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WO1996037684A1 - Inhibiteur d'hydrates de clathrate et procede permettant d'inhiber la formation des hydrates de clathrate dans lequel il est utilise - Google Patents

Inhibiteur d'hydrates de clathrate et procede permettant d'inhiber la formation des hydrates de clathrate dans lequel il est utilise Download PDF

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Publication number
WO1996037684A1
WO1996037684A1 PCT/JP1996/001396 JP9601396W WO9637684A1 WO 1996037684 A1 WO1996037684 A1 WO 1996037684A1 JP 9601396 W JP9601396 W JP 9601396W WO 9637684 A1 WO9637684 A1 WO 9637684A1
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WO
WIPO (PCT)
Prior art keywords
clathrate
meth
vinyl
hydrate inhibitor
clathrate hydrate
Prior art date
Application number
PCT/JP1996/001396
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English (en)
Inventor
Takashi Namba
Toshiaki Kuriyama
Masashi Yukitake
Hiroya Kobayashi
Original Assignee
Nippon Shokubai Co., Ltd.
Rf Rogalandsforskning
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 Nippon Shokubai Co., Ltd., Rf Rogalandsforskning filed Critical Nippon Shokubai Co., Ltd.
Priority to AU57798/96A priority Critical patent/AU5779896A/en
Publication of WO1996037684A1 publication Critical patent/WO1996037684A1/fr

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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
    • C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
    • C08F271/02—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00 on to polymers of monomers containing heterocyclic nitrogen
    • 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
    • C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
    • 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
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/22—Hydrates inhibition by using well treatment fluids containing inhibitors of hydrate formers

Definitions

  • the present invention relates to clathrate hydrate inhibitors and a methodof inhibitingthe formationof clathrate hydrates using them.
  • the invention is useful in inhibiting the formation of clathrate hydrates, for example, in pipe lines for production for oil and natural gas and for transporting them, in cooling water circulating in factories, in cooling water for various engines, etc.
  • a method of adding large amounts of low-molecularweight substances, such as ethylene glycols, urea and inorganic salts, as clathrate hydrate inhibitors capable of taking the place of methanol to inhibit the precipitation and growth of clathrate hydrates has beenproposed.
  • Ethyleneglycolortriethylenglycol is sometimes preferred to methanol since it is more easily recovered and does not pollute the gas or condensate (light oil fractions), but they cost more than methanol. Therefore, ethylene glycols can be favourable over methanol only in some cases in which the total production cost is decreased.
  • such low-molecular weight substances must be added in large amounts, likemethanol.
  • thermodynamic inhibitors The most significant difference between the methods of adding such macromolecular compounds and the methods of adding methanol and other low-molecular weight substances lies in the mechanisms inhibiting the formation of clathrate hydrates. Precisely, large amounts of methanol and other low-molecular weight substances are added to systems by which the formation of clathrate hydrates is completely and thermodynamically inhibited or, that is, the formationis completelyinhibiteddue to the freezing-pointdepression inthe systems. Such additives are referred to as thermodynamic inhibitors.
  • additives of macromolecular compounds are referred to as kinetic inhibitors, which inhibit not completely the formation of clathrate hydrates but retard and inhibit the formation of clathrate hydrates for a certain period of time or control the crystal systems and the sizes of the clathrate hydrates being formed, thereby inhibiting the clogging of pipe lines for a certain period of time.
  • the macromolecular compounds are characterized in that they can exhibit a high inhibiting effect even when added in much smaller amounts than the low-molecular weight substances.
  • the object of the present invention is to provide a clathrate hydrate inhibitor which is stable in the system that may form clathrate hydrates, and which has the high ability to retard the formation of clathrate hydrates and to inhibit the growth thereof.
  • Another object of the invention is to provide a method of inhibiting the formation of clathrate hydrates, which is stably applicable to the systemthat may form clathrate hydrates, which is highly effective in retarding the formation of clathrate hydrates and in inhibiting the growth thereof and which is cost-effective.
  • the clathrate hydrate inhibitor in the present invention is aclathratehydrateinhibitorwhichcomprisesamacromolecular compound (A) having from 5-membered to 15-membered ring pendant which is directly connected to the polymer main chain through one of the atoms within the ring and a vinyl polymer (B) , which are bonded to each other. It is desirable that the clathrate hydrate inhibitor is obtained by polymerizing vinyl monomers (b) in the presence of a macromolecular compound (A) having from 5-membered to 15- membered ring pendant is directly connected to the polymer main chain through one of the atoms within the ring.
  • the vinyl monomer (b) is radically polymerized. It is also desirable that the vinyl monomers (b) are alkyl (meth)acrylates, N-alkyl (meth)acryla ides, or N,N-dialkyl (meth)acryiamides.
  • the clathrate hydrate inhibitor in the present invention is also a clathrate hydrate inhibitor which comprises a copolymer of ethylenically unsaturated monomers (a) having from 5-membered to 15-memberd ring pendant which is directly connected to the ethylenically unsaturated group through one of the atoms with the ring and alkyl (meth) acrylates, N-alkyl (meth)- acrylar ⁇ ides, or N,N-dialkyl (meth)acrylamides (b') whose alkyl chain has C3-C6 carbon atoms.
  • a ethylenically unsaturated monomers
  • a having from 5-membered to 15-memberd ring pendant which is directly connected to the ethylenically unsaturated group through one of the atoms with the ring and alkyl (meth) acrylates, N-alkyl (meth)- acrylar ⁇ ides, or N,N-dialkyl (meth
  • the copolymer comprises ethylenically unsaturate monomers (a) having from 5-membered to 15-membered ring pendant is directly connected to the ethylenically unsaturated group through one of the atoms within the ring, at 60 mol% or more.
  • the ethylenically unsaturated monomers (a) comprise one or more selected from the group consisting of N-vinyl pyrrolidinone, N-vinyl piperidinone, N-vinylcaprolactam, N- vinyloxazolidone, and N-vinyl- methyloxazolidone.
  • Another aspect of the present invention is a method of inhibiting the formation of clathrate hydrates by adding the above-mentioned clathrate hydrate inhibitorto a systemcapable of forming clathrate hydrates.
  • the clathrate hydrate inhibitor is added to a system capable of forming clathratehydrates, after havingbeen dissolvedinwater and/or a water-miscible solvent.
  • the clathrate hydrate inhibitor is added to a system capable of forming clathrate hydrates, in an amount of from 0.01 to 30 parts by weight relative to 100 parts of the free water existing in the system.
  • the clathrate hydrate inhibitor of the present invention comprises a macromolecular compound (A) having from 5-membered to 15-memberedring pendant is directlyconnected to the polymer main chain through one of the atoms within the ring and a vinyl polymer (B) , which are bonded to each other.
  • the macromolecula compound (A) and the vinyl polymer (B) may be contained in the form of a mixture.
  • the macromolecular compound (A) which is used in the present invention, includes, for example, homopolymers and copolymers to be obtained by polymerizing one or more ethylenically unsaturated monomers (a) having from 5-membered to 15-membered ring pendant which is directly connected to the ethylenically unsaturated group through one of the atoms within the ring, which are selected from the group consisting of vinyl lactams, e.g., N-vinyl-2-pyrrolidinone,N-vinyl-2-piperidinone, N-vinyl-caprolactam; vinyl oxazolidones, e.g., N-vinyl oxazolidone, N-vinyl-5-methyloxazolidone; vinyl imidazole, vinylcarbazole, vinylpyridine, styrene, 2-vinyl-l,3-dioxolane, vinyl norbornene etc.
  • vinyl lactams e.
  • One or more and the same or different monomers of the above-mentioned ones can be used in the present invention.
  • macromolecularcompounds (A) those which are obtained by polymerizing monomers (a) having lactam- or oxazolidone- structured cyclic pendants, such as N-vinyl-2-pyrrolidinone,
  • N-vinyl-2-piperidinone N-vinyl-caprolactam, N-vinyloxazolidone, N-vinyl-
  • 5--methyloxazolidone, etc. are preferred,as their ability to inhibit the formation of clathrate hydrates is high.
  • the macromolecular compound (A) for use in the present invention also includes copolymers to be obtained by radical polymerization of the above-mentioned monomers (a) and comonomers copolymerizable with the monomers (a).
  • the proportion of the monomers (a) is desirably 10 mol% or more.
  • the comonomers copolymerizable with the monomers (a) include unsaturated hydrocarbons such as ethylene, propylene, etc.; acrylic compounds such as (meth)acrylic acid, (meth)acrylates, dimethylaminoethyl (meth)acrylate, etc.; aerylamide compounds such as (meth)aerylamide, N-alkyl (meth)aerylamide, N, N-dialkyl (meth)aerylamide, diethylaminopropyl (meth)acrylamide, etc.; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether etc.; vinyl acetate, etc.
  • unsaturated hydrocarbons such as ethylene, propylene, etc.
  • acrylic compounds such as (meth)acrylic acid, (meth)acrylates, dimethylaminoethyl (meth)acrylate, etc.
  • aerylamide compounds such as (meth)aeryl
  • lower alkyl (meth)acrylates such as methyl (meth)aerylate, ethyl (meth)aerylate, n-propyl (meth)aerylate, isopropyl (meth)aerylate, n-butyl acrylate, isobutyl acrylate, tert.- butyl acrylate; N-alkyl (meth)aerylamide such as N-(n-butyl), (meth)acrylamide N-(isobutyl) (meth)aerylamide; N,N-dialkyl (meth)acrylamide such as N, N-diethyl (methy)acrylamide, vinyl ethers such as butyl vinyl ether, since the stability of the clathrate hydrate inhibitor to be obtained from these in the system capable of forming clathrate hydrates is much improved.
  • the molecular weight of the macromolecular compound (A) is preferably from 5,000 to 500,000, more preferably from 20,000 to 200,000. If the compound (A) has a molecular weight smaller than 5,000, the ability of the clathrate hydrate inhibitor comprising it to inhibit the formation and growth of clathrate hydrates will be often poor.
  • the viscosity of the system to which the clathrate hydrate inhibitor comprising it is added is extremely increasedortheviscosityofthesolution itselfoftheclathrate hydrate inhibitorcomprising it is also extremelyincreasedwith the result that the addition of the solution of the clathrate hydrate inhibitor to a system capable of forming clathrate hydrates will be often difficult.
  • the vinyl polymer (B) for use in the present invention includes (co)polymers of unsaturated hydrocarbons such as ethylene, propylene, etc.; acrylic compounds such as (meth)acrylic acid, (meth)acrylates, dimethylaminoethyl acrylate, etc.; acrylamide compounds such as (meth)acrylamide, diethylaminopropyl acrylamide, etc.
  • the molecular weight of the vinyl polymer.(B) is preferably from 5,000 to 500,000, more preferably from 20,000 to 200,000. If the vinyl polymer (B) has amolecularweightsmallerthan5,000, theability of the clathrate hydrate inhibitor comprising it to inhibit the formation and growth of clathrate hydrates will be often poor.
  • the vinyl polymer (B) has a molecular weight larger than 500,000, the viscosityof the systemto which the clathrate hydrate inhibitor comprising it is added is extremely increased or the viscosity of the solution itself of the clathrate hydrate inhibitor comprising it is also extremely increased with the result that the addition of the solution of the clathrate hydrate inhibitor to a systemcapable of forming clathratehydrates will be often difficult.
  • the clathrate hydrate inhibitor of the present invention can be obtained, for example;
  • Thevinylmonomers (b) tobe usedinthemethod (i) include, for example, unsaturated hydrocarbons such as ethylene, propylene, etc.; acrylic compounds such as (meth)acrylic acid, (meth)acrylates, dimethylaminoethyl acrylate, etc.; acrylamide compounds such as (meth)acrylamide, N-alkyl (meth)acrylamide, N,N-dialkyl (meth)acrylamide, diethylaminopropyl acrylamide, etc.
  • alkyl (meth)acrylates N-alkyl (meth)acrylamides, or N,N- dialkyl (meth)acrylamides in which the alkyl group may be linear or branched
  • alkyl ( ⁇ neth)acrylates can be used.
  • the alkyl group in the ester moiety generally has from 1 to 24 carbon atoms.
  • the alkyl (meth)aerylates those where the alkyl group in the ester moiety has from 4 to 18 carbon atoms are preferred since they are easily available and easily handled.
  • N-alkyl (meth)acrylamid or N,N-dialkyl (meth)acrylamide are preferred since the ability of the resulting clathrate hydrate inhibitor to inhibit the formation and growth of clathrate hydrates is high.
  • They include, for example, N-butyl (meth)acrylamide, N,N-diethyl (methy)acrylamide.
  • the molecular weight of the macromolecular compound (A) to be used in the method (i) or that of the vinyl polymer (B) to be used in themethod (ii) is from5,000 to 500,000, preferably from.20,000to200,000. If the compound (A) orthevinylpolymer (B) has a molecular weight smaller than 5,000, the ability of the resulting clathrate hydrate inhibitor to inhibit the formation and growth of clathrate hydrates will be often poor.
  • the viscosity of thesystem to which the resulting clathrate hydrate inhibitor is added is extremely increased or the viscosity of the solution itself of the resulting clathrate hydrate inhibitor is also extremely increased with the result that the addition of the solution of the clathrate hydrate inhibitor to a system capable of forming clathrate hydrates will be often difficult.
  • the method (i) of radical polymerizationof vinylmonomers (b) in the presence of a macromolecular compound (A) includes, for example, a method of directly polymerizing a mixture comprising amacromolecularcompound (A) andvinyl monomers (b); a method of polymerizing a dispersion of a macromolecular compound (A) as swollen with vinyl monomers (b) in a solvent; a method of polymerizing a homogeneous system comprising a macromolecularcompound (A) andvinyl monomers (b) bothdissolved in a solvent; a method of polymerizing a suspension of vinyl monomers (b) in a solution of a macromolecular compound (A) as dissolved inasolventthat dissolvesthemacromolecularcompound (A) but does not dissolve vinyl monomers (b); a method of polymerizing vinyl monomers (b) in a suspension of a high- molecular compound (A) as suspended in a solvent that dissolves
  • the ratio of the macromolecular compound (A) to the vinyl monomers (b) is such that the vinyl monomers (b) are from 0.1 to 500 parts by weight, preferably from 10 to 200 parts.by weight, relative to 100 parts by weight of the macromolecular compound (A) .
  • themodification of the high-molecularcompound (A) withthevinyl monomers (b) is effected highlyand theability of the resulting clathrate hydrate inhibitor to inhibit the formation of clathrate hydrates is high.
  • the method (ii) of radical polymerization of monomers (a) having from 5-membered to 15-membered cyclic pendants in the molecule in the presence of a vinyl polymer (B) includes, for example, a method of directly polymerizing a mixture comprising a vinyl polymer (B) and monomers (a) having from 5-membered to 15-membered cyclic pendants in the molecule; a method of polymerizing a dispersion of a vinyl polymer (B) as swollenwith monomers (a) and dispersedin a solvent; amethodof polymerizing a homogeneous systemcomprisinga vinyl polymer (B) andmonomers (a) both dissolved in a solvent; a method of polymerizing a suspension of monomers (a) in a solution of a vinyl polymer (B) as dissolved in a solvent that dissolves the vinyl polymer (B) but does not dissolve monomers (a); a method of polymerizing monomers (a) in
  • the ratio of the vinyl polymer (B) to the monomers (a) is such that the monomers (a) are from 0.1 to 500 parts by weight, preferably from 10 to 200 parts by weight, relative to 100 parts by weightof the vinyl polymer (B) .
  • the modification of vinyl polymer (B) with the monomers (a) is effected highly and the ability of the resulting clathrate hydrate inhibitor to inhibit the formation of clathrate hydrates is high.
  • solvents are used for the polymerization in the methods (i) and (ii), they are not specifically defined.
  • aqueous solutions of salt such as saline, seawater, etc.
  • aliphatic hydrocarbons such as hexane, etc.
  • alicyclic hydrocarbons suchas cyclohexane, etc.
  • aromatic hydrocarbons such as benzene, toluene, xylene, etc.
  • alcohols such as methanol, ethanol, 2-propanol, etc.
  • glycols such as ethylene glycol, diethylene glycol etc.
  • ethers such as diethyl ether, etc.
  • cyclic ethers such as dioxane, dioxolane, tetrahydrofuran, etc.
  • esters such as ethyl acetate, butyl acetate, etc.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl
  • halogen-containing organic solvents such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.
  • halogen-containing organic solvents such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.
  • aqueous solutions of salt such as saline and seawater, as well as methanol, ethanol, ehylene glycol, and dioxolane, as being highly safe.
  • the polymerization in the method (i) preferably employed is the method of directly polymerizing a mixture comprising amacromolecularcompound (A) andvinyl monomers (b) ; and for the polymerization in the method (ii), preferably employed is the method of directly polymerizing a mixture comprisingavinyl polymer (B) and monomers (a) .
  • these methods are industrially advantageous in that they do not require solventsandtherefore donotrequire anystepofremoving solvents.
  • the methods of obtaining the polymers as a solution or dispersion (emulsion) in aqueous mediaor in organic solvents with low toxicity, e.g, alcohols and glycols, are also preferrable for handling and safety consideration.
  • the meansof formingradicalsto beemployedfortheradical polymerization in the methods (i) and (ii) are not also specifically defined.
  • employable are peroxides such as hydrogenperoxide, benzoyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, 3,5,5- trimethylhexanoyl peroxide, t-butyl peroxide-2-ethyl hexanoate, dicumyl peroxide, etc.; azo compounds such as azobisisobutyronitrile, 2,2-azobis(2,4- dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4- dimethylvaleronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, etc.; redox initiators such as sulfite/so
  • the clathrate hydrate inhibitor thus obtained participates in the inhibition of the formation and the growth of clathrate hydrates by what mechanism but it may be considered that the monomers react with the polymer in the clathrate hydrate inhibitorwherebythe polymer is modifiedwith the monomers and the ability of the thus-modified polymer to inhibit the formation and the growth of clathrate hydrates is much more improved than that of the non-modified polymer.
  • the effect is especially remarkable when vinyl monomers (b) are radically polymerized in the presence of a macromolecular compound (A) and especiallywhen thevinylmonomers (b) are alkyl (meth)acrylates.
  • the clathrate hydrate inhibitor of the present invention is a copolymer comprising ethylenically unsaturated monomers (a) having from 5-membered to 15-membered ring pendant is directly connected to the ethylenically unsaturated group through one of the atoms within the ring and vinyl monomers (b)
  • the vinyl monomers (b) should be one ormore selected from the group consisting from alkyl (meth)acrylates, N-alkyl (meth)acrylamides, and N,N-dialkyl (meth)acrylamides whose alkyl groups have 3 to 6 carbon atoms (b').
  • the ethylenicallyunsaturatedmonomers (a) which areused inthepresentinventioninclude, forexample, theN-vinyl-lactam compounds include N-vinyl-2-pyrrolidinone, N-vinyl-2- piperidinone, N-vinyl-caprolactam, etc.; the oxazolidone ring- containing compounds include N-vinyloxazolidone, N-vinyl-5- methyloxazolidone, etc. ; vinyl imidazole, vinylcarbazole, vinylpyridine, styrene, 2-vinyl-l,3-dioxolane, vinylnorbornene etc.
  • polymers to beobtainedby polymerizingmonomers (a) having lactam-, or oxazolidone-structured ring pendants, such as N-vinyl- 2-pyrrolidinone, N-vinyl-caprolactam, N- vinyloxazolidone, N- vinyl-5-methyloxazolidone, N-vinyl-4- methyloxazolidone etc., are preferred, as their ability to inhibit the formation of clathrate hydrates is high.
  • C3 - C6 alkyl (meth)acrylates (b 1 ) which are used for the clathrate hydrate inhibitorofthe present invention, comprising a copolymer of ethylenically unsaturated monomers (a) and C3 - C6 alkyl (meth)acrylates (b'), include, for example, propyl (meth)acryl te, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate. Oneormoreofthesecanbeused. Ofthese, butyl (meth)acrylate and pentyl (meth)acrylate are preferred, since the ability of the copolymers to be obtained from these to inhibit the formation of clathrate hydrates is high.
  • N-alkyl (meth)acrylamides (b'), which are used for the clathrate hydrate inhibitorofthe present invention, comprising a copolymer of ethylenically unsaturated monomers (a) and N- alkyl (meth)aerylamides (b' ), include, for example, N-(n-propyl) (meth)acryamide, N-(isopropyl) (meth)acryamide, N-(n-butyl) (meth)acrylamide, N-(isobutyl) (meth)acrylamide.
  • butyl (meth)acrylate and pentyl (meth)acrylate are preferred, since the ability of the copolymers to be obtained from these to inhibit the formation of clathrate hydrates is high.
  • the molecular weight of the copolymer to be used in the present invention is from 5,000 to 500,000, preferably from 20,000 to 200,000. If the copolymer has a molecular weight smaller than 5,000, the ability of the resulting clathrate hydrate inhibitor to inhibit the formation and growth of clathratehydrateswill beoftenpoor.
  • the viscosity of the system to which the resulting clathrate hydrate inhibitor is added is extremely increased or the viscosity of the solution itself of the resulting clathrate hydrate inhibitor is also extremely increased with the result that the addition of the solution of the clathrate hydrate inhibitor to a systemcapable of forming clathrate hydrates will be often difficult.
  • the copolymer comprises ethylenically unsaturatedmonomers (a) at 90 mol% ormore, since the abilityofthe copolymertoinhibittheformationofclathrate hydrates is remarkably high and since the solubility of the copolymer in the system capable of forming clathrate hydrates is high.
  • the means of polymerizing the monomers to obtain the copolymer for use in the present invention are not specifically defined.
  • any conventional polymerization methods of, for example, radical polymerization, ionic polymerization, etc. can be employed.
  • the polymerization may be conducted in the absence of solvents or in the presence of solvents or dispersion media.
  • any other conventionalpolymerizationmodesof, forexample, precipitation polymerization, emulsion polymerization, suspension polymerization, etc. can also be employed.
  • the solvents and dispersion media are not specifically defined.
  • employable are water; aqueous solutions of salt such as saline, seawater, etc.; aliphatic hydrocarbons such as hexane, etc.; alicyclic hydrocarbons such as cyclohexane, etc.; aromatic hydrocarbons suchasbenzene, toluene, xylene, etc.
  • alcohols such asmethanol, ethanol, 2-propanol, etc.
  • ethers such as diethyl ether, etc.
  • cyclicethers such asdioxane, dioxolane, tetrahydrofuran, etc.
  • esters such as ethyl acetate, butyl acetate, etc.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
  • sulfoxides such as dimethylsulfoxide, etc.
  • amides such as dimethylformamide, etc.
  • halogen-containing organic solvents such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.
  • water, aqueous solutions of salt such as saline and seawater, as well as ethanol and dioxolane, as being highly safe.
  • the method to be conducted in the absence of solvents is industrially advantageous since it does not require any step of removing solvents. Where the removal of the heat of polymerization is difficult or where the purification of the reaction products is needed, it is more desirableto employ suspensionpolymerization and precipitation polymerization.
  • the clathrate hydrate inhibitor thus obtained participates in the inhibition of the formation and the growth of clathrate hydrates by what mechanism but it may be considered that, since the structure of the alkyl group having from 3 to 6 carbon atoms in the side chain of the (meth)acrylate (b* ) is similarto thatofhydrocarbons, suchaspropane, pentane, etc., which are typical guest molecules that cause the formation of clathratehydrates inpipe lines throughwhichoil and natural gas arebeingproduced, thesidechainwillhavethesimilareffect as such guest molecules, and thus, the formation field of clathrate hydrate will converge around the ' clathrate hydrate inhibitor, and, as a result, theclathratehydrate inhibitorwill function extremely efficiently.
  • the method of adding the clathrate hydrate inhibitor of the present invention to a system capable of forming clathrate hydrates is notalsospecificallydefined.
  • Theclathratehydrate inhibitor may be directly added to the system by itself or may be addedtheretoin anyformof solution, dispersionorsuspension thereof. Where monomers are radically polymerized in the presence of a polymer, the resultingclathrate hydrate inhibitor may be added like in the above, after the homopolymers formed during the radical polymerization have been removed.
  • the "system capable of forming clathrate hydrates" as referred to herein indicates a system comprising substances capable of formingclathrate hydrates, asdissolved in anaqueous medium, such as that described in Long, J., Lederhos, A., Sum, A., Christiansen, R., Sloan, E.D.; Prep. 73rd Ann. GPA Conv., 1994, pp. 1-9.
  • the system of this type shall give clathrate hydrates as precipitated therein, when left under particular pressure and temperatureconditions.
  • the substances capable of forming clathrate hydrates include, for example, gases such as carbondioxide, nitrogen, oxygen, hydrogensulfide, argon, xenon, ethane, propane, butane, etc., and liquids such as tetrahydrofuran, etc.
  • gases such as carbondioxide, nitrogen, oxygen, hydrogensulfide, argon, xenon, ethane, propane, butane, etc.
  • liquids such as tetrahydrofuran, etc.
  • the aqueous mediumin the systemin includes wateraswellas aqueous solutionsofsaltsuchas saline, seawater, etc.
  • the "system capable of forming clathrate hydrates" as referred to herein also includes systems of suspension or dispersionwhereanaqueousphasecomprisinggases suchasethane, propane, etc.
  • an aqueous medium such as water, seawater or the like has been suspended or dispersed in an oil phase comprising liquefied gas, oil or the like and such systems where a gaseous phase comprising natural gas or the like additionallyexistsinthe aqueousphase, such asthoseinnatural gas wells and oil wells.
  • the amount of the clathrate hydrate inhibitor of the present invention to be added to the system capable of forming clathratehydrates maybegenerallyfrom0.01to30partsbyweight relative to 100 parts of the free water existing in the system. If its amount is less than 0.01 parts by weight, the clathrate hydrateinhibitorcouldnotoftenexhibitsufficientlyits effect. On the other hand, even if its amount is more than 30 parts by weight, not only the effect of the inhibitor is often saturated and could no more be enhanced in proportion to the amount of the inhibitor added but also the viscosity of the system to which the inhibitor has been added would often be increased much to thereby noticeably lower the fluidity of the system. For these reasons, such smaller or larger amounts of the clathrate hydrate inhibitor to be added are unfavorable.
  • the clathrate hydrate inhibitorof the present invention maycontainvariousadditives, suchas rustinhibitors, lubricants, dispersing agents, etc.
  • a mixture comprised of 6 ml of a sample solution as prepared by dissolving a sample to be tested in an artificial seawater (for this, referred to was ASTM D1141-90) at a concentration of 0.5 % by weight and 2 ml of tetrahydrofuran was put into a test tube of 13 mm x 100 mm along with 3/8-inch stainless balls, and the test tube was hermeticallysealedinsuchawaythatnoairbabblesweretherein. Then, the test tube was set in a water tank and rotated therein at 0°C andat a rotationspeedof 15 rpm, whereuponthe timeneeded before the stainless balls in the test tube were no more moved at all (ball stop time) was measured. On the basis of the time thus measured, the sample was evaluated. The longer the time, the higherthe clathrate hydrate inhibitingeffect of the sample tested.
  • the flask was put into an oil bath at 60°C, in which the solution in the flask was heated up to 60°C. After the temperature of the solution was stabilized at 60°C, 1 ml of 10 wt.%-solution of a radical polymerization initiator, 2,2- azobis(2,4-dimethylvaleronitrile) (V-65, produced by Wako Pure Chemicals Co. ) intoluenewas addedto thesolutionwhilestirring it.
  • V-65 2,2- azobis(2,4-dimethylvaleronitrile)
  • the flask was put into an oil bath at 60°C, in which the solution in the flask was heated up to 60°C. After the temperature of the solution was stabilized at 60°C, 2 ml of 10 wt.%-solution of a radical polymerization initiator, 2,2- azobis(2,4-dimethylvaleronitrile) (V-65) in toluene was added to the solution while stirring it.
  • V-65 2,2- azobis(2,4-dimethylvaleronitrile)
  • the flask was put into an oil bath at 60°C, in which the solution in the flask was heated up to 60°C. After the temperature of the solution was stabilized at 60°C, 0.1 ml of 10 wt.%-solution of a radical polymerization initiator, 2,2- azobis(2,4-dimethylvaleronitrile) (V-65) in toluene was added to the solution while stirring it.
  • V-65 2,2- azobis(2,4-dimethylvaleronitrile)
  • the tipof thenitrogen-introducingtube wasministerto the solution, through which nitrogen was bubbled thereinto for 10 minutes to purge away the dissolved oxygen from the system. After this, the tip of the nitrogen- introducing tube was drawn up above the liquid surface.
  • the flask was put into an oil bath at 60°C, in which the solution in the flask was heated up to 60°C. After the temperature of the solution was stabilized at 60°C, 1 ml of 10 wt.%-solution of a radical polymerization initiator, 2,2- azobis(2,4-dimethylvaleronitrile) (V-65, produced by Wako Pure Chemicals Co. ) intoluenewas addedto thesolutionwhilestirring it.
  • V-65 2,2- azobis(2,4-dimethylvaleronitrile)
  • a clathrate hydrate inhibitor sample (5) was produced in the same manner as in Example 4, except that 25 g of N-vinyl- pyrrolidone and 1.4 g of butyl acrylate were used.
  • a clathrate hydrate inhibitor sample (6) was produced in the same manner as in Example 1, except that 25 g of N-vinyl- pyrrolidone and 0.7 g of butyl acrylate were used.
  • Vinyl pyrrolidone-1-butene copolymer (ANTARON® P-904, obtained from ISP Japan, Co.) was directly used by itself and evaluated in accordance with the above-mentioned test method, which revealed that the ball stop time for this was 24 hours. Comparative Example 3>
  • a comparative, clathratehydrate inhibitorsample (3) was produced in the same manner as in Example 4 , except that 2.2 g of ethyl acrylate was used in place of 2.8 g of butyl acrylate.
  • a comparative, clathratehydrate inhibitor sample (4) was produced in the same manner as in Example 4 , except that 4.0 g of 2-ethylhexyl acrylate was used in place of 2.8 g of butyl acrylate.
  • the present invention is useful in inhibiting the formation of clathrate hydrates, for example, in pipe lines for production for oil and natural gas and for transporting them, in cooling wather circulating in factories, in cooling water for various engines, etc.
  • the clathrate hydrate inhibitor of the present invention is stable in the system that may form clathrate hydrates, and has the high ability to retard the formation of clathrate hydrates and to inhibit the growth thereof.

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Abstract

L'invention porte sur (1) des inhibiteurs d'hydrates de clathrate comprenant un composé macromoléculaire dans la partie pendante du noyau à 5 à 15 chaînons est directement relié à la chaîne polymère principale par l'intermédiaire d'un des atomes à l'intérieur du noyau, comme par exemple, le pyrrolidone polyvinylique, le pipéridinone polyvinylique, le caprolactame polyvinylique, etc. modifié par des monomères vinyliques; ou un composé macromoléculaire obtenu par copolymérisation des monomères dans lesquels la partie pendante du noyau à 5 à 15 chaînons est directement reliée au groupe éthyléniquement non saturé par l'intermédiaire d'un des atomes à l'intérieur du noyau, comme par exemple, le vinylpyrrolidinone, le vinylcaprolactame et le C3 - C6 alkyle (méth) acrylate; et sur (2) le procédé permettant d'inhiber la formation des hydrates de clathrate dans lequel lesdits inhibiteurs sont utilisés.
PCT/JP1996/001396 1995-05-26 1996-05-24 Inhibiteur d'hydrates de clathrate et procede permettant d'inhiber la formation des hydrates de clathrate dans lequel il est utilise WO1996037684A1 (fr)

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JP7/127757 1995-05-26
JP12775795 1995-05-26
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6222083B1 (en) 1999-10-01 2001-04-24 Exxonmobil Upstream Research Company Method for inhibiting hydrate formation
US6319971B1 (en) 1997-05-22 2001-11-20 Rf-Procom A/S Composition for controlling clathrate hydrates and a method for controlling clathrate hydrate formation
WO2002084072A1 (fr) * 2001-04-11 2002-10-24 Kuraray Specialities Europe Gmbh Additifs utilises pour inhiber la formation d'hydrates de gaz
EP1220821A4 (fr) * 1999-10-12 2004-08-25 Isp Investments Inc Inhibition de la corrosion et d'hydrates de gaz lors du transport d'eau et d'hydrocarbures dans un pipeline
CN106190060A (zh) * 2015-05-25 2016-12-07 西北大学 一种复配型天然气水合物抑制剂
CN110467701A (zh) * 2019-08-26 2019-11-19 西北大学 一种天然气水合物抑制剂、复配抑制剂及其制备方法
CN113583645A (zh) * 2021-06-30 2021-11-02 中国石油大学(华东) 水合物抑制剂及其应用
CN115353584A (zh) * 2022-09-23 2022-11-18 中国科学院广州能源研究所 一种基于环状乙烯基共聚物的复合水合物动力学抑制剂及其应用
CN116535571A (zh) * 2023-05-29 2023-08-04 中国石油大学(北京) 一种水合物动力学抑制剂及其制备方法和应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1423433A (fr) * 1964-01-20 1966-01-03 Gen Aniline & Film Corp Utilisation en teinture de copolymères greffés de n-vinyl lactames
US3244658A (en) * 1960-11-16 1966-04-05 Gen Aniline & Film Corp Process of preparing a stable aqueous emulsion
GB1409145A (en) * 1973-07-26 1975-10-08 Gaf Corp Stable aqueous emulsions of polymeric n-vinyl lactams
WO1993025798A1 (fr) * 1992-06-11 1993-12-23 Shell Internationale Research Maatschappij B.V. Procede d'inhibition de la formation d'hydrates de gaz
WO1994012761A1 (fr) * 1992-11-20 1994-06-09 Colorado School Of Mines Procede de regulation d'hydrates de clathrate dans des systemes a fluide
WO1995019408A1 (fr) * 1994-01-13 1995-07-20 Bp Exploration Operating Company Limited Inhibition de formation d'hydrates

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3244658A (en) * 1960-11-16 1966-04-05 Gen Aniline & Film Corp Process of preparing a stable aqueous emulsion
FR1423433A (fr) * 1964-01-20 1966-01-03 Gen Aniline & Film Corp Utilisation en teinture de copolymères greffés de n-vinyl lactames
GB1409145A (en) * 1973-07-26 1975-10-08 Gaf Corp Stable aqueous emulsions of polymeric n-vinyl lactams
WO1993025798A1 (fr) * 1992-06-11 1993-12-23 Shell Internationale Research Maatschappij B.V. Procede d'inhibition de la formation d'hydrates de gaz
WO1994012761A1 (fr) * 1992-11-20 1994-06-09 Colorado School Of Mines Procede de regulation d'hydrates de clathrate dans des systemes a fluide
WO1995019408A1 (fr) * 1994-01-13 1995-07-20 Bp Exploration Operating Company Limited Inhibition de formation d'hydrates

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6319971B1 (en) 1997-05-22 2001-11-20 Rf-Procom A/S Composition for controlling clathrate hydrates and a method for controlling clathrate hydrate formation
US6222083B1 (en) 1999-10-01 2001-04-24 Exxonmobil Upstream Research Company Method for inhibiting hydrate formation
EP1220821A4 (fr) * 1999-10-12 2004-08-25 Isp Investments Inc Inhibition de la corrosion et d'hydrates de gaz lors du transport d'eau et d'hydrocarbures dans un pipeline
WO2002084072A1 (fr) * 2001-04-11 2002-10-24 Kuraray Specialities Europe Gmbh Additifs utilises pour inhiber la formation d'hydrates de gaz
CN106190060A (zh) * 2015-05-25 2016-12-07 西北大学 一种复配型天然气水合物抑制剂
CN110467701A (zh) * 2019-08-26 2019-11-19 西北大学 一种天然气水合物抑制剂、复配抑制剂及其制备方法
CN110467701B (zh) * 2019-08-26 2020-10-27 西北大学 一种天然气水合物抑制剂、复配抑制剂及其制备方法
CN113583645A (zh) * 2021-06-30 2021-11-02 中国石油大学(华东) 水合物抑制剂及其应用
CN113583645B (zh) * 2021-06-30 2022-08-02 中国石油大学(华东) 水合物抑制剂及其应用
CN115353584A (zh) * 2022-09-23 2022-11-18 中国科学院广州能源研究所 一种基于环状乙烯基共聚物的复合水合物动力学抑制剂及其应用
CN115353584B (zh) * 2022-09-23 2023-11-10 中国科学院广州能源研究所 一种基于环状乙烯基共聚物的复合水合物动力学抑制剂及其应用
CN116535571A (zh) * 2023-05-29 2023-08-04 中国石油大学(北京) 一种水合物动力学抑制剂及其制备方法和应用

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