010295857A1 (en) * 2009-09-18 2012-03-08 Phillips 66 Company Mercury removal from water

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2759924A (en) * 1952-01-02 1956-08-21 Eastman Kodak Co Preparation of cellulose phosphates
KR880002755A (en) * 1986-08-04 1988-05-11 이소-클리어시스템즈코오포레이숀 Method for preparing a mixture for removing heavy metals and a method for removing heavy metals by the mixture and the mixture
JPH07100373A (en) * 1993-09-30 1995-04-18 Toyo Denka Kogyo Kk Adsorbent
JP2000504767A (en) * 1996-02-14 2000-04-18 アクゾ ノーベル ナムローゼ フェンノートシャップ Preparation of substances with high absorption capacity for water and salt solutions
JP2003225559A (en) * 2001-06-21 2003-08-12 Japan Science & Technology Corp Adsorbent made from plant biomass
JP2010082497A (en) * 2008-09-29 2010-04-15 Lion Corp Water treating agent and method for treating water

Patent Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB899284A (en) * 1957-11-01 1962-06-20 Atomic Energy Authority Uk Improved phosphorylated cellulose and method of obtaining it
GB1001603A (en) 1961-04-10 1965-08-18 Fmc Corp Separation, purification and recovery processes
GB1445754A (en) * 1972-11-20 1976-08-11 Elepon Kakoki Co Method of adsorbing heavy metal ions
JPS58161926A (en) * 1982-03-18 1983-09-26 Sumitomo Chem Co Ltd Method for recovering uranium
CZ21197A3 (en) * 1997-01-22 1997-10-15 Eco Agua Servis Prazak Michal Process for removing dissolved compounds of nickel and other heavy metals from water
US6512110B1 (en) 1997-06-10 2003-01-28 Xyrofin Oy Process for the production of xylose from a paper-grade hardwood pulp
US6579977B1 (en) 1997-12-01 2003-06-17 Eisu Innovative Gesellschaft Fur Technik Und Umweltschutz Mbh Biosorbents and process for producing the same
DE19753196A1 (en) 1997-12-01 1999-07-08 Eisu Innovative Ges Fuer Techn Production of cellulosic biosorbents, used for removing heavy metals from aqueous solution
DE19850286A1 (en) 1998-10-30 2000-05-04 Eisu Innovative Ges Fuer Techn Production of cellulosic biosorbents, used for removing heavy metals from aqueous solution
DE19859746A1 (en) 1998-12-23 2000-06-29 Georg Haertel Materials, for removing heavy metals and organic pollutants from contaminated water, contain cellulose or starch derivative
US6761272B1 (en) 1999-05-28 2004-07-13 Helmut Körber Filters consisting of filter paper or paper-type nonwoven material
JP2002192186A (en) * 2000-12-22 2002-07-10 Fuji Photo Film Co Ltd Heavy metal trapping method and heavy metal recovering method
US20050175758A1 (en) * 2002-04-09 2005-08-11 Helmut Korber Rapid-action agent for preparing cold and hot beverages from drinking water
US20070093654A1 (en) 2003-10-31 2007-04-26 Kowa Co., Ltd. Cellulose II phosphate ester and metal-adsorbing material using the same
TWI320029B (en) * 2004-02-24 2010-02-01 Method for removal of arsenic from water
RU2291113C1 (en) * 2005-07-19 2007-01-10 Учреждение образования "Белорусский государственный технологический университет" Method of purification of waste water from ions of chromium (iii) and (iv)
RU2334802C2 (en) * 2006-11-17 2008-09-27 ОАО "Соликамский магниевый завод" Method of extraction and concentration of thorium out of spent melt of saline sprinkler filter - process waste of chlorinate treatment of loparit concentrate
TW200938494A (en) * 2007-12-17 2009-09-16 Applied Process Technology Inc Removal of selenium in contaminated wastewater streams
MX2008012759A (en) * 2008-10-03 2010-04-05 Ct De Investigacion En Materia Filtrating material based on flavonoids for removing fluorine (f), arsenic (as), copper (cu), lead (pb), chromium (cr) and zinc (zn) from water effluents.
CN101508426A (en) * 2009-03-24 2009-08-19 中南大学 Method for separating tellurium from tellurium slag
US20100252509A1 (en) * 2009-04-01 2010-10-07 Kipers Kenneth C Filter Medium for Metal-Working Liquids
GR1006922B (en) * 2009-09-07 2010-07-30 Δημητριος Βασιλειου Βαγενας Biological filter for removing hydrogen sulphide, ammonia, iron and manganese from drinkable water with no use of mechanical aeration
AU2010295857A1 (en) * 2009-09-18 2012-03-08 Phillips 66 Company Mercury removal from water

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2670711A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2659296A1 (en) * 2016-09-14 2018-03-14 Universidad De Valladolid MULTILECHE PILOT PROCESS AND PLANT FOR BIOMASS FRACTIONATION (Machine-translation by Google Translate, not legally binding)
WO2018050941A1 (en) * 2016-09-14 2018-03-22 Universidad De Valladolid Multi-bed pilot plant and process for biomass fractionation

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SG193010A1 (en) 2013-09-30
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CA2828777A1 (en) 2012-08-09
SG10201600783UA (en) 2016-03-30
EP2670711A1 (en) 2013-12-11
AU2012212392A1 (en) 2013-05-09
CL2013002208A1 (en) 2014-06-27
JP2014505592A (en) 2014-03-06
CN103476710A (en) 2013-12-25
PE20140631A1 (en) 2014-05-29
EA201370173A1 (en) 2014-01-30
US20140073775A1 (en) 2014-03-13
BR112013019640A2 (en) 2020-08-04
US9694343B2 (en) 2017-07-04
JP6076264B2 (en) 2017-02-08

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