WO2010020698A2 - Equipment for quick dispersion of polyacrylamide powder for fracturing operations - Google Patents

Equipment for quick dispersion of polyacrylamide powder for fracturing operations Download PDF

Info

Publication number
WO2010020698A2
WO2010020698A2 PCT/EP2009/063961 EP2009063961W WO2010020698A2 WO 2010020698 A2 WO2010020698 A2 WO 2010020698A2 EP 2009063961 W EP2009063961 W EP 2009063961W WO 2010020698 A2 WO2010020698 A2 WO 2010020698A2
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
fracturing
polyacrylamide
installation
flow rate
Prior art date
Application number
PCT/EP2009/063961
Other languages
French (fr)
Other versions
WO2010020698A3 (en
Inventor
Peter Nichols
Original Assignee
S.P.C.M. Sa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by S.P.C.M. Sa filed Critical S.P.C.M. Sa
Priority to EP09748740.9A priority Critical patent/EP2513411B1/en
Priority to BR112012007702-3A priority patent/BR112012007702B1/en
Priority to DK09748740.9T priority patent/DK2513411T3/en
Priority to AU2009284121A priority patent/AU2009284121B2/en
Priority to CN200980161957.1A priority patent/CN102713131B/en
Priority to CA2775168A priority patent/CA2775168C/en
Publication of WO2010020698A2 publication Critical patent/WO2010020698A2/en
Publication of WO2010020698A3 publication Critical patent/WO2010020698A3/en
Priority to IN2473DEN2012 priority patent/IN2012DN02473A/en
Priority to US13/446,846 priority patent/US8800659B2/en

Links

Classifications

    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
    • E21B21/06—Arrangements for treating drilling fluids outside the borehole
    • E21B21/062—Arrangements for treating drilling fluids outside the borehole by mixing components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/50—Mixing liquids with solids
    • B01F23/53—Mixing liquids with solids using driven stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • B01F27/81—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis the stirrers having central axial inflow and substantially radial outflow
    • B01F27/812—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis the stirrers having central axial inflow and substantially radial outflow the stirrers co-operating with surrounding stators, or with intermeshing stators, e.g. comprising slits, orifices or screens
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/71—Feed mechanisms
    • B01F35/717—Feed mechanisms characterised by the means for feeding the components to the mixer
    • B01F35/71775—Feed mechanisms characterised by the means for feeding the components to the mixer using helical screws
    • 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
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
    • E21B21/06—Arrangements for treating drilling fluids outside the borehole
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/25—Methods for stimulating production
    • E21B43/26—Methods for stimulating production by forming crevices or fractures
    • E21B43/2607—Surface equipment specially adapted for fracturing operations
    • 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
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/24—Homopolymers or copolymers of amides or imides
    • C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide

Definitions

  • the permeability and production areas therefore need to be increased by way of stimulation operations and fracturing in particular.
  • Hydraulic fracturing is designed to create an additional level of permeability and an increased gas production surface areas. Indeed, low permeability, natural barriers of compact layers, impermeability due to drilling operations greatly limit production. These fracturing operations started in 1960 in the Appalachian Mountains and today over one million operations have taken place in the USA.
  • the injection water usually contains a significant amount of additives, each with a defined function.
  • the injected composition includes: clay swelling inhibitors such as potassium chloride biocides to prevent bacteria, particularly sulphate-reducing bacteria, from developing and capable of forming viscous masses reducing the injection areas.
  • Aldehydes are the most commonly used biocides as glutaraldehyde, acrolein, etc... oxygen scavengers such as ammonium bisulphite to prevent the destruction of other components due to oxidation and corrosion of the injection lines, - corrosion inhibitors to protect the lines from oxidation by residual quantities of oxygen.
  • oxygen scavengers such as ammonium bisulphite to prevent the destruction of other components due to oxidation and corrosion of the injection lines, - corrosion inhibitors to protect the lines from oxidation by residual quantities of oxygen.
  • N n dimethylformamide
  • lubricants such as petroleum distillates
  • - gelling agents such as guar gum and hydroxyethyl cellulose
  • iron-chelating agents such as citric acid, EDTA
  • phosphonates - scale control products
  • friction reducers to reduce the pressure drop in turbulent media and significantly increase the flow rate for the same power and pipe diameter.
  • Acid treatment is often performed before or during injection to treat cementation residue or to dissolve part of the rock in place in order to provide better access to the field.
  • the sand injected is of a particular size, usually between 40 and 100 mesh.
  • oil- soluble polymers are used, particularly polymethyl methacrylate or carbohydrate polymers.
  • polyacrylamides When the medium is water, very high molecular weight polymers such as polyacrylamides and ethylene oxide polymers are used. Preference is generally given to polyacrylamides for cost and sourcing reasons. Polyacrylamides
  • polyacrylamides are increasingly used in other applications, and especially where their thickening effect on water based system is desired.
  • polyacrylamides covers acrylamide homopolyers as well as all the copolymers containing both acrylamide and other monomers such as: acids such as (metha)acrylic acid, AMPS (2-Acrylamido-2-methylpropane sulfonic acid), etc cationic monomers such as the ammonium salts of trimethylethyl methacrylate, diallyl dimethyl ammonium chloride, etc
  • polymers can be modified by: branching with branching agents in sufficiently low quantities to maintain the solubility - Hydrophobic monomers giving associative polymers
  • the polymers used must have the highest molecular weight possible while keeping very good solubility.
  • the polymer of choice is an acrylamide sodium acrylate copolymer (70% 30% molar ratio) with a molecular weight close to 20 million.
  • reverse emulsions of these polymers are used with a concentration of active matter between 20 and 50%. These emulsions are stable in storage for about 6 months and dissolve very quickly (few minutes) in water under stirring. They allow a in line injection in the fracturing water before the high pressure pump and are practically fully dissolved in a few minutes both immediately and in the injection line.
  • the quantities of polymers injected can be between 250 and 2,000 ppm of active matter and the fracturing time between 2 and 15 hours with several stages of injections (2 to 20).
  • the use of emulsions is today generalised over the entire territory of USA-Canada- Mexico and is spreading into other countries according to new reserves to be exploited.
  • the constant demand is to only consume the water from the field and to treat the water produced which is made up of 60 to 80% of the water injected.
  • powder polymers avoid injecting both hydrocarbons and surface active agents to be treated in the water produced.
  • the problem to be solved is then how to dissolve substantial quantities of polymers in short periods of time, i.e. 0.5 to 5 tonnes of polymers in 4 to 10 hours with quick start up (10 to 30 minutes).
  • the concentration of mother solution reach a maximum of 5 g/litre. Furthermore, it is not possible to design operations requiring for discontinuous dispersions which would involve volumes of several hundreds of m to be stored with operation times of 3 to 4 hours.
  • the Applicant has engineered a compact and transportable installation, quick to start up and independent, allowing to dissolve at high concentration, in very short periods of time, substantial quantities of polyacrylamide powder and designed to be used in fracturing operations on gas or oil fields whereby the installation successively includes: a polymer storage area a vertical polymer transfer hopper - a supply overflow pipe feeding a polymer dosing system fed by the above pipe a polymer dispersion device including:
  • a dispersed polymer slicing and discharge chamber including:
  • Such an installation is sufficiently compact to fit in a container, on the platform of a truck.
  • the quantity of polymer to be dissolved would vary according to the capacity of the well to be fractured.
  • the bags of powder are stored at the rear of the platform. In practice, this relates to bags of 25 kg for low capacities or 750 kg for higher capacities.
  • the installation is, in this case, equiped with a bag hoisting system and a hopper and an additional horizontal transfer screw, preceding the vertical hopper and into which the contents of the bags is poured.
  • the dosing system is a screw feeder allowing a flow rate in practice of 100 or 300 kg/h according to the equipment used.
  • the installation In order to convey the polymer from the hopper into the doser, the installation is equipped with an overflow pipe of a diameter of 100 to 200 mm according to the equipment used.
  • a dispersion device similar to the one used in the invention has been described by the Applicant in document WO 2008/107492 incorporated by reference, for Enhanced Oil Recovery (EOR) or flocculation applications.
  • PSU Polymer Slicing Unit
  • the polyacrylamide has a molecular weight of at least 10 million, preferably more than 15 million.
  • the polymer in suspension obtained at the outlet of the dispersion device (PSU) is then stored in a vertical tank, also used for degassing, and with an effective volume of between 1 and 5 m 3 according to the volume to be injected.
  • the tank is in general fitted with a low level gauge and a high level gauge to prevent unwanted tripping or stopping of the PSU according to the demand.
  • the storage time of the polymer suspension in the tank is between 10 and 20 minutes, advantageously approximately 15 minutes.
  • the invention also relates to a hydraulic gas or oil well fracturing process by injection of fracturing made of fracturing water/polyacrylamide in solution, implementing the installation described above and providing a significant drag reduction effect.
  • the injection of the fracturing water/polymer mix in solution into the rock is performed at pressure between 50 and 600 bars, advantageously approximately 400 bars.
  • Figure 1 is a schematic representation of the dispersion installation of the invention according to the embodiment described above for bags of 750 kg with a PSU 300.
  • Figure 2 is a schematic representation of the dispersion installation of the invention according to the embodiment described above for bags of 25kg with a PSU 100.
  • a fracturing operation is to be performed in the following conditions: instant flow rate: 15 m 3 /min, (900 m 3 /h) - diameter of pipe: 6 inches - injection speed: 13.7 m/sec, number of successive injections: 5 polymer concentration: 300 ppm, total fracturing time: 13 hours.
  • FIG. 1 The construction chosen is made up according to figures Ia and Ib of: a rail with (1) with a hoist to unload big bags of 750 kg (4 big bags for one operation) a hopper (2) under the big bag with a horizontal screw, 0 150, pitch 150 mm, at a speed of 100 rpm a vertical hopper (3) with a screw 0 200, pitch 200 mm, speed: 80 rpm to bring the powder fed by the previous screw into the hopper - an overflow pipe of 0 150 (4) supplying a screw feeder with a flow rate of
  • the total injection pressure is of
  • a PSU 100 type dispersion device can be used allowing for a flow rate of a solution at 20 g/litre of 5m 3 /h and a powder flow rate of 100 Kg/h.
  • the quantity of polymer to be stored will be 1,000 kg, brought in bags of 25 kg.
  • the installation would include: a mixer hopper (1) with central vertical screw of 2m 3 .
  • the bags are emptied into a cone at the base of the hopper and the product is introduced into the hopper by the vertical screw an overflow pipe (2) of 0 100 supplying a screw feeder at a maximum flow rate of 100 kg/h a PSU 100 (3) to put 100 kg of polymer per hour into suspension in a volume of water of 5 m 3 giving a concentration of 20 g/litre.
  • This dispersion device is equiped with cutting blades spaced 500 microns apart, at a speed of 4,500 rpm
  • a degassing tank with effective volume of 1.25 m 3 (4) with a holding time of 15 minutes providing start up in a very short time of less than 15 minutes.
  • This tank is equipped with a low and high level gauge to start up or stop the dispersion device according to the demand a Moineau pump (5) with a flow rate of 5 m 3 /h with variable speed control enabling injection of the solution at the suction of the Triplex fracturing pump.
  • the injection is performed via a 4-inch pipe with a flow rate of 200m /h and a concentration of 500 ppm.
  • Two wells are treated on the same site : one with an emulsion of 70-30 acrylamide/acrylic acid molar mass, of molecular weight of 18 million , at a concentration of 30% active matter, the other with a powder of the same specifications but with a 10% moisture content.
  • the pressure at the well bottom is 95 bars.
  • the injection pressures to obtain a flow rate of 200m 2 /h are 190 bars for the emulsion and 185 bars for the powder.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mining & Mineral Resources (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Fluid Mechanics (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

Compact and transportable installation, quick to start up and independent, allowing to dissolve at high concentration, in very short periods of time, substantial quantities of polyacrylamide powder and designed to be used in fracturing operations on gas or oil fields whereby the installation successively includes: - a polymer storage area - a vertical polymer transfer hopper - a supply overflow pipe feeding - a polymer dosing system fed by the above pipe - a PSU type polymer dispersion device - a tank for storage and degassing of the polymer in solution - a volumetric pump to inject and dose the solution of polymer obtained at the suction of the high pressure pump enabling the fracturing work.

Description

EQUIPMENT FOR QUICK DISPERSION OF POLYACRYLAMIDE POWDER FOR FRACTURING OPERATIONS
Gas production from clayey shale reservoirs (schist) which has been a growing method for several years requires fracturing of the reservoirs to ensure cost-effective gas production.
The reserves in this sector are huge and over extremely large areas formerly not recoverable such as coal streaks, fine sand or schist. In the USA, these unconventional resources increased from 28% in 1998 to 46% of the total natural gas produced in the
USA. The main huge basins are known as Barnett Shale, Fayette Ville Shale, Mowry
Shale, Marcellus Shale, etc.
The production techniques have often evolved from vertical wells to horizontal wells, reducing the number of production wells. However, in all cases, the permeability is insufficient to naturally produce a quantity of gas making the operations cost-effective.
The permeability and production areas therefore need to be increased by way of stimulation operations and fracturing in particular.
Hydraulic fracturing
Hydraulic fracturing is designed to create an additional level of permeability and an increased gas production surface areas. Indeed, low permeability, natural barriers of compact layers, impermeability due to drilling operations greatly limit production. These fracturing operations started in 1960 in the Appalachian Mountains and today over one million operations have taken place in the USA.
Engineering, design and implementation technologies have become increasingly sophisticated and require equipment enabling to perform these operations in shorter times with detailled analysis of the results. Specific simulators are capable of forecasting very accurate results.
Fracturing operation
These operations involve injecting high pressure water at a very high flow rate to create fractures within the production wells.
When the fractures are open, sand or beads of a particular size are injected to prevent these fractures from closing and to maintain the production surface areas thus created. The injection water usually contains a significant amount of additives, each with a defined function. Generally speaking, the injected composition includes: clay swelling inhibitors such as potassium chloride biocides to prevent bacteria, particularly sulphate-reducing bacteria, from developing and capable of forming viscous masses reducing the injection areas.
Aldehydes are the most commonly used biocides as glutaraldehyde, acrolein, etc... oxygen scavengers such as ammonium bisulphite to prevent the destruction of other components due to oxidation and corrosion of the injection lines, - corrosion inhibitors to protect the lines from oxidation by residual quantities of oxygen. Preference is given to N, n dimethylformamide, lubricants such as petroleum distillates, - gelling agents such as guar gum and hydroxyethyl cellulose, iron-chelating agents such as citric acid, EDTA, phosphonates, - scale control products such as phosphates, phosphonates or ethylene glycol, friction reducers to reduce the pressure drop in turbulent media and significantly increase the flow rate for the same power and pipe diameter.
Acid treatment is often performed before or during injection to treat cementation residue or to dissolve part of the rock in place in order to provide better access to the field. The sand injected is of a particular size, usually between 40 and 100 mesh.
Friction reducer
The drag reduction (friction reduction) phenomenon in turbulent flow was discovered by B. A Toms in 1946 ("Toms effect") even though previous descriptions ascertained that certain additives seemed to enhance high speed flows.
These products are therefore used to reduce pressure drop in line. When the medium is made up of hydrocarbons, oil- soluble polymers are used, particularly polymethyl methacrylate or carbohydrate polymers.
When the medium is water, very high molecular weight polymers such as polyacrylamides and ethylene oxide polymers are used. Preference is generally given to polyacrylamides for cost and sourcing reasons. Polyacrylamides
Initially developed for flocculation applications (water treatment, mineral treatment, paper mills, etc), polyacrylamides are increasingly used in other applications, and especially where their thickening effect on water based system is desired.
This development is of particular interest for Enhanced Oil Recovery, Cosmetics and Thickeners for textile printing, etc.
In the description hereinafter and the subsequent claims, the generic term of polyacrylamides covers acrylamide homopolyers as well as all the copolymers containing both acrylamide and other monomers such as: acids such as (metha)acrylic acid, AMPS (2-Acrylamido-2-methylpropane sulfonic acid), etc cationic monomers such as the ammonium salts of trimethylethyl methacrylate, diallyl dimethyl ammonium chloride, etc
These polymers can be modified by: branching with branching agents in sufficiently low quantities to maintain the solubility - Hydrophobic monomers giving associative polymers
Monomers with both anionic and cationic charges (zwitteronic monomers) Associations of anionic and cationic monomers (amphoteric), etc Monomers giving comb polymers.
The Person skilled in the art is well aware of these sets of products described in numerous patents.
For friction reduction, the polymers used must have the highest molecular weight possible while keeping very good solubility.
The polymer of choice is an acrylamide sodium acrylate copolymer (70% 30% molar ratio) with a molecular weight close to 20 million.
For their ease of handling, reverse emulsions (W/O) of these polymers are used with a concentration of active matter between 20 and 50%. These emulsions are stable in storage for about 6 months and dissolve very quickly (few minutes) in water under stirring. They allow a in line injection in the fracturing water before the high pressure pump and are practically fully dissolved in a few minutes both immediately and in the injection line.
The quantities of polymers injected can be between 250 and 2,000 ppm of active matter and the fracturing time between 2 and 15 hours with several stages of injections (2 to 20). The use of emulsions is today generalised over the entire territory of USA-Canada- Mexico and is spreading into other countries according to new reserves to be exploited.
Powder polyacrylamides
Environmental pressure has become increasingly strong both in terms of the water used for this operation and the water produced.
The constant demand is to only consume the water from the field and to treat the water produced which is made up of 60 to 80% of the water injected.
The use of powder polymers avoid injecting both hydrocarbons and surface active agents to be treated in the water produced.
The problem to be solved is then how to dissolve substantial quantities of polymers in short periods of time, i.e. 0.5 to 5 tonnes of polymers in 4 to 10 hours with quick start up (10 to 30 minutes).
Using standard dispersion equipment with dispersion with an ejector, a wetting shovel or a spray of water around a pneumatic transport system, the concentration of mother solution reach a maximum of 5 g/litre. Furthermore, it is not possible to design operations requiring for discontinuous dispersions which would involve volumes of several hundreds of m to be stored with operation times of 3 to 4 hours.
It was therefore necessary to find way allowing very quick in line dispersion of substantial quantities of polymer at a very high concentration while reducing as much as possible the size of the equipment which must be transportable, i.e. small enough to fit on the platform of a truck.
To do this, the Applicant has engineered a compact and transportable installation, quick to start up and independent, allowing to dissolve at high concentration, in very short periods of time, substantial quantities of polyacrylamide powder and designed to be used in fracturing operations on gas or oil fields whereby the installation successively includes: a polymer storage area a vertical polymer transfer hopper - a supply overflow pipe feeding a polymer dosing system fed by the above pipe a polymer dispersion device including:
• a polymer wetting cone connected to a primary water inlet circuit
• at the lower end of the cone: • a dispersed polymer slicing and discharge chamber including:
- a rotor driven by a motor and equiped with blades
- a fixed stator made up of evenly spaced plates
• over all or part of the periphery of the chamber, is a ring supplied by a secondary water circuit, the ring communicating with the chamber so as to ensure the spray of pressurised water over the plates of the stator thereby allowing for the release of the sliced and swollen polymer at the surface of the said plates
- a tank for storage and degassing of the polymer in solution
- a volumetric pump to inject and dose the solution of polymer obtained at the suction of the high pressure pump enabling the fracturing work.
Such an installation is sufficiently compact to fit in a container, on the platform of a truck.
Obviously, the quantity of polymer to be dissolved would vary according to the capacity of the well to be fractured. The bags of powder are stored at the rear of the platform. In practice, this relates to bags of 25 kg for low capacities or 750 kg for higher capacities.
When the powder is stored in bags of 750 kg, the installation is, in this case, equiped with a bag hoisting system and a hopper and an additional horizontal transfer screw, preceding the vertical hopper and into which the contents of the bags is poured. According to the invention, the dosing system is a screw feeder allowing a flow rate in practice of 100 or 300 kg/h according to the equipment used.
In order to convey the polymer from the hopper into the doser, the installation is equipped with an overflow pipe of a diameter of 100 to 200 mm according to the equipment used. A dispersion device similar to the one used in the invention has been described by the Applicant in document WO 2008/107492 incorporated by reference, for Enhanced Oil Recovery (EOR) or flocculation applications.
The Applicant observed that throught few modifications, along with the above- mentioned information, this device called PSU (Polymer Slicing Unit) could be adapted to fracturing.
It is therefore practically possible to use powder polyacrylamides of different particle sizes for fracturing operations.
The polyacrylamide has a molecular weight of at least 10 million, preferably more than 15 million.
The specifications of the PSUs which can be used for this invention are summarized in the following table:
Figure imgf000007_0001
Table 1 The polymer in suspension obtained at the outlet of the dispersion device (PSU) is then stored in a vertical tank, also used for degassing, and with an effective volume of between 1 and 5 m3 according to the volume to be injected. The tank is in general fitted with a low level gauge and a high level gauge to prevent unwanted tripping or stopping of the PSU according to the demand.
The storage time of the polymer suspension in the tank is between 10 and 20 minutes, advantageously approximately 15 minutes.
The invention also relates to a hydraulic gas or oil well fracturing process by injection of fracturing made of fracturing water/polyacrylamide in solution, implementing the installation described above and providing a significant drag reduction effect.
The injection of the fracturing water/polymer mix in solution into the rock is performed at pressure between 50 and 600 bars, advantageously approximately 400 bars.
The invention shall be made apparent from the following examples of embodiments supported by the appended figures.
Figure 1 is a schematic representation of the dispersion installation of the invention according to the embodiment described above for bags of 750 kg with a PSU 300. Figure 2 is a schematic representation of the dispersion installation of the invention according to the embodiment described above for bags of 25kg with a PSU 100.
Example 1
A fracturing operation is to be performed in the following conditions: instant flow rate: 15 m3/min, (900 m3/h) - diameter of pipe: 6 inches - injection speed: 13.7 m/sec, number of successive injections: 5 polymer concentration: 300 ppm, total fracturing time: 13 hours.
270 Kg/ hour of polyacrylamide must therefore be injected over a total time excluding stops between phases of approximately 10 hours i.e. approximately 3 tonnes of powder. The equipment must be as compact as possible to fit on the platform of a truck of 12m x
2m30 H= 3m.
The construction chosen is made up according to figures Ia and Ib of: a rail with (1) with a hoist to unload big bags of 750 kg (4 big bags for one operation) a hopper (2) under the big bag with a horizontal screw, 0 150, pitch 150 mm, at a speed of 100 rpm a vertical hopper (3) with a screw 0 200, pitch 200 mm, speed: 80 rpm to bring the powder fed by the previous screw into the hopper - an overflow pipe of 0 150 (4) supplying a screw feeder with a flow rate of
300 kg/h
- a PSU 300 (5) as described in document WO 2008/107492, supplied at the top point at a flow rate of 5m3/h and at the lower point at 10m3/h. In order to increase the dispersion speed, the space between the cutting blades is reduced to 500 microns and the rotor speed is increased to 4,500 rpm the suspension obtained in the dispersion device is sent into a vertical tank (6) used for degassing giving a holding time of 15 minutes, i.e. effective volume of 4 m3 and total volume of 5 m3 equipped with a high level gauge and a low level gauge stopping and starting the dispersion device according to the product demand. This storage time allows for the installation to be started up in less than
20 minutes a Moineau pump (7) with a flow rate of 15 m /h equipped with a variable speed control allowing for variation of this flow rate and controlled by the central control department which determines the quantity used according to the head loss found this Moineau pump is connected to the suction of the main injection pump of the fracturing system.
By varying the flow rate of the volumetric pump injecting the polymer solution, one finds that the same result on the improvement of the injection of pressure is obtained as with an emulsion.
That is, in this case, with a field pressure of 110 bars, the total injection pressure is of
265 bars in both cases. Without the polymer the pressure would be approximately 420 bars. Example 2
For small capacity operations, a PSU 100 type dispersion device can be used allowing for a flow rate of a solution at 20 g/litre of 5m3/h and a powder flow rate of 100 Kg/h.
For operations over 10 hours, the quantity of polymer to be stored will be 1,000 kg, brought in bags of 25 kg.
The installation would include: a mixer hopper (1) with central vertical screw of 2m3. The bags are emptied into a cone at the base of the hopper and the product is introduced into the hopper by the vertical screw an overflow pipe (2) of 0 100 supplying a screw feeder at a maximum flow rate of 100 kg/h a PSU 100 (3) to put 100 kg of polymer per hour into suspension in a volume of water of 5 m3 giving a concentration of 20 g/litre. This dispersion device is equiped with cutting blades spaced 500 microns apart, at a speed of 4,500 rpm A degassing tank with effective volume of 1.25 m3 (4) with a holding time of 15 minutes providing start up in a very short time of less than 15 minutes. This tank is equipped with a low and high level gauge to start up or stop the dispersion device according to the demand a Moineau pump (5) with a flow rate of 5 m3/h with variable speed control enabling injection of the solution at the suction of the Triplex fracturing pump.
The injection is performed via a 4-inch pipe with a flow rate of 200m /h and a concentration of 500 ppm.
Two wells are treated on the same site : one with an emulsion of 70-30 acrylamide/acrylic acid molar mass, of molecular weight of 18 million , at a concentration of 30% active matter, the other with a powder of the same specifications but with a 10% moisture content. The pressure at the well bottom is 95 bars. With 500 ppm of active matter, it is observed that the injection pressures to obtain a flow rate of 200m2/h are 190 bars for the emulsion and 185 bars for the powder.

Claims

1/ Compact and transportable installation, quick to start up and independent, allowing to dissolve at high concentration, in very short periods of time, substantial quantities of polyacrylamide powder and designed to be used in fracturing operations on gas or oil fields whereby the installation successively includes: a polymer storage area a vertical polymer transfer hopper
- a supply overflow pipe feeding - a polymer dosing system fed by the above pipe a PSU type polymer dispersion device
- a tank for storage and degassing of the polymer in solution
- a volumetric pump to inject and dose the solution of polymer obtained at the suction of the high pressure pump enabling the fracturing work.
2/ Installation according to claim 1 wherein the polymer batching device is a screw batcher with a flow rate of 100 kg/h .
3/ Installation according to claim 1 wherein the polymer batching device is a screw batcher with a flow rate of 300 kg/h .
4/ Hydraulic gas or oil well fracturing process by injection of a mixture of fracturing water/polyacrylamide in solution, implementing the installation of one of the claims 1 to 3.
5/ Process according to claim 4 wherein the polyacrylamide as a molecular weight of at least 10 million, preferably more than 15 million.
6/ Process according to claim 4 wherein the polymer dispersion is done at a concentration of at least 10 g/1, in less than 10 minutes with a polyacrylamide flow rate of 100 kg/h.
11 Process according to claim 4 wherein the polymer dispersion is done at a concentration of at least 10 g/1, in less than 10 minutes with a polyacrylamide flow rate of 300 kg/h.
8/ Process according to claim 1 wherein the storage time of the polymer is between 10 and 20 minutes, advantageously approximately 15 minutes, 9/ Process according to claim 4 wherein the injection of the fracturing water/polyacrylamide in solution mix is performed at a pressure between 50 and 600 bars, advantageously 400 bars.
PCT/EP2009/063961 2009-10-19 2009-10-23 Equipment for quick dispersion of polyacrylamide powder for fracturing operations WO2010020698A2 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP09748740.9A EP2513411B1 (en) 2009-10-19 2009-10-23 Equipment for quick dispersion of polyacrylamide powder for fracturing operations
BR112012007702-3A BR112012007702B1 (en) 2009-10-19 2009-10-23 FAST POLYCRYLAMIDE DISPOSAL EQUIPMENT AND WELL FRACTING PROCESS
DK09748740.9T DK2513411T3 (en) 2009-10-19 2009-10-23 APPLICATION FOR FAST DISPERSING POLYACRYLAMIDE POWDER FOR FRACTURING PROCESSES
AU2009284121A AU2009284121B2 (en) 2009-10-19 2009-10-23 Equipment for quick dispersion of polyacrylamide powder for fracturing operations
CN200980161957.1A CN102713131B (en) 2009-10-19 2009-10-23 Equipment for quick dispersion of polyacrylamide powder for fracturing operations
CA2775168A CA2775168C (en) 2009-10-19 2009-10-23 Equipment for quick dispersion of polyacrylamide powder for fracturing operations
IN2473DEN2012 IN2012DN02473A (en) 2009-10-19 2012-03-21
US13/446,846 US8800659B2 (en) 2009-10-19 2012-04-13 Equipment for quick dispersion of polyacrylamide powder for fracturing operations

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0957308 2009-10-19
FR0957308A FR2951493B1 (en) 2009-10-19 2009-10-19 RAPID DISSOLUTION MATERIALS FOR POWDERED POLYACRYLAMIDES FOR FRACTURING OPERATIONS

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/446,846 Continuation US8800659B2 (en) 2009-10-19 2012-04-13 Equipment for quick dispersion of polyacrylamide powder for fracturing operations

Publications (2)

Publication Number Publication Date
WO2010020698A2 true WO2010020698A2 (en) 2010-02-25
WO2010020698A3 WO2010020698A3 (en) 2010-06-24

Family

ID=41707506

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/063961 WO2010020698A2 (en) 2009-10-19 2009-10-23 Equipment for quick dispersion of polyacrylamide powder for fracturing operations

Country Status (11)

Country Link
US (1) US8800659B2 (en)
EP (1) EP2513411B1 (en)
CN (1) CN102713131B (en)
AU (1) AU2009284121B2 (en)
BR (1) BR112012007702B1 (en)
CA (1) CA2775168C (en)
DK (1) DK2513411T3 (en)
FR (1) FR2951493B1 (en)
IN (1) IN2012DN02473A (en)
PL (1) PL2513411T3 (en)
WO (1) WO2010020698A2 (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013150203A1 (en) 2012-04-03 2013-10-10 S.P.C.M. Sa New aqueous fracturing fluid composition and fracturing method implementing the fluid
EP2660420A1 (en) 2012-05-04 2013-11-06 S.P.C.M. Sa Improved equipment adapted for dissolution of polymer in fracturing operations
FR2994706A1 (en) * 2012-08-27 2014-02-28 Spcm Sa ADDITIVE PREPARATION CENTER FOR HYDRAULIC FRACTURING OPERATIONS AND HYDRAULIC FRACTURING METHOD USING THE PREPARATION CENTER
US9452395B2 (en) 2010-02-16 2016-09-27 S.P.C.M. Sa Water-soluble polymer dispersion appliance
EP3141692A1 (en) 2015-09-11 2017-03-15 S.P.C.M. Sa Equipment and method allowing the direct use of powdered polymer in hydraulic fracturing
WO2020079148A1 (en) 2018-10-18 2020-04-23 Basf Se Process of fracturing subterranean formations
WO2020079149A1 (en) 2018-10-18 2020-04-23 Basf Se Method of providing homogeneous aqueous polyacrylamide concentrates and use thereof
WO2021209148A1 (en) 2020-04-17 2021-10-21 Basf Se Process for making an aqueous injection fluid
WO2021209150A1 (en) 2020-04-17 2021-10-21 Basf Se Processes and devices for making aqueous wellbore treating fluids
WO2021209149A1 (en) 2020-04-17 2021-10-21 Basf Se Process and devices for making aqueous wellbore treating fluids
US11560510B2 (en) 2020-04-30 2023-01-24 Spcm Sa Aqueous fracturing fluid composition and fracturing process using the composition
WO2023156293A1 (en) 2022-02-17 2023-08-24 Basf Se Improved process and device for making aqueous wellbore treating fluids
US11850560B2 (en) 2020-03-04 2023-12-26 Zl Eor Chemicals Ltd. Polymer dispersion system for use in a hydraulic fracturing operation

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107398093B (en) * 2012-06-21 2021-07-13 桑科能源股份有限公司 Dispersion and conditioning technology for thick fine tailings dewatering operation
US10464071B2 (en) 2013-09-18 2019-11-05 Schlumberger Technology Corporation System and method for preparing a treatment fluid
US9593565B2 (en) * 2013-09-18 2017-03-14 Schlumberger Technology Corporation Wellsite handling system for packaged wellsite materials and method of using same
CN103821493B (en) * 2014-01-08 2016-08-17 李磊 The continuous mixture of acidizing and fracturing fluid is for delivery method
US9498662B2 (en) * 2014-02-18 2016-11-22 Leonard E. Doten Polymer gel emulsion injection system
US9982523B2 (en) 2014-08-26 2018-05-29 Gas Technology Institute Hydraulic fracturing system and method
US9581004B2 (en) * 2014-08-26 2017-02-28 Gas Technology Insitute Hydraulic fracturing system and method
SG11201703172XA (en) 2014-10-31 2017-05-30 Chevron Usa Inc Polymer compositions
US9902894B2 (en) 2014-10-31 2018-02-27 Chevron U.S.A. Inc. Polymer compositions
CN104389576B (en) * 2014-11-11 2017-10-03 山东索普威石油技术有限责任公司 A kind of field apparatus and its method of work that fracturing process is laid for proppant earthworm cellular type
FR3033642B1 (en) * 2015-03-11 2018-07-27 S.P.C.M. Sa DEVICE FOR ON-LINE CONTROL OF THE QUALITY OF A SOLUBLE POLYMER SOLUTION MADE FROM REVERSE EMULSION OR POWDER OF SUCH POLYMER
CN105275440B (en) * 2015-11-02 2018-03-20 中庆能源工程技术有限公司 Slug combination thing is used in a kind of oil field profile control transfer drive plugging system, method and closure
US11773315B2 (en) 2016-03-01 2023-10-03 Schlumberger Technology Corporation Well treatment methods
EP3445723A1 (en) 2016-04-21 2019-02-27 Basf Se Amphoteric polymer, process for production thereof, and use thereof, to treat aqueous dispersions
CA3117346A1 (en) 2018-10-31 2020-05-07 Basf Se Enhanced dewatering of mining tailings employing chemical pre-treatment
US10920535B1 (en) 2019-09-17 2021-02-16 Halliburton Energy Services, Inc. Injection method for high viscosity dry friction reducer to increase viscosity and pump efficiency

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0238723A2 (en) * 1986-03-26 1987-09-30 Diatec Polymers doing business as Diatec Environmental Method of rapidly dissolving polymer gels in water
EP0665050A1 (en) * 1993-01-05 1995-08-02 Halliburton Company Apparatus and method for gel production
WO2004007894A2 (en) * 2002-07-11 2004-01-22 Coody Richard L Apparatus and method for accelerating hydration of particulate polymer
US20040136262A1 (en) * 2001-05-14 2004-07-15 Wilson Stephen Wilfred Apparatus and method for wetting powder
US20040218463A1 (en) * 2003-04-30 2004-11-04 Allen Thomas E. Gel mixing system
US20040256106A1 (en) * 2003-06-19 2004-12-23 Phillippi Max L. Method and apparatus for hydrating a gel for use in a subterranean well field of the invention
US20060176771A1 (en) * 2005-02-04 2006-08-10 Spx Corporation Agitation system and method for dry solids addition to fluid
EP1743913A1 (en) * 2005-07-11 2007-01-17 PolymerLatex GmbH Continuous process and apparatus for preparing aqueous polymer dispersions
WO2008107492A1 (en) * 2007-10-12 2008-09-12 S.P.C.M. Sa Device for preparing a dispersion of water-soluble polymers in water, and method implementing the device

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7794135B2 (en) * 2004-11-05 2010-09-14 Schlumberger Technology Corporation Dry polymer hydration apparatus and methods of use

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0238723A2 (en) * 1986-03-26 1987-09-30 Diatec Polymers doing business as Diatec Environmental Method of rapidly dissolving polymer gels in water
EP0665050A1 (en) * 1993-01-05 1995-08-02 Halliburton Company Apparatus and method for gel production
US20040136262A1 (en) * 2001-05-14 2004-07-15 Wilson Stephen Wilfred Apparatus and method for wetting powder
WO2004007894A2 (en) * 2002-07-11 2004-01-22 Coody Richard L Apparatus and method for accelerating hydration of particulate polymer
US20040218463A1 (en) * 2003-04-30 2004-11-04 Allen Thomas E. Gel mixing system
US20040256106A1 (en) * 2003-06-19 2004-12-23 Phillippi Max L. Method and apparatus for hydrating a gel for use in a subterranean well field of the invention
US20060176771A1 (en) * 2005-02-04 2006-08-10 Spx Corporation Agitation system and method for dry solids addition to fluid
EP1743913A1 (en) * 2005-07-11 2007-01-17 PolymerLatex GmbH Continuous process and apparatus for preparing aqueous polymer dispersions
WO2008107492A1 (en) * 2007-10-12 2008-09-12 S.P.C.M. Sa Device for preparing a dispersion of water-soluble polymers in water, and method implementing the device

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9452395B2 (en) 2010-02-16 2016-09-27 S.P.C.M. Sa Water-soluble polymer dispersion appliance
WO2013150203A1 (en) 2012-04-03 2013-10-10 S.P.C.M. Sa New aqueous fracturing fluid composition and fracturing method implementing the fluid
US9067182B2 (en) 2012-05-04 2015-06-30 S.P.C.M. Sa Polymer dissolution equipment suitable for large fracturing operations
EP2660420A1 (en) 2012-05-04 2013-11-06 S.P.C.M. Sa Improved equipment adapted for dissolution of polymer in fracturing operations
EA025089B1 (en) * 2012-05-04 2016-11-30 С.П.С.М. Са Equipment for dissolution of polymers suitable for large-scale operations of hydraulic fracturing
CN103628852B (en) * 2012-08-27 2017-05-10 S.P.C.M.股份公司 Centre for the preparation of additives for hydraulic fracturing operations and hydraulic fracturing process employing the preparation centre
US9328599B2 (en) 2012-08-27 2016-05-03 S.P.C.M. Sa Centre for the preparation of additives for hydraulic fracturing operations and hydraulic fracturing process employing the preparation centre
CN103628852A (en) * 2012-08-27 2014-03-12 S.P.C.M.公司 Centre for the preparation of additives for hydraulic fracturing operations and hydraulic fracturing process employing the preparation centre
EP2703598A1 (en) * 2012-08-27 2014-03-05 S.P.C.M. Sa Centre for the preparation of additives for hydraulic fracturing operations and hydraulic fracturing process employing the preparation centre
FR2994706A1 (en) * 2012-08-27 2014-02-28 Spcm Sa ADDITIVE PREPARATION CENTER FOR HYDRAULIC FRACTURING OPERATIONS AND HYDRAULIC FRACTURING METHOD USING THE PREPARATION CENTER
EP3141692A1 (en) 2015-09-11 2017-03-15 S.P.C.M. Sa Equipment and method allowing the direct use of powdered polymer in hydraulic fracturing
US10253596B2 (en) 2015-09-11 2019-04-09 S.P.C.M. Sa Equipment and method enabling to directly use powder polymer in hydraulic fracturing
US11608468B2 (en) 2018-10-18 2023-03-21 Basf Se Process of fracturing subterranean formations
WO2020079149A1 (en) 2018-10-18 2020-04-23 Basf Se Method of providing homogeneous aqueous polyacrylamide concentrates and use thereof
WO2020079148A1 (en) 2018-10-18 2020-04-23 Basf Se Process of fracturing subterranean formations
US11725102B2 (en) 2018-10-18 2023-08-15 Basf Se Method of providing homogeneous aqueous polyacrylamide concentrates and use thereof
US11850560B2 (en) 2020-03-04 2023-12-26 Zl Eor Chemicals Ltd. Polymer dispersion system for use in a hydraulic fracturing operation
WO2021209148A1 (en) 2020-04-17 2021-10-21 Basf Se Process for making an aqueous injection fluid
WO2021209150A1 (en) 2020-04-17 2021-10-21 Basf Se Processes and devices for making aqueous wellbore treating fluids
WO2021209149A1 (en) 2020-04-17 2021-10-21 Basf Se Process and devices for making aqueous wellbore treating fluids
US11560510B2 (en) 2020-04-30 2023-01-24 Spcm Sa Aqueous fracturing fluid composition and fracturing process using the composition
WO2023156293A1 (en) 2022-02-17 2023-08-24 Basf Se Improved process and device for making aqueous wellbore treating fluids

Also Published As

Publication number Publication date
US8800659B2 (en) 2014-08-12
CA2775168A1 (en) 2010-02-25
CA2775168C (en) 2017-05-09
DK2513411T3 (en) 2017-09-04
AU2009284121A1 (en) 2012-04-12
FR2951493A1 (en) 2011-04-22
CN102713131A (en) 2012-10-03
US20120199356A1 (en) 2012-08-09
PL2513411T3 (en) 2017-08-31
FR2951493B1 (en) 2011-12-09
AU2009284121B2 (en) 2014-07-17
BR112012007702A2 (en) 2016-08-23
WO2010020698A3 (en) 2010-06-24
CN102713131B (en) 2015-07-22
IN2012DN02473A (en) 2015-08-21
BR112012007702B1 (en) 2019-02-19
EP2513411A2 (en) 2012-10-24
EP2513411B1 (en) 2017-05-10

Similar Documents

Publication Publication Date Title
CA2775168C (en) Equipment for quick dispersion of polyacrylamide powder for fracturing operations
CA2806404C (en) Improved polymer dissolution equipment suitable for large fracturing operations
EP2197974B1 (en) Installation for enhanced oil recovery using water-soluble polymers, method implementing same
CA2700244C (en) Installation for enhanced oil recovery using water-soluble polymers, method implementing same
CN103628852B (en) Centre for the preparation of additives for hydraulic fracturing operations and hydraulic fracturing process employing the preparation centre
CN106522910B (en) Apparatus and method capable of directly utilizing powdered polymer in hydraulic fracturing
AU2013280162B2 (en) Dispersion and conditioning techniques for thick fine tailings dewatering operations
US11725102B2 (en) Method of providing homogeneous aqueous polyacrylamide concentrates and use thereof
US10920535B1 (en) Injection method for high viscosity dry friction reducer to increase viscosity and pump efficiency

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980161957.1

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09748740

Country of ref document: EP

Kind code of ref document: A2

WWE Wipo information: entry into national phase

Ref document number: 2009284121

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 2473/DELNP/2012

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 2775168

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 2009284121

Country of ref document: AU

Date of ref document: 20091023

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2009748740

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2009748740

Country of ref document: EP

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112012007702

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112012007702

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20120403