Classifications

• • 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
  • C08F220/52—Amides or imides
  • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
  • C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
• • 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
  • C09K8/532—Sulfur
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
  • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
  • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
  • C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
• • 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
  • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2101/00—Nature of the contaminant
  • C02F2101/10—Inorganic compounds
  • C02F2101/101—Sulfur compounds
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
  • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
  • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
  • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
  • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus

Definitions

• the invention relates to a process for the inhibition and/or dispersion of inorganic sulphide scales by use of synthetic copolymers.
• the copolymers of the invention have particular applicability in inhibiting and/or dispersing zinc sulphide, lead sulphide and iron sulphide.
• ions such as Ca 2+ , Mg 2+ and, in the case of oilfield formation water, Ba 2+ , Sr 2+ , Zn 2+ , Pb 2+ and Fe 2+ .
• relatively insoluble species such as carbonates, sulphates and sulphides may deposit from solution as scale.
• Such deposition may be particularly acute when sulphate-containing seawater, pumped underground to aid oil recovery, comes into contact with formation water.
• a formation water contains sulphide ions
• H 2 S hydrogen sulphide
• ZnS zinc sulphide
• PbS lead sulphide
• FeS, FeS 2 iron sulphide
• Exotic scales such as zinc sulphide, lead sulphide and iron sulphide can be removed using an acid treatment to restore the rate of oil recovery.
• acid treatment of exotic scale poses a severe risk due to the generation of H 2 S gas within the well.
• U.S. Pat. No. 4,762,626 discloses the use of a hydroxethylacrylate/acrylic acid copolymer as a zinc sulphide scale inhibitor in oil well production processes.
• the copolymers have an average molecular weight within a range of 1,000 to 20,000 Da.
• Wells can typically be treated with between 2 and 100 ppm of the copolymer on an active basis.
• U.S. Pat. No. 5,171,459 discloses the use of a scale inhibitor comprising of a phosphate ester or phosphonate, for CaCO 3 inhibition combined with a alkyldiphenylether sulphonate for dispersing sulphide scales/deposits.
• the sulphide dispersant comprises mono- and/or disulphonated alkyldiphenylether, wherein the alkyl substituent has from 4 to 30 carbon atoms and can be branched or linear.
• the dispersant and inhibitor are treated with between 1 and 50 ppm each and can treat a water with the zinc and/or lead concentration up to around 200 ppm.
• US 2005/0067164 A1 discloses copolymer derived from a cationic monomer that inhibits and controls zinc sulphide and iron sulphide scales formed when zinc bromide brines are used as completion fluids.
• the copolymer in the invention contains an acrylamide unit and a diallyldimethylammonium salt thereof.
• the copolymers have an average molecular weight within a range of 500,000 and 5,000,000 Da.
• the copolymers of the invention may also be used to treat scales of calcium, barium, magnesium etc, such as barium sulphate, calcium sulphate and calcium carbonate.
• the copolymer as part of a carrier fluid is present in amounts between 15 and 100,000 ppm.
• the copolymer is typically between 0.02 and 2 mol-%.
• US 2009/0143252 A1 discloses a monomer with a general formula (as specified within the patent) that is part of a homopolymer, where a part of the monomer (“A” within the general formula) can be a straight or branched alkyl chain ranging from 1 to 10 carbon atoms, or is a copolymer of monomers such as acrylate, acrylamide or methacrylamide to disperse metal sulphides prior to their forming scales. Terpolymers of dimethyldiallylammonium salt, 2-hydroxypropyl acrylate and acrylic acid could also be used for this purpose.
• the homopolymers and copolymers in the invention have an average molecular weight within a range of 5000 and 5,000,000 Da.
• the method of treating is described in the invention as being introduced into crude oil at a concentration of between 1 and 10,000 ppm.
• the object of the invention was to provide copolymers which can be used for the inhibition and/or dispersion of inorganic sulphide scales.
• the copolymers of the invention should have particular applicability in inhibiting and/or dispersing zinc sulphide, lead sulphide and iron sulphide. They should be notable for improved biodegradability compared to the copolymers of the prior art.
• copolymers comprising of sulphonic acid acrylic units, acrylamide units and phosphonic acid units and, optionally, cyclic amide units perform in the desired manner.
• the invention therefore provides for the use of a copolymer, comprising
• the invention provides for a process for the inhibition and/or dispersion of inorganic sulphide scales, the process comprising adding to water being within an oil or gas containing formation a copolymer comprising
• the use and the process are conducted with a copolymer comprising additionally 1 to 10 mol-%, based on the weight of the copolymer, of structural units of formula (2)
• n 3, 4 or 5.
• the use and the process are conducted with a copolymer comprising additionally 1 to 10 mol-% of structural units of formula (3)
• R 1 and R 2 independently of one another, are hydrogen or C 1 -C 4 -alkyl.
• monomers comprising an olefinically unsaturated hydrocarbon substituted ammonium salt group, wherein the expression hydrocarbon encompasses groups containing oxygen, are present in the copolymer in an amount of preferably below 1 mol-%, particularly 0.001 to 1 mol-%, especially 0.001 to 0.1 mol-%. They are particularly preferably completely absent.
• the proportion by weight of vinylphosphonic acid or salts thereof is preferably from 0.8 to 6, especially from 1 to 4 mol-%.
• Suitable salts of vinylphosphonic acid are preferably the alkali metal or ammonium (NH 4 + ) salts thereof.
• the proportion of structural units which are derived from compounds of the formula (1) in all embodiments of the invention is preferably from 45 to 70, especially from 50 to 65 mol-%.
• the proportion of structural units which are derived from compounds of the formula (5) is preferably from 5 to 45, especially from 10 to 40 mol-%.
• Formula (5) preferably represents acrylic acid and/or acrylamide. If formula (5) represents only acrylamide, the proportion thereof is preferably from 5 to 45, especially from 10 to 40 mol-%. If formula (5) represents a mixture of acrylic acid and acrylamide, the proportion of acrylic acid is preferably from 1 to 10 mol-%, especially from 2 to 5 mol-%, and the proportion of acrylamide provides for the difference up to the total molar amount as described above.
• the proportion of structural units which are derived from compounds of the formula (3) is preferably from 1 to 10, particularly from 2 to 8, especially from 3 to 7 mol-%.
• the proportion of structural units which are derived from compounds of the formula (2) is preferably from 1 to 10, particularly from 2 to 8, especially from 3 to 7 mol-%.
• Suitable copolymers comprise (molar %).
• the monomer units may be in any sequence in the copolymers. They may be either random polymers or block polymers.
• the molecular weights (number average) of the copolymers according to the invention are preferably from 100,000 to 10,000,000 g/mol, in particular from 500,000 to 5,000,000 g/mol. Molecular weight is to be determined by GPC against polyacrylic acid as standard.
• the relative viscosity and the k value of the copolymer may also serve as indicator for the molecular weight.
• the copolymer is dissolved in a certain concentration (generally 0.5%) and the efflux time at 25° C. is determined by means of an Ubbelohde capillary viscometer. This value gives the absolute viscosity of the solution ( ⁇ c ).
• the absolute viscosity of the solvent is ⁇ 0 .
• the ratio of the two absolute viscosities gives the relative viscosity
• the k value can be determined as a function of the concentration by means of the following equation:
• copolymers according to the invention can be prepared by copolymerization of compounds of the formulae (1), (2) and (3), (5) and vinyl phosphonic acid, in the stated molar ratios.
• copolymers according to the invention can be prepared by the conventional polymerization methods, such as solution polymerization, mass polymerization, emulsion polymerization, inverse emulsion polymerization, precipitation polymerization or gel polymerization. They are preferably the product of a free-radical copolymerization of the compounds of the formulae (1), (2) and (3), (5) and vinyl phosphonic acid.
• the polymerization is preferably carried out as solution polymerization in water and as precipitation polymerization.
• the conditions of precipitation polymerization are employed.
• the copolymer is obtained directly in solid form and can be isolated by distilling off the solvent or filtering with suction and drying.
• Water-miscible organic solvents which are suitable here are in particular water-soluble alkanols, i.e. those having 1 to 4 carbon atoms, such as methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol and isobutanol, but preferably tert-butanol.
• the water content of the lower alkanols used here as solvent should not exceed 6 mol-%, since otherwise agglomeration may occur during the polymerization.
• a water content of 0 to 3 mol-% is employed.
• the amount of the solvent to be used depends to a certain degree on the type of comonomers used. As a rule, from 200 to 1000 g of the solvent are used per 100 g of total monomers.
• the aqueous monomer solution is emulsified in a known manner in a water-immiscible organic solvent, such as cyclohexane, toluene, xylene, heptane or high-boiling gasoline fractions, with the addition of from 0.5 to 8 mol-%, preferably from 1 to 4 mol-%, of known emulsifiers of the w/o type and polymerized with conventional free radical initiators.
• a water-immiscible organic solvent such as cyclohexane, toluene, xylene, heptane or high-boiling gasoline fractions
• water-soluble monomers or mixtures thereof are polymerized at elevated temperatures to give high molecular weight copolymers by first emulsifying the monomers or the aqueous solutions thereof, with the addition of water-in-oil emulsifiers, in water-immiscible organic solvent forming the continuous phase, and heating this emulsion in the presence of free radical initiators.
• the comonomers to be used may be emulsified as such in the water-immiscible organic solvent or they may be used in the form of an aqueous solution which contains from 100 to 5 mol-% of comonomers and from 0 to 95 mol-% of water, the composition of the aqueous solution depending on the solubility of the comonomers in water and on the intended polymerization temperature.
• the weight ratio of water to the monomer phase can be varied within wide limits and is as a rule from 70:30 to 30:70.
• a water-in-oil emulsifier is added to the mixtures.
• emulsifiers are those which have a relatively low HLB value.
• the oil phase used can in principle be any inert water-insoluble liquid, i.e. in principle any hydrophobic organic solvent. In general, hydrocarbons whose boiling point is in the range from 120 to 350° C. are used.
• hydrocarbons may be saturated, linear or branched paraffin hydrocarbons, as are predominantly present in petroleum fractions, it also being possible for these to comprise the usual proportions of naphthene hydrocarbons.
• aromatic hydrocarbons such as, for example, toluene or xylene, and mixtures of the abovementioned hydrocarbons may also be used as the oil phase.
• a mixture of saturated normal paraffin and isoparaffin hydrocarbon which comprises up to 20 mol-% of naphthenes is preferably used.
• Copolymers having a particularly high degree of polymerization in the base chains are obtained as polymerization is carried out in aqueous solution by the so-called gel polymerization method. From 15 to 60% strength aqueous solutions of the comonomers are obtained with known suitable catalysts without mechanical mixing, with utilization of the Trommsdorff-Norrisch effect.
• the quality properties of the polymers can be further improved.
• copolymers prepared by this method and present in the form of aqueous gels can be dissolved directly in water after mechanical comminution using suitable apparatuses and can be used. However, they can also be obtained in solid form after removal of the water by known drying processes and not dissolved again in water until they are used.
• the polymerization reaction is carried out in the temperature range from ⁇ 60° C. to 200° C., preferably from 10 to 120° C., it being possible to employ either atmospheric pressure or superatmospheric pressure.
• the polymerization is carried out in an inert gas atmosphere, preferably under nitrogen.
• High-energy electromagnetic or corpuscular radiation or conventional chemical polymerization initiators can be used for initiating the polymerization, for example organic peroxides, such as benzyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide or cumyl hydroperoxide, azo compounds, such as azobisisobutyronitrile or 2′-azobis(2-amidopropane)dihydrochloride, and inorganic peroxy compounds, such as (NH 4 ) 2 S 2 O 8 or K 2 S 2 O 8 or H 2 O 2 , if required in combination with reducing agents, such as sodium bisulfite and iron(II) sulfate, or redox systems which comprise an aliphatic or aromatic sulfinic acid, such as benzenesulfinic acid or toluenesulfinic acid or derivatives of these acids, such as, for example, Mannich adducts or sulfinic acid, alde
• moderators may be added to the polymerization batches, said moderators harmonizing the course of the reaction by flattening the reaction rate/time diagram. They thus lead to an improvement in the reproducibility of the reaction and therefore make it possible to prepare uniform products having extremely small quality deviations.
• suitable moderators of this type are nitrilotrispropionylamide, monoalkylamines, dialkylamines or trialkylamines, such as, for example, dibutylamine.
• Such moderators can advantageously also be used in the preparation of the copolymers according to the invention.
• regulators i.e. those compounds which influence the molecular weight of the polymers prepared, can be added to the polymerization batches.
• Known regulators which may be used are, for example, alcohols, such as methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol and amyl alcohols, alkyl mercaptans, such as, for example, dodecyl mercaptan and tert-dodecyl mercaptan, isooctyl thioglycolate and some halogen compounds, such as, for example, carbon tetrachloride, chloroform and methylene chloride.
• copolymers according to the invention are outstandingly suitable in the inhibition and/or dispersion of inorganic sulphide scales, particularly in inhibiting and/or dispersing zinc sulphide, lead sulphide and iron sulphide scales. Their biodegradability is considerably superior to that of the copolymers of the prior art.
• copolymers of the invention effectively inhibit and/or disperse by way of controlling the aggregation of inorganic scale formations within hydrocolloids, such as the formation water brines in oil wells and reservoirs.
• the copolymers of the invention show particular applicability in the inhibition and/or dispersion of zinc sulphide, lead sulphide and iron sulphide scales.
• copolymers of the invention can prevent the aggregation of inorganic sulphide scales through either continuous injection into an oil well as a neat chemical, or as part of a carrier fluid such as brine.
• the amount of the copolymer required will depend upon how severe the sulphide scale in an oil well or reservoir is.
• the copolymers according to the invention are preferably used in concentrations of 1 to 10,000 ppm, in particular from 10 to 1000 ppm by weight based on the weight of the aqueous system susceptible to scale formation.
• the copolymers of the invention can additionally be blended with scale inhibitors that are used for more conventional scales, such as, but not limited to, calcium carbonate and barium sulphate.
• scale inhibitors such as, but not limited to, calcium carbonate and barium sulphate.
• the performance of the copolymers of the invention as sulphide scale inhibitors are not lessened by the presence of conventional scale inhibitors and neither is the performance of the conventional scale inhibitors lessened by the presence of the copolymers of the invention as sulphide scale inhibitors.
• Suitable conventional scale inhibitors include diethylenetriamine penta(methylene phosphonic acid), or nitrilo(methylene phosphonic acid) although any phosphonate scale inhibitor can be used as well as a number of polymer based scale inhibitors. These can include methacrylic diphosphonate homopolymer, acrylic acid-allyl ethanolamine diphosphonate copolymer, SVS (sodium vinyl sulphate)-acrylic acid-allyl ammonia diphosphonate terpolymer, acrylic acid-maleic acid-DETA (diethylene triamine)allyl phosphonate terpolymer, polyaspartic acid, polycarboxylates.
• a formulation contains 25-30 wt.-% water or solvent, 0.5-10 wt.-% copolymers of the invention for sulphide scale inhibition, 1-25 wt.-% of a conventional scale inhibitor and 5-50 wt.-% glycol based solvent.
• a formulation contains 25-30 wt.-% water or solvent, 0.5-10 wt.-% copolymers of the invention for sulphide scale inhibition, 0.5-5 wt.-% ethanolamine phosphoric acid conventional scale inhibitor, 0.5-20 wt.-% phosphonic, sulphonic and carboxylic acid conventional scale inhibitor and 5-50 wt.-% glycol based solvent.
• composition of the copolymers used as ZnS/PbS scale inhibitor/dispersant were as follows (percentages denote mol-%):
• Polymer 1 58% AMPS, 38% Acrylic Amide, 2% n-Vinyl Formamide, 2% Vinyl Phosphonic Acid. Number average molecular mass 4-5 Million g mol ⁇ 1 .
• Polymer 2 78% AMPS, 38% Acrylic Amide, 2% n-Vinyl Formamide, 2% Vinyl Phosphonic Acid. Number average molecular mass 4-5 Million g mol ⁇ 1 .
• Polymer 3 83% AMPS, 5% n-Vinyl Pyrrolidone, 5% n-Vinyl Formamide, 5% Acrylic Amide, 2% Vinyl Phosphonic Acid. Number average molecular mass 0.5-1 Million g mol ⁇ 1 .
• the cation brine contained NaCl, CaCl 2 , MgCl 2 , KCl, Zn(CH 3 COO) 2 and Pb(CH 3 COO) 2 .
• the anion brine contained only NaS.
• the respective ZnS/PbS scale inhibitor/dispersant copolymer was then added to the anion brine.
• the cation brine was subsequently mixed with the anion brine at a 50:50 volume mix in a glass jar.
• the jars were placed into a 90° C. water bath and monitored over 24 hours.
• concentrations of Zn and Pb were determined using ICP. These are expressed as Pb or Zn Inhibition Efficiency relative to a blank and control sample of the brine. For this determination, a sample of the liquid which is above the precipitate, if any, is taken.
• the liquid is analyzed for Zn and Pb content using ICP. The higher the Zn and Pb concentration is, the higher the Efficiency is.
• the examples 1-12 below use different copolymers/terpolymers as indicated.
• ICP Inductively Coupled Plasma
• the analyte is introduced via a nebuliser to create a fine spray and in combination with Argon gas creates a plasma.
• the plasma then passes through a torch, where, depending upon which elements are present within the plasma, emit a characteristic wavelength.
• the characteristic wavelength is detected using a spectrometer (Optical Emission Spectrometer, OES) that is linked to the ICP instrument.
• OES Optical Emission Spectrometer
• the results obtained were as follows.
• the ppm values refer to weight ppm of the respective polymer based on the total weight of the brine.
• control values were obtained through analyzing a sample made up of 50% cations and 50% anions by ICP straight away, i.e. without time delay. This of course leads to some scale formation and thus a loss of Zinc and Lead concentration.
• ICP-OES inductively coupled plasma optical emission spectrometry
• the samples may not have nebulized fully as a result of the higher viscosity from the relatively higher inhibitor concentrations present. This can lead to a reduction in the Zinc and Lead concentrations that are detected by ICP-OES and accounts for the decline in efficiency at higher polymer concentrations.
• the concentrations of Zinc and Lead are not corrected from the loss of sample during the nebulization of the sample. If an internal standard was employed the instrument can correct the concentrations of Zinc and Lead.
• the ‘matrix matching’ correction would account for the salinity interferences of the brine such as spectral interferences and reduced ionisation of the analytes in the plasma, however variation in the nebulisation of the samples would not have been accounted for.
• Examples 7-12 again used copolymers 1-3 as listed above at the same concentrations, as well as the same test conditions, however they use harsher water chemistry, as shown below;

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