WO2023242077A1 - Procédé de fabrication de polymères hydrosolubles destinés à être utilisés comme agents d'encapsulation de schiste pour fluides de forage - Google Patents

Procédé de fabrication de polymères hydrosolubles destinés à être utilisés comme agents d'encapsulation de schiste pour fluides de forage Download PDF

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WO2023242077A1
WO2023242077A1 PCT/EP2023/065571 EP2023065571W WO2023242077A1 WO 2023242077 A1 WO2023242077 A1 WO 2023242077A1 EP 2023065571 W EP2023065571 W EP 2023065571W WO 2023242077 A1 WO2023242077 A1 WO 2023242077A1
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monomers
monomer
water
vessel
mol
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Oscar Lafuente Cerda
Roland Reichenbach-Klinke
Markus WOHLFAHRT
Christian Scholz
Silke Flakus-Taube
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/10—Aqueous solvent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/04—Azo-compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • C08F4/34—Per-compounds with one peroxy-radical

Definitions

  • the present invention relates to a method for making water-soluble polymers in powder form, which comprise at least two different ethylenically unsaturated monomers, namely an ethyleni- cally unsaturated monomer comprising at least one OH-group or an oxyalkylene group, and another monomer, by dosing the monomers over an aqueous solution comprising at least one radical initiator and drying the obtained polymer.
  • the invention also relates to the use of these polymers in the field of oil drilling, in particular as shale encapsulators and/or shale inhibitors.
  • Incorporating hydroxyl functions in a water-soluble polymer contributes interesting properties for certain industrial sectors.
  • examples include cation precipitation prevention agents, in particular in saline waters used in gas and oil extraction operations, surface agents on paper coatings or clay, and shale inhibitors or shale encapsulators in the oil drilling field.
  • the cuttings generated by drilling are transported by the drilling fluid to the surface where they are separated from the drilling fluid and the drilling fluid thereafter is re-injected into the wellbore.
  • the formations drilled through often comprise shale and clay.
  • Clay and shale react with the water phase of a drilling fluid to promote stickiness, increase swelling, and induce sloughing. It is therefore known in the art to add shale and clay stabilizers to the drilling fluid. Such stabilizers adhere to the cuttings and the wellbore wall.
  • This encapsulation can effectively seal their surfaces and inhibits their reaction with the drilling fluid, minimizing sticking, swelling, and sloughing, and increasing borehole stability.
  • hydroxyl functions pose many difficulties, particularly if one wishes to obtain high molecular weights.
  • the hydroxyl functions may generate transfer phenomena and therefore ultimately create cross-linking problems.
  • the carboxyl function present in the acrylic acid may lead to unwanted esterification reactions. This esterification, whether it occurs during or after polymerization, causes the formation of an insoluble product that is therefore unsuitable for its use.
  • Polymers in powder or bead form are increasingly sought out and desired on an industrial level, since they are easy to transport and have a very high concentration of active material. Furthermore, they have a much longer lifetime relative to polymers in liquid or emulsion form, and have the advantage of not needing to contain additional protective agents such as biocides.
  • Document JP-1981-161413 describes a synthesis method by inverse suspension of nonlinear polymers containing hydroxyalkyl monomers.
  • the cross-linking effect of the alcohol functions is exploited therein to thus obtain auto-cross-linking and therefore a water-swellable polymer.
  • US 2017/0204210 A1 discloses water-soluble polymers in bead or powder form which are obtained by inverse suspension or emulsion polymerization in the presence of a transfer agent. They may be used as shale inhibitors in course of drilling.
  • the polymers comprise at least two different ethylenically unsaturated monomers, namely an ethylenically unsaturated monomer comprising an OH-group, such as for example hydroxypropyl acrylate, and another monomer, in particular acrylic acid.
  • the amount of the OH-containing monomer is limited to less than 20 mol%.
  • water is evaporated, and polymer beads can be separated from the organic phase.
  • the document comprises a comparative example in which the synthesis was carried out by solution polymerization followed by drying the aqueous solution.
  • a mixture of acrylic acid, hydroxypropyl acrylate, water and NaOH was added into a reactor, thereafter initiators and a transfer agent were added and the mixture polymerized. Due to crosslinking, the obtained polymer powder contained more than 2 wt. % of insoluble amounts.
  • the inverse suspension and inverse emulsion polymerization require working with organic solvents. It is desirable to avoid working with organic solvents. Moreover, surfactants and emulsion stabilizers are needed for this process. These compounds are costly and can have negative impacts on the final application of the product.
  • the process described above involves many different steps. It starts with the generation of the emulsion, followed by the polymerization itself. Then the polymer beads need to be filtered off and dried from residual water and solvent. Finally, there is a distillation step to recycle the solvent. All these steps make the process lengthy, costly and also not very robust.
  • WO 2011/118728, CN 113 072 666, CN 111 072 666, JP H03 197519 A, US 2013/289171 and EP 0344589 disclose methods to prepare an aqueous solution of water-soluble polymers. However, the obtained water-soluble polymer is not dried to prepare the powder form. And none of these prior art documents disclose the use and the advantages of the water-soluble copolymers in powder form in the field of oil drilling, in particular as shale encapsulators and/or shale inhibitors.
  • the present invention relates to a method for preparing a water-soluble polymer in powder form by radically polymerizing at least two water-soluble, monoethylenically unsaturated monomers (A) and (B), wherein
  • At least two water-soluble, monoethylenically unsaturated monomers (A) and (B) are used, wherein
  • the R 2 group is a C1-C12 hydrocarbon group comprising at least an OH pendant group, preferably a Ci-Ce hydrocarbon group, and most preferably a C1-C4 hydrocarbon group.
  • at least one monomer (A) is selected from hydroxyalkyl (meth)acrylates, hydroxyalkyl (meth) acrylamide and amino alcohol (meth)acrylates, wherein the term “alkyl” is a linear alkyl group comprising 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, most preferably 1 to 4 carbon atoms.
  • At least one monomer (A) is a hydroxyalkyl (meth)acrylate selected from hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, for example 2,3-dihydroxypropyl methacrylate.
  • At least one monomer (A) is a hydroxyalkyl (meth) acrylamide selected from hydroxymethyl (meth)acrylamide, hydroxyethyl (meth)acrylamide, hydroxypropyl (meth)acrylamide, and hydroxybutyl (meth)acrylamide.
  • At least one monomer (A) is an amino alcohol (meth)acrylates, for example N-[tris(hydroxymethyl)aminomethane] (meth)acrylamide.
  • At least one monomer (A) is hydroxypropyl (meth)acrylate.
  • the water-soluble polymer comprises 0.1 to 30 mol % of at least one monomer (A), preferably 5 to 25 mol %, most preferably 15 to 25 mol %, relating to the total of all monomers.
  • At least one monomer (B) may be selected from:
  • an anionic monomer preferably chosen from among acrylic acid, methacrylic acid, itaconic acid, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid (ATBS), said monomers being in acid form, partially salified or totally salified;
  • a non-ionic monomer preferably chosen from among acrylamide, methacrylamide, N,N'- dimethlacrylamide, N-vinyl pyrrolidone, N-vinyl formamide, methacrylates, diacetoneacrylamide and N-isopropylacrylamide.
  • At least one of monomer (B) is a cationic monomer.
  • the cationic monomer amounts to less than 10 mol %, relating to the total of all monomers.
  • Suitable cationic monomers (B) are monomers comprising ammonium groups, in particular ammonium derivatives of N-(o-aminoalkyl) (meth)acrylamides or L-aminoalkyl (meth)acrylic esters.
  • the radicals R 9 are Ci-C4-alkyl, preferably methyl, or a group of the general formula -R 11 -SO 3 H, where R 11 is a preferably linear Ci- to C4-alkylene group or a phenylene group, with the proviso that generally not more than one of the substituents R 9 is a substituent having sulfonic acid groups.
  • the three substituents R 9 are particularly preferably methyl groups, i.e. the monomer has a group -N(CHs)3 + .
  • X' in the above formula is a monovalent anion, for example Cl'. X' can of course also be a corresponding fraction of a polyvalent anion, although this is not preferred.
  • Suitable cationic monomers (B) of the general formula (I) or (II) comprise salts of 3-trimethylammonium propylacrylamides or 2-trimethylammonium ethyl (meth)acrylates, for example the corresponding chlorides, such as 3-trimethylammonium propylacrylamide chloride (DIMAPAQUAT) and 2- trimethylammonium ethyl methacrylate chloride (MADAME-QUAT).
  • DIMAPAQUAT 3-trimethylammonium propylacrylamide chloride
  • MADAME-QUAT 2- trimethylammonium ethyl methacrylate chloride
  • monomer (B) is (meth)acrylic acid or a salt thereof.
  • the water-soluble polymer comprises 70 to 99.9 mol % of at least one monomer (B), preferably 75 to 95 mol %, most preferably 75 to 85 mol %, relating to the total of all monomers.
  • the water-soluble polymer comprises 75-85 mol% of (meth)acrylic acid or a salt thereof and 15-25 mol % of monomer (A) as previously defined.
  • the water-soluble polymer may also comprise further monomers, besides monomers (A) and (B).
  • the water-soluble polymer only contains monomers (A) and (B).
  • the water-soluble polymer prepared via the process of the present invention comprises the monomers indicated above in the amounts as also indicated above including preferred embodiments.
  • the weight average molecular weight (M w ) of the water-soluble polymer is selected by the skilled artisan according to its intended use. For many applications high molecular weights are desirable. In one embodiment, the molecular weight (M w ) of the water-soluble polymer is in the range of 500,000 to 1 ,500,000 g/mol, preferably 600,000 to 1 ,200,000 g/mol.
  • the water-soluble polymer obtained comprises less than 2 wt.% of insoluble amounts.
  • the molecular weight, the viscosity and the insoluble amounts of the polymer prepared are analyzed as will be described below.
  • the present invention relates to a method for preparing a water-soluble polymer in powder form by radically polymerizing at least two water-soluble, monoethylenically unsaturated monomers (A) and (B), wherein
  • the method for preparing the water-soluble polymer in powder form comprises at least steps i) to iv).
  • an aqueous base fluid is added into the reaction vessel.
  • the vessel is then heated before proceeding to step ii).
  • the vessel is heated to a temperature between 45 to 85 °C, preferably between 55 and 85 °C, more preferably between 55 and 70 °C.
  • aqueous base fluid is intended to cover any solution comprising water.
  • the aqueous base fluid may additionally comprise an organic solvent miscible with water.
  • the aqueous base fluid comprises at least 50 wt.% of water, preferably at least 80 wt.%, most preferably at least 95 wt.%, relating to the total of all components of the aqueous base fluid.
  • the aqueous base fluid is only water.
  • step ii) at least one radical initiator is added into the reaction vessel and the radical initiator(s) is dissolved in the aqueous base fluid.
  • the radical initiator(s) has a 10h /2 temperature in water of 20 to 70 °C, preferably 40 to 60 °C.
  • the radical initiator(s) is selected from 2,2'-[Azobis(1-methylethyliden)]bis[4,5-dihydro-1 H- imidazoldihydrochlorid (Wako VA-044, which has a 10h t1/2 temperature in water of 44°C;); 2,2'-Azobis[2-methylpropionamidin]dihydrochloride (WakoV50, which has a 10h t1/2 temperature in water 56°C) and sodium peroxodisulphate.
  • the radical initiator is 2,2'-[Azobis(1-methylethyliden)]bis[4,5-dihydro-1 H-imidazoldihydrochlorid (Wako VA- 044).
  • step iii) the monomers are continuously dosed into the reaction vessel.
  • the monomers in step iii) are dosed into the vessel via a dropping funnel, via a pump, such as a peristaltic pump, or via any other dosing means known to the skilled person.
  • the monomers are continuously dosed into the reaction vessel over the course of 15 to 120 min, preferably 30 to 90 min, and more preferably 45 to 75 min.
  • the dosage rate of the monomers may be controlled to not exceed the desired upper limit of the vessel temperature.
  • the monomers are dosed into the reaction vessel as a monomer mixture.
  • the monomers are dosed into the reaction vessel separately. When the monomers are added separately, they may be dosed at the same dosing rate or at different dosing rates.
  • up to 30 wt.% of the monomers used in the method are added into the reaction vessel before the radical initiator(s).
  • the vessel is cooled after the start of the reaction between the monomers and the radical initiator(s), in order to control the desired upper limit of the vessel temperature.
  • the cooling is carried out by using a cooling jacket or a recirculating cooler or adding cold water into the vessel, or any other cooling means known to the skilled person.
  • the salt when at least one of the monomers is a salt of (meth)acrylic acid, the salt may be pre-prepared and then added to the reaction vessel. Alternatively, the reactants may be added to the reaction vessel separately. In a preferred embodiment, when at least one of the monomers is sodium acrylate, the sodium acrylate may be pre-prepared and then added to the reaction vessel. Or alternatively, acrylic acid and NaOH may be added separately into the vessel.
  • the reaction vessel is stirred for 30 min to 3 h at a temperature between 45 to 85 °C after competition of the monomers dosage, preferably between 55 and 85 °C, more preferably between 55 and 70 °C.
  • an additional amount of radical initiator(s) is added into the vessel after completion of the monomers dosage.
  • the final polymer concentration in the reaction vessel, before step iv) is in the range from 18 to 35 wt.%, preferably from 18 to 30 wt.%
  • the temperature of the vessel is maintained equal or less than 100 °C by means of cooling, such as using a cooling jacket or a recirculating cooler or adding cold water into the vessel.
  • the maximum temperature of the vessel is equal or less than 90 °C at any point during the method, preferably equal or less than 85 °C.
  • the obtained water-soluble polymer is removed from the vessel and it is dried.
  • the polymer is dried using a drum dryer.
  • the polymer is dried by means of a drum dryer for 30 s to 5 min at a temperature of 110 to 180 °C.
  • the invention also relates to the use of water-soluble polymers, as described by a process as described above, in the field of oil drilling.
  • the invention related to the use of the water-soluble polymers as shale encapsulated and/or shale inhibitors in oil drilling operations.
  • the powder comprising the water-soluble polymers may be dissolved in an aqueous fluid to prepare the wellbore treatment fluid.
  • the aqueous base fluid may comprise freshwater or a brine, optionally selected from seawater, saturated NaCI, and KCI.
  • the aqueous base fluid is not a calcium brine having a calcium content above 500 mg/L.
  • the dilution rates may vary and should be based on the depletion rate of the shale encapsulator or the shale inhibitor.
  • the concentration of water-soluble polymers in the wellbore treatment fluid used in oil drilling operations may range between 1 .4 and 11.4 kg/m 3 .
  • the powder comprising the water-soluble polymers may be pre-dissolved to a concentration of 11 .4 to 14.2 kg/m 3 , before the final dilution into the wellbore treatment fluid.
  • the pH of the wellbore treatment fluid comprising the water-soluble polymers is kept below 10.
  • the invention related to the use of water-soluble polymers, as described by a process as described above, in the fields of gas recovery (or extraction), oil recovery (or extraction), paper manufacturing, water treatment, or agriculture.
  • gas recovery or extraction
  • oil recovery or extraction
  • paper manufacturing or water treatment
  • or agriculture or agriculture
  • the molecular weight distribution of the polymer samples was analyzed by gel permeation chromatography. A combination of three different columns was used (Shodex OHpak SB-G, Shodex SB-807HQ and Shodex SB-806HQ). The eluent was a mixture of 0.05 M ammonium formiate I methanol (80:20 Vol%) at a flow rate of 0.5 ml/min. Detection was performed by refractive index.
  • the amount of unpolymerized monomers was analyzed by HPLC.
  • a Nucleosil C18 column by Machery Nagel was used.
  • a mixture of methanol and 0.05 M aqueous KH2 O4 solution with pH of 3.5 was used as eluent.
  • aqueous solution comprising 5 wt.% of the polymer was prepared and the viscosity was determined by means of a Brookfield HV viscometer at 25°C and rotating speed of 20 rpm with spindle No. 1.
  • the content of insolubles in the polymer powders was measured according to the following procedure:
  • the polymer solution was filtered through a 200 pm stainless steel screen.
  • the insoluble content is rated as ⁇ 1 wt.%. If the screen is covered but the solution was filtered through the insoluble content is reported as ⁇ 2 wt.%. If the solution does not filter through the screen, the screen is dried and weighed. The insoluble content is calculated from the difference of the initial weight of the filter screen and the one after filtration and drying.
  • a commercially available copolymer made by the bead polymerization process was used.
  • the product has a viscosity of 140 mPas (measured in 5 wt.% aqueous solution by Brookfield HV viscometer at 25 °C and rotating speed of 20 rpm with spindle 1). Residual acrylic acid was determined by HPLC as 0.11 wt.% and residual HPA as 0.01 wt.%.
  • the molecular weight (M w ) was measured by GPC as 823,000 Da.
  • the insoluble content was determined as ⁇ 1 wt.%.
  • Comparative example 2 Solution polymerization Copolymer of sodium acrylate (79.5 mol %) and hydroxypropyl acrylate (20.5 mol %) by solution polymerization.
  • the temperature was increased to 75 °C and maintained at this temperature for 2 h.
  • the polymer solution was again analyzed for unreacted monomers by HPLC and molecular weight by gel permeation chromatography. A residual amount of 0.52 wt.% acrylic acid and 0 wt.% HPA was found.
  • the final polymer solution had an active content of 13.5 wt.% and a viscosity of 24 000 mPas at 20°C.
  • the resulting powder had a viscosity of 4050 mPas (measured in 5 wt.% aqueous solution by Brookfield HV viscometer at 25°C and rotating speed of 20 rpm with spindle 1).
  • the molecular weight (M w ) was measured by GPC as 1 ,900,000 Da.
  • M w molecular weight
  • Copolymer of sodium acrylate (79.5 mol %) and hydroxypropyl acrylate (20.5 mol %) made by the process according to the present invention.
  • the final polymer solution had a viscosity of 31 000 mPas (20°C, Brookfield HV 20 rpm) and a solid content of 18.4 wt.%. pH was measured as 5.7.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • a lab drum dryer type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH
  • the resulting powder had a viscosity of 820 mPas (5 wt.% aqueous solution). Residual acrylic acid was determined by HPLC as 0.38 wt.% and residual HPA as 0 wt.%. The molecular weight (M w ) was measured by GPC as 1 ,191,000 Da. The insoluble content was determined as ⁇ 2 wt.%.
  • Copolymer of sodium acrylate (79.5 mol %) and hydroxypropyl acrylate (20.5 mol %) made by the process according to the present invention.
  • the final polymer solution had a viscosity of 15 000 mPas (20°C) and a solid content of 18.2 wt.%. pH was measured as 5.7.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • the viscosity of a 5 wt.% aqueous solution of the resulting powder was measured as 230 mPas.
  • Residual acrylic acid was determined by HPLC as 0.32 wt.% and residual HPA as 0 wt.%.
  • the molecular weight (M w ) was measured by GPC as 834,000 Da.
  • the insoluble content was determined as ⁇ 2 wt.%.
  • Copolymer of sodium acrylate (79.5 mol %) and hydroxypropyl acrylate (20.5 mol %) made by the process according to the present invention.
  • the monomer solution as described above was added via the dropping funnel within 90 min, maintaining a temperature rise to maximum 65°C.
  • the reaction mixture was stirrer at 60°C for further 60 min.
  • the final polymer solution had a viscosity of 9 000 mPas (50°C) and a solid content of 22.8 wt.%. pH was measured as 6.1.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • the viscosity of a 5 wt.% aqueous solution of the resulting powder was measured as 300 mPas.
  • Residual acrylic acid was determined by HPLC as 0.12 wt.% and residual HPA as 0.01 wt.%.
  • the molecular weight (M w ) was measured by GPC as 701 ,000 Da.
  • the insoluble content was determined as ⁇ 2 wt.%.
  • Copolymer of sodium acrylate (85 mol %) and hydroxypropyl acrylate (15 mol %) made by the process according to the present invention.
  • the final polymer solution had a viscosity of 114 000 mPas (20°C) and a solid content of 23.0 wt.%. pH was measured as 4.9.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • the viscosity of a 5 wt.% aqueous solution of the resulting powder was measured as 600 mPas.
  • Residual acrylic acid was determined by HPLC as 0.12 wt.% and residual HPA as 0.01 wt.%.
  • the molecular weight (M w ) was measured by GPC as 1 ,116,000 Da.
  • the insoluble content was determined as ⁇ 1 wt.%.
  • Copolymer of sodium acrylate (75 mol %) and hydroxypropyl acrylate (25 mol %) made by the process according to the present invention.
  • the final polymer solution had a viscosity of 152 000 mPas (20°C) and a solid content of 24.1 wt.%. pH was measured as 4.9.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • the viscosity of a 5 wt.% aqueous solution of the resulting powder was measured as 600 mPas. Residual acrylic acid was determined by HPLC as 0.1 wt.% and residual HPA as 0.01 wt.%.
  • the molecular weight (M w ) was measured by GPC as 1 ,097,000 Da.
  • the insoluble content was determined as ⁇ 2 wt.%.
  • Copolymer of sodium acrylate (79.5 mol %) and hydroxypropyl acrylate (20.5 mol %) made by the process according to the present invention.
  • the synthesis route was modified in this example. Instead of preparing a combined monomer solution, acrylic acid, HPA, and a NaOH solution were charged separately into the reactor. A minor amount of sodium acrylate and HPA was already initially present in the reactor (30 wt.% relating to the total of monomers). 4400 g water were placed in a 10 L reaction vessel fitted with a cooling jacket, stainless steel stirrer, pH control and thermometer. The stirrer was started and 340 g 50 wt.% aq. NaOH, 324 g acrylic acid and 152 g HPA were charged into the reactor. Under nitrogen purging and further stirring the liquid was heated to 54 °C.
  • the final polymer solution had a viscosity of 30 000 mPas (20°C) and a solid content of 22 wt.%. pH was measured as 4.5.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • the viscosity of a 5 wt.% aqueous solution of the resulting powder was measured as 300 mPas.
  • Residual acrylic acid was determined by HPLC as 0.08 wt.% and residual HPA as 0 wt.%.
  • the molecular weight (M w ) was measured by GPC as 944,000 Da.
  • the insoluble content was determined as ⁇ 2 wt.%.
  • the product was not dried but the copolymer as such used for the tests.
  • the addition of NaOH was adjusted to keep the pH between 5 - 5.5.
  • the dosage of the monomers was finished after 80 min.
  • the final polymer solution had a viscosity of 124 000 mPas (20°C) and a solid content of 24.4 wt.%. pH was measured as 5.5.
  • the viscosity of a 5 wt.% aqueous solution was measured as 320 mPas.
  • Residual acrylic acid was determined by HPLC as 0.13 wt.% and residual HPA as 0 wt.%.
  • the molecular weight (M w ) was measured by GPC as 1,200,000 Da.
  • Copolymer of sodium acrylate (79.5 mol %) and hydroxypropyl acrylate (20.5 mol %) made by the process according to the present invention.
  • the final polymer solution had a viscosity of 10 000 mPas (20°C) and a solid content of 25 wt.%. pH was measured as 5.2.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • the viscosity of a 5 wt.% aqueous solution of the resulting powder was measured as 90 mPas.
  • Residual acrylic acid was determined by HPLC as 0.08 wt.% and residual HPA as 0.007 wt.%.
  • the molecular weight (M w ) was measured by GPC as 663,000 Da.
  • the insoluble content was determined as ⁇ 1 wt.%.
  • Copolymer of sodium acrylate (79.5 mol %) and hydroxypropyl acrylate (20.5 mol %) made by the process according to the present invention.
  • the final polymer solution had a viscosity of 80 000 mPas (20°C) and a solid content of 25 wt.%. pH was measured as 4.6.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • the viscosity of a 5 wt.% aqueous solution of the resulting powder was measured as 350 mPas.
  • Residual acrylic acid was determined by HPLC as 0.12 wt.% and residual HPA as 0 wt.%.
  • the molecular weight (M w ) was measured by GPC as 1 ,141 ,000 Da.
  • the insoluble content was determined as ⁇ 1 wt.%.
  • Copolymer of sodium acrylate (79.5 mol %) and hydroxypropyl acrylate (20.5 mol %) made by the process according to the present invention.
  • the final polymer solution had a viscosity of 100 000 mPas (20°C) and a solid content of 24.5 wt.%. pH was measured as 4.2. The viscosity of a 5 wt.% aqueous solution was measured as 180 mPas. Residual acrylic acid was determined by HPLC as 0.21 wt.% and residual HPA as 0 wt.%. The molecular weight (M w ) was measured by GPC as 1 ,000,000 Da.
  • the final polymer solution had a viscosity of 82 000 mPas (20°C) and a solid content of 23.3 wt.%.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • the viscosity of a 5 wt.% aqueous solution of the resulting powder was measured as 990 mPas.
  • Residual acrylic acid was determined by HPLC as 0.08 wt.% and residual HPA as 0 wt.%.
  • the molecular weight (M w ) was measured by GPC as 1 ,218,000 Da.
  • the insoluble content was determined as ⁇ 1 wt.%.
  • Copolymer of sodium acrylate (79.5 mol %) and hydroxypropyl acrylate (20.5 mol %) made by the process according to the present invention.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • the viscosity of a 5 wt.% aqueous solution of the resulting powder was measured as 1500 mPas.
  • Residual acrylic acid was determined by HPLC as 0.08 wt.% and residual HPA as 0 wt.%.
  • the molecular weight (M w ) was measured by GPC as 1,176,000 Da.
  • Copolymer of sodium acrylate (79.5 mol %) and hydroxypropyl acrylate (20.5 mol %) made by the process according to the present invention.
  • the final polymer solution had a viscosity of 44 000 mPas (20°C) and a solid content of 23.1 wt.%. pH was measured as 5.3.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • the viscosity of a 5 wt.% aqueous solution of the resulting powder was measured as 400 mPas.
  • Residual acrylic acid was determined by HPLC as 0.07 wt.% and residual HPA as 0 wt.%.
  • the molecular weight (M w ) was measured by GPC as 1,049,000 Da.
  • Copolymer of sodium acrylate (79.5 mol %) and hydroxypropyl acrylate (20.5 mol %) made by the process according to the present invention.
  • the final polymer solution had a viscosity of 24 000 mPas (20°C) and a solid content of 23.0 wt.%. pH was measured as 5.7.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • the viscosity of a 5 wt.% aqueous solution of the resulting powder was measured as 300 mPas.
  • Residual acrylic acid was determined by HPLC as 0.1 wt.% and residual HPA as 0 wt.%.
  • the molecular weight (M w ) was measured by GPC as 950,000 Da.
  • Copolymer of sodium acrylate (79.5 mol %) and hydroxypropyl acrylate (20.5 mol %) made by the process according to the present invention.
  • the final polymer solution had a viscosity of 16 800 mPas (20°C) and a solid content of 25 wt.%. pH was measured as 6.1.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • the viscosity of a 5 wt.% aqueous solution of the resulting powder was measured as 260 mPas.
  • Residual acrylic acid was determined by HPLC as 0.34 wt.% and residual HPA as 0 wt.%.
  • the molecular weight (M w ) was measured by GPC as 878,000 Da.
  • the insoluble content was determined as ⁇ 1 wt.%.
  • Inventive example 15 Copolymer of sodium acrylate (79.5 mol %) and hydroxypropyl acrylate (20.5 mol %) made by the process according to the present invention.
  • the final polymer solution had a viscosity of 55 000 mPas (20°C) and a solid content of 25 wt.%. pH was measured as 5.7.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • the viscosity of a 5 wt.% aqueous solution of the resulting powder was measured as 600 mPas.
  • Residual acrylic acid was determined by HPLC as 0.34 wt.% and residual HPA as 0 wt.%.
  • the molecular weight (M w ) was measured by GPC as 851 ,000 Da.
  • the insoluble content was determined as ⁇ 1 wt.%.
  • Inventive example 16 Copolymer of sodium acrylate (79.5 mol %) and hydroxypropyl acrylate (20.5 mol %) made by the process according to the present invention.
  • the final polymer solution had a viscosity of 43 000 mPas (20°C) and a solid content of 22.8 wt.%. pH was measured as 6.2.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • the viscosity of a 5 wt.% aqueous solution of the resulting powder was measured as 490 mPas.
  • Residual acrylic acid was determined by HPLC as 0.36 wt.% and residual HPA as 0 wt.%.
  • the molecular weight (Mw) was measured by GPC as 1 ,263,000 Da.
  • the insoluble content was determined as ⁇ 1 wt.%.
  • Copolymer of sodium acrylate (79.5 mol %) and hydroxypropyl acrylate (20.5 mol %) made by the process according to the present invention.
  • the final polymer solution had a viscosity of 52 000 mPas (20°C) and a solid content of 22.8 wt.%. pH was measured as 6.2.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • the viscosity of a 5 wt.% aqueous solution of the resulting powder was measured as 690 mPas.
  • Residual acrylic acid was determined by HPLC as 0.22 wt.% and residual HPA as 0 wt.%.
  • the molecular weight (Mw) was measured by GPC as 1 ,295,000 Da.
  • the insoluble content was determined as ⁇ 1 wt.%.
  • Copolymer of sodium acrylate (79.5 mol %) and hydroxypropyl acrylate (20.5 mol %) made by the process according to the present invention.
  • the final polymer solution had a viscosity of 14 000 mPas (20°C) and a solid content of 23.5 wt.%. pH was measured as 6.2.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • the viscosity of a 5 wt.% aqueous solution of the resulting powder was measured as 290 mPas.
  • Residual acrylic acid was determined by HPLC as 0.37 wt.% and residual HPA as 0 wt.%.
  • the molecular weight (M w ) was measured by GPC as 1 ,101 ,000 Da.
  • the insoluble content was determined as ⁇ 1 wt.%.
  • Inventive example 19 Copolymer of sodium acrylate (79.5 mol %) and hydroxypropyl acrylate (20.5 mol %) made by the process according to the present invention.
  • the final polymer solution had a viscosity of 18 000 mPas (20°C) and a solid content of 23.5 wt.%. pH was measured as 6.2.
  • the solution was dried with a lab drum dryer (type Merto Drum L, producer Manual Vakuum Apparate, Holland Merten GmbH) at a temperature of 170°C and rotation speed of 1 rpm.
  • the viscosity of a 5 wt.% aqueous solution of the resulting powder was measured as 370 mPas.
  • Residual acrylic acid was determined by HPLC as 0.19 wt.% and residual HPA as 0 wt.%.
  • the molecular weight (M w ) was measured by GPC as 1 ,086,000 Da.
  • the insoluble content was determined as ⁇ 1 wt.%.
  • Shale inhibition is achieved by certain additives to drilling fluids which prevent clays or shale from taking-up water (i.e. from swelling) and by providing cuttings integrity.
  • the level of shale inhibition provided by different drilling fluid additives and formulations is routinely assessed by test such as cuttings dispersion.
  • test such as cuttings dispersion.
  • a good indication of the inhibitive properties of an additive can be obtained by a modification of the standard oilfield cuttings dispersion test based on API RP 131 Section 23: Shale-particle disintegration test by hot rolling. This test is used to screen the effectiveness of inhibitor additives to maintain the integrity of the cuttings and minimize the interaction of fluids with the shale sections during the drilling and completions operations.
  • a known weight of shale cuttings (size 2 to 5 mm, approx. 25 g) is added to a measured volume of the aqueous fluid to be tested (approximately 175 ml) in a container.
  • the container is rotated (hot rolling for about 16 h at 93°C) such that the cuttings are in constant state of agitation in the fluid; this encourages breakdown and dispersion of the cuttings if they become softened due to interaction with the test fluid.
  • After hot rolling for 16 h the container is cooled to room temperature and the fluid containing the cuttings is poured over a 0.5 mm sieve, the retained shale pieces are recovered, and washed with 4 wt.
  • an aqueous drilling fluid typically is a suspension of finely divided bentonite in water. Therefore, as starting material for the drilling fluid to be tested, an aqueous suspension of bentonite (10 wt.%) is prepared.
  • the drilling fluid is split in 2 parts and each part is added in a 250 ml glass bottle,
  • the aged drilling fluid with cuttings is poured across the sieve and the cuttings are washed with a 4 wt.% KCI solution, until the washing solution is clear after running through the sieve with cuttings,
  • Table 1 shows the results of the dispersion tests carried out for samples of each of the examples above described able 1: Results of the samples’ analysis

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Abstract

L'invention concerne un procédé de fabrication de polymères hydrosolubles sous forme de poudre, qui comprennent au moins deux monomères éthyléniquement insaturés différents, à savoir un monomère éthyléniquement insaturé comprenant au moins un groupe OH ou un groupe oxyalkylène, et un autre monomère, par dosage des monomères sur une solution aqueuse comprenant au moins un amorceur radicalaire et séchage du polymère obtenu. Et l'utilisation de ces polymères dans le domaine du forage pétrolier, en particulier en tant qu'agents d'encapsulation de schiste et/ou en tant qu'inhibiteurs de schiste.
PCT/EP2023/065571 2022-06-14 2023-06-12 Procédé de fabrication de polymères hydrosolubles destinés à être utilisés comme agents d'encapsulation de schiste pour fluides de forage WO2023242077A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3385839A (en) * 1963-02-18 1968-05-28 Bayer Ag Cation-active copolymers of hydroxyalkyl and primary amino-alkyl acrylates and methacrylates
JPS56161413A (en) 1980-05-19 1981-12-11 Kao Corp Production of self-crosslinking water-absorbing resin
EP0344589A1 (fr) 1988-05-31 1989-12-06 BASF Aktiengesellschaft Utilisation de polymères solubles dans l'eau comme adhésifs
JPH03197519A (ja) 1989-12-26 1991-08-28 Hoechst Gosei Kk アセトアセトキシ基含有水溶性高分子化合物の製造方法
WO2011118728A1 (fr) 2010-03-25 2011-09-29 株式会社日本触媒 Nouveau copolymère et son procédé de production
US20130289171A1 (en) 2012-04-30 2013-10-31 H.B. Fuller Company Curable aqueous composition
US20170204210A1 (en) 2014-08-08 2017-07-20 S.P.C.M. Sa Water-soluble hydroxyalkyl polymer obtained by a method of inverse suspension or inverse emulsion polymerisation
CN111072666A (zh) 2018-10-19 2020-04-28 北京鼎材科技有限公司 有机电致发光材料及其应用
CN111138584A (zh) * 2020-01-14 2020-05-12 河北工业大学 一种酸洗废液再生剂及其制备方法
CN113072666A (zh) 2020-01-06 2021-07-06 江苏苏博特新材料股份有限公司 一种高减水型聚羧酸超塑化剂的制备方法及应用

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3385839A (en) * 1963-02-18 1968-05-28 Bayer Ag Cation-active copolymers of hydroxyalkyl and primary amino-alkyl acrylates and methacrylates
JPS56161413A (en) 1980-05-19 1981-12-11 Kao Corp Production of self-crosslinking water-absorbing resin
EP0344589A1 (fr) 1988-05-31 1989-12-06 BASF Aktiengesellschaft Utilisation de polymères solubles dans l'eau comme adhésifs
JPH03197519A (ja) 1989-12-26 1991-08-28 Hoechst Gosei Kk アセトアセトキシ基含有水溶性高分子化合物の製造方法
WO2011118728A1 (fr) 2010-03-25 2011-09-29 株式会社日本触媒 Nouveau copolymère et son procédé de production
US20130289171A1 (en) 2012-04-30 2013-10-31 H.B. Fuller Company Curable aqueous composition
US20170204210A1 (en) 2014-08-08 2017-07-20 S.P.C.M. Sa Water-soluble hydroxyalkyl polymer obtained by a method of inverse suspension or inverse emulsion polymerisation
EP3177654B1 (fr) 2014-08-08 2018-06-13 S.P.C.M. Sa Polymere hydroxyalkyle hydrosoluble obtenu par un procede de polymerisation en suspension inverse ou en emulsion inverse
CN111072666A (zh) 2018-10-19 2020-04-28 北京鼎材科技有限公司 有机电致发光材料及其应用
CN113072666A (zh) 2020-01-06 2021-07-06 江苏苏博特新材料股份有限公司 一种高减水型聚羧酸超塑化剂的制备方法及应用
CN111138584A (zh) * 2020-01-14 2020-05-12 河北工业大学 一种酸洗废液再生剂及其制备方法

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