WO1994025727A1 - Inhibition de l'hydrate - Google Patents

Inhibition de l'hydrate Download PDF

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Publication number
WO1994025727A1
WO1994025727A1 PCT/GB1994/000952 GB9400952W WO9425727A1 WO 1994025727 A1 WO1994025727 A1 WO 1994025727A1 GB 9400952 W GB9400952 W GB 9400952W WO 9425727 A1 WO9425727 A1 WO 9425727A1
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WIPO (PCT)
Prior art keywords
additive
group
amino
derivative
additives
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PCT/GB1994/000952
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English (en)
Inventor
Simon Neil Duncum
Antony Roland Edwards
Kevin Raymond Gordon
Christopher Brunsden Holt
Alexander Lips
Christopher George Osborne
Original Assignee
Bp Exploration Operating Company Limited
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.)
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Publication date
Priority claimed from GB939309132A external-priority patent/GB9309132D0/en
Priority claimed from GB939309106A external-priority patent/GB9309106D0/en
Priority claimed from GB939322209A external-priority patent/GB9322209D0/en
Application filed by Bp Exploration Operating Company Limited filed Critical Bp Exploration Operating Company Limited
Publication of WO1994025727A1 publication Critical patent/WO1994025727A1/fr

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    • 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
    • C09K8/02—Well-drilling compositions
    • C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
    • 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
    • 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 hydrate inhibitors and a method for inhibiting the formation of hydrates in particular to a method for inhibiting the formation of hydrates in the petroleum and natural gas industries.
  • 5 Hydrates are formed of two components, water and certain gas molecules, e.g. alkanes of 1-4 carbons, especially methane and ethane, such as those found in natural gas. These 'gas' hydrates will form under certain conditions, i.e. when the water is in the presence of the gas and when the conditions of high pressure and 10 low temperature reach respective threshold values.
  • the gas may be in the free state or dissolved in a liquid state, for example, as a liquid hydrocarbon.
  • Hydrate formation in the field may cause blocked pipelines, valves and other process equipment.
  • the problem is particularly of concern as natural gas and gas condensate resources are discovered where operating conditions surpass these threshold values, i.e. in deep cold water and on- 20 shore in colder climates.
  • Hydrates can also form in association with the underground hydrocarbon reservoir thus impeding production by blockage of reservoir pores.
  • Hydrate formation may also occur during natural gas cryogenic liquefaction and separation.
  • a typical situation where hydrate formation can occur is in offshore operations where produced fluids are transported in a long vertical pipeline, for example, a riser system.
  • Such produced fluids normally include light gases known to form hydrates and water.
  • a temperature of 4.5 a C and a pressure of 150 psi would be sufficient for hydrate formation.
  • Electrolytes for example, ammonia, aqueous sodium chloride, brines and aqueous sugar solutions may be added to the system.
  • ethanol or other polar organic substances for example, ethylene glycol or other glycols may be used.
  • Methanol injection has been widely used to inhibit hydrate formation. However, it is only effective if a sufficiently high concentration is present since at low concentrations there is the problem of facilitation of hydrate formation. Also for methanol to be used economically under cold environmental conditions there must be early separation and expulsion of free water from the well in order to minimise methanol losses in the water phase.
  • a method for inhibiting or retarding hydrate formation comprises adding an additive (hereinafter called the Additive) which is at least one of (i) a hydrophilic colloid (ii) a cyclic compound with at least one -(C-O)-O- group in a ring, and (iii) an amino carbohydrate, and preferably also at least one of (iv) an amino acid or derivative thereof, (v) an amino alcohol or derivative thereof, (vi) a glycol ether or derivative thereof (vii) a hydroxy acid or a derivative thereof, and (viii) a corrosion inhibitor and (ix) a polymer of an ethylenically unsaturated compound, the Additive being added in an amount effective to inhibit or retard hydrate formation, to a medium susceptible to hydrate formation.
  • an additive hereinafter called the Additive
  • the Additive which is at least one of (i) a hydrophilic colloid (ii) a cyclic compound with at least one -(C-O)
  • the hydrophilic colloid is an organic solid which is soluble in boiling water, e.g. to at least 10 g/1 or dispersible in boiling water and may be soluble (at least 10 g/1) or dispersible in water at 20 B C. It usually absorbs water strongly, e.g. to at least three times such as 3-15 times its weight of water at 20 fi C, and swells in water. It can form a colloidal solution or dispersion in water and may have an average molecular weight of at least 10,000, e.g. 100,000-10,000,000. It may be a polysaccharide, e.g. with at least 4 carbohydrate units, especially one with at least some galactose units, e.g.
  • the polysaccharide may be a natural gum, e.g. guar, agar, arabic, locust bean, karaya, carob or tragacanth gum, or a cellulosic material, such as starch, which may be unmodified or modified as an alkyl ether, e.g. methyl or ethyl cellulose or hydroxyalkyl ether, e.g. hydroxyethyl cellulose or carboxy alkylated starch, e.g. carboxy methyl cellulose (CMC).
  • alkyl ether e.g. methyl or ethyl cellulose or hydroxyalkyl ether, e.g. hydroxyethyl cellulose or carboxy alkylated starch, e.g. carboxy methyl cellulose (CMC).
  • CMC carboxy methyl cellulose
  • the polysaccharide may also be a synthetic, e.g. biosynthetic gum, the result of a microbiological process, e.g. fermentation; xanthan gum, which can be made by fermentation of dextrose with Xanthomonas campestris cultures is preferred, especially water soluble versions of xanthan gum.
  • the colloid may also be proteinaceous, in particular gelatin or carrageenan (a seaweed extract), e.g. x-carrageenan.
  • the colloid may also be a polyuronic acid or salt thereof, e.g. sodium or ammonium salt or ester thereof, such as a hydroxy alkyl ester (e.g. of propylene glycol), especially with beta-D-mannuronic acid residues; alginic acid and especially sodium alginate is preferred.
  • Additive (ii) is a cyclic compound with at least one -(C-0)- 0- group in a ring.
  • Such additives are usually cyclic lactones or carbonate esters, preferably with 4-8 atoms in total in the ring containing the -(C-O)-O group.
  • the additives are preferably of formula -R 6 -O a (C-0)-0- , where a is 0 or 1 and R 6 is a divalent organic group especially with at least one chain of carbon atoms, whose terminal members are bonded to the -(0) a (C-0)-0- group.
  • the group R° is preferably a hydrocarbyl group, e.g. of 2-20 carbons, especially 2-8 carbons.
  • R ⁇ may be an alkylene group of 2-10 carbons, preferably forming with the -(0) a (C-0)-0- group a 4-8, especially 6 or 7 membered ring in particular in lactones;
  • Group R° is especially an alkylene group with one terminal CH2 group, in particular that attached to the non carbonyl oxygen atom in a lactone, but preferably group R° is an alkylene group with 2 terminal CH2 groups
  • R° may be 1,2 ethylene, 1,3 propylene, 1,4 butylene, 1,4-pentylene, 1,5-pentylene and 6-methyl-l,5-pentylene.
  • R° may also be cycloalkylene group e.g.
  • R° may also be a divalent aromatic group e.g. of 6- 10 carbons such as a divalent hydrocarbyl group e.g.
  • the group R° may be attached to a hydrocarbyl polymer with the or each -0 a (C-0)-0- group present as part of a ring, pendant on or fused to the hydrocarbyl polymer chain.
  • the rings usually have 5-8 ring atoms.
  • the above groups R° may be unsubstituted by any non hydrocarbylsubstituents, and any alkyl chains present are usually of less than 8 e.g. less than 4 carbons.
  • Examples of the cyclic compounds which are lactones are propiolactone, gamma butyrolactone, gamma valerolactone, 6- caprolactone and the lactone of 2-hydroxymethyl benzoic acid
  • examples of the cyclic carbonates are those from ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,2 and 1,3- butanediols, cyclohexane 1,2-diol and o-catechol, though polyvinyl carbonate may also be used e.g. that derived from "polyvinyl alcohol” (formed by hydrolysis of polyvinyl acetate).
  • Additive (iii) is an amino carbohydrate in which an amino group is preferably a secondary or especially primary amino group ( H2) , especially the additive containing at least 1 amino group per carbohydrate ring.
  • the amino group is usually bonded directly to a carbon atom in the carbohydrate ring or is separated therefrom by a carbon atom e.g. as in an amino methyl carbohydrate.
  • the Additive contains at least one carbohydrate ring which may be a pentose or especially a hexose ring, and the amino group is especially a 2-amino group in the ring.
  • amino carbohydrates examples include glycosamine and fructosamine, as well as polymers thereof such as chitosan, (polyglucosamine, formed by enzymic hydrolysis of chitin) ; the polymers may have molecular weights of 10,000 to 5 million e.g. 30,000-200,000 or 100,000-5 million such as 500,000 to 3 million.
  • the Additives (i), (ii) or (iii) may be used above or mixed with each other or preferably mixed with at least one of the additives (iv)-(viii), especially (viii) .
  • the Additive (iv)-(vii) (and often viii) is usually at least difunctional, e.g. with 2-4 functional groups.
  • It preferably has a structure including an oxygen atom in an ether group or hydroxyl group and at least one of another oxygen atom in an ether or keto group and a nitrogen atom in an amino group, said 0 and N and/or 0 atoms being spaced by 1-6, preferably 2-5, especially 2 or 3 carbon atoms, which may be in an aliphatic, cycloaliphatic or aromatic group.
  • the Additive (iv) may be an amino acid or derivative thereof, in particular one with at least one asymmetric carbon atom; the Additive may be in the racemic form, but is preferably optically active, i.e. in D or especially L-form.
  • the Additive (iv) may be in the form of the free carboxylic acid (including a carboxylic anion form, e.g. as a sodium or potassium salt) or as a derivative of said carboxylic acid, e.g. as an amide (e.g. with ammonia or with a primary amine which may or may not be a hydroxyamine) or hydrazide (e.g. with hydrazine) or an ester, e.g.
  • the amino acid (or derivative) is preferably an alpha amino carboxylic acid, especially with the amino and carboxylic acid groups bonded to an aliphatic carbon atom, especially a -CH- group.
  • the amino group in the amino acid may also be in a non alpha position relative to the acidic group, e.g.
  • the Additive may contain an amino group in H2 or NH3 form (whether as a salt, e.g. hydrochloride or hydrobro ide or zwitter ion form) or an N-acyl derivative thereof, such as with an alkanoic acid, e.g. of 1-10 carbons such as acetic acid, or an aromatic acid, e.g.
  • a carbonate half ester such as a monoalkyl carbonate, e.g. mono tert butyl carbonate or an aromatic or aralkyl carbonate, e.g. phenyl carbonate or benzyl carbonate.
  • Derivatives of the amino acid with an N-hydroxy alkyl group, e.g. of 1-4 carbons, e.g. 1 or 2 carbons such as hydroxymethyl may also be used; such derivatives may also involve an NH ring in which the hydroxy 1 and acid groups are substituents as in hydroxy proline.
  • the Additive (iv) is however preferably of formula (I) R- CH(NH2)C00H (or a derivative thereof), wherein R represents hydrogen or an aromatic, aralkyl, heterocyclic, heterocyclic aliphatic, cycloaliphatic or aliphatic group.
  • the aromatic group preferably has 6-20 carbons, e.g. 6-10 carbons, such as phenyl optionally substituted by amino, hydroxyl carboxylic or alkyl, e.g. of 1-6 carbons such as methyl or ethyl or alkoxy, e.g. of 1-6 carbons such as methoxy or ethoxy.
  • the aralkyl group preferably comprises an aromatic group as described above and the alkyl part of the aralkyl group preferably has 1-4 carbons such as methyl or 1 or 2 ethyl.
  • the heterocyclic ring in the heterocyclic or heterocyclic alkyl group may be a nitrogen heterocyclic ring with 1-3 ring nitrogens as in a 1,3-imidazole ring.
  • the cycloaliphatic group may have 5-8 carbons, e.g. cyclohexyl or cyclopentyl.
  • the group R is especially an aliphatic group, e.g. of 1-6 carbon atoms, in particular a saturated hydrocarbyl group, e.g.
  • the amino acid which is the Additive (iv) or from which it is derived may be a basic amino acid with 2 or 3 amino groups and 1 carboxylic acid group, such as ornithine, lysine, arginine or guanidine or histidine, especially in its L-form, or an acidic amino acid with 2 or 3 carboxylic acid groups and 1 amino group, such as glutamic or aspartic acid or amide, especially in its In ⁇ form.
  • the amino acid, which the Additive (iv) is or from which it is derived has 1 amino and 1 carboxylic group (or derivative thereof) especially one of formula I, in which R is alkyl or hydroxyalkyl, alkoxyalkyl, mercaptoalkyl or alkylmercaptoalkyl group or in the case of mercaptoalkyl groups (as in cysteine) the corresponding disulphide (as in cystine); such amino acids are preferably in their L forms.
  • the Additive is thus preferably serine, threonine, valine, leucine, isoleucine, homoserine, methionine, cysteine or cystine; L-serine is preferred.
  • the Additive of formula 1 may also be of formula II
  • R * - * is OH, OCH3, OC 2 H 5 , NHNH 2 or H
  • R 4 is NH 2 or NH3
  • each of X, Y and Z is hydrogen or Oil and n is a number in the range 0 to 6, or a polymer thereof when R * - * is NH2 and may be phenylalanine or tyrosine or their carboxylic acid derivatives.
  • X, Y and Z represents an alkoxy, acyloxy, keto, amino or carboxyl group such as an alkoxy group of 1-6 carbons, e.g.
  • group R does not comprise an aromatic group.
  • the amino acid may also be an amino sulphonic acid, e.g. with an aliphatic group, e.g. of 1-10 carbons, aromatic group, e.g. of 6-16 carbons or cycloaliphatic group, e.g. of 5-7 carbons, to which the amino and sulphonic groups are attached.
  • Taurine and amino benzene sulphonic acid may be used.
  • the Additive (v) may also be an hydroxyamine, which is usually an aliphatic compound with 2-10 carbon atoms, especially 3-6 carbon atoms, in particular a saturated aliphatic compound.
  • the Additives (v) may contain 1-5 hydroxyl groups, e.g. 1, 2 or 3 hydroxy groups and 1-3 amino groups, e.g. 1 or 2 amino groups, which may be of formula NR-'-R- ⁇ , where R-- and R*-- are as defined above.
  • the Additive (v) may be a secondary or tertiary amine, but is preferably a primary amine, e.g.
  • the hydroxyamine may be used as such or in the form of a salt with an inorganic acid, e.g. hydrochloric acid or an organic acid, e.g. an aliphatic mono or di carboxylic acid such as one with 1-10 carbon atoms, e.g.
  • acetic or propionic acid or maleic or oxalic acid or an organic sulphonic acid or organic sulphate half ester each of which usually contains 1-20 carbons in the organic group, which is preferably a hydrocarbyl group such as alkyl e.g. of 1-8 carbons such as methyl or ethyl especially for the sulphonic acid, or of 1-24 such as 8-22 carbons such as octyl, lauryl and stearyl, especially for the half ester, or may be aryl of 6-20 carbons such as phenyl or tolyl or aralkyl of 7-21 carbons such as benzyl.
  • a hydrocarbyl group such as alkyl e.g. of 1-8 carbons such as methyl or ethyl especially for the sulphonic acid, or of 1-24 such as 8-22 carbons such as octyl, lauryl and stearyl, especially for the half ester, or may be aryl of 6
  • Additives (v) are tris-(2 hydroxyethyl) amine, tyrosinol or valinol (e.g. the L isomer) and especially tris- hydroxymethyl-methylamine (HOCH2)3C H2 and its corresponding ammonium chloride and lauryl sulphate salt.
  • the Additive (vi) may also be an ether, which contains at least 1 such as 1-6 ether oxygen atoms and 0-6, e.g. 1 oxygen atoms in a hydroxyl group, the number of ether oxygen atoms being preferably at least the same as and especially 0-3 more than the number of hydroxyl oxygen atoms.
  • the Additives (vi) are glycol ethers, derived structurally from a diol, e.g. an aliphatic diol of 2-4 carbon atoms such as ethylene glycol or 1,3- propylene glycol, or structurally from a self condensate thereof, e.g. di or triethylene glycol, or mixtures of said diols.
  • a diol e.g. an aliphatic diol of 2-4 carbon atoms such as ethylene glycol or 1,3- propylene glycol
  • a self condensate thereof e.g. di or triethylene glycol, or mixtures of said diols.
  • One or both hydroxyl groups from such diols (or condensate thereof) may be etherified, e.g. with an alkyl group such as one with 1-10 carbons, e.g. methyl, ethyl, n-propyl or n-butyl.
  • Additives (vi) are the reaction products of an alkanol with ethylene oxide and/or propylene oxide.
  • One or more hydroxyl groups in the ether may be acylated, e.g. with an aliphatic or aromatic acyl group with 1-10 or 6-16 carbon atoms respectively such as acetyl or benzoyl.
  • Examples are 2-butoxyethanol (monobutyl glycol ether) and 2(2 ⁇ --butoxy ethoxy) ethanol (mono butyldiethylene glycol ether) and their corresponding acetates.
  • the Additive (vii) is a hydroxy acid (especially a hydroxy carboxylic acid) which may be an aliphatic, aromatic, cycloaliphatic, cycloaliphatic-aliphatic or araliphatic compound with 1-20, 6-20, 5-7, 5-25 or 7-20 carbon atoms respectively.
  • the aliphatic hydroxy acid is an alpha hydroxy acid, e.g. of 2-6 carbons such as glycollic, lactic or citric acid, while the aromatic and araliphatic acids may be salicylic, p- hydroxybenzoic or 2-(p-hydroxyphenyl) propionic acid.
  • Derivatives of the additive (vii) on the carboxyl group may be used such as salts, e.g.
  • esters [e.g. with an alcohol with 1 hydroxyl group or with a polyol (though esters from polyols are preferably absent)], amides or hydrazides, in particular when the additive (vii) contains at least one group -COX where X*'- is as defined below.
  • the hydroxy acid is a cycloaliphatic-aliphatic compound, especially one with at least one of a keto and an olefinic unsaturated group, in particular abscisic acid or a derivative thereof of formula
  • X*-- represents OR ⁇ , wherein R-- * is hydrogen or alkyl, e.g. of 1-6 carbons optionally hydroxy substituted, such as methyl, ethyl or 2-hydroxyethyl, or X represents amino (e.g. H ) or hydrazido (e.g.NHNH 2 ).
  • the additive (viii) is a corrosion inhibitor, e.g. for steel and usually one suitable for use in anaerobic environments, and is especially a nitrogenous one with 1 or 2 nitrogen atoms.
  • the corrosion inhibitor may be a primary, secondary or tertiary amine, or a quaternary ammonium salt, usually in all cases with at least one hydrophobic group, usually a benzene ring or a long chain alkyl group e.g.
  • the inhibitor preferably has surfactant activity and especially surface wetting activity. It may be a quaternary ammonium salt, a long chain aliphatic hydrocarbyl N-heterocyclic compound or a long chain amine.
  • the quaternary salt may be an (optionally alkyl substituted) benzyl trialkyl ammonium halide, in particular when at least 1 and especially 1 or 2 alkyl groups is of 1-20, in particular 8-20 carbons such as cetyl and the other alkyl groups are of 1-6 carbons such as methyl or ethyl; examples are benzyl alkyldimethyl ammonium chloride and Benzalkonium chlorides.
  • the aliphatic hydrocarbyl group in the heterocyclic compound usually has 8-24 carbons in the hydrocarbyl group, preferably a linear saturated or mono or diethylenically unsaturated hydrocarbyl group; cetyl-, stearyl and especially oleyl- groups are preferred.
  • the N- heterocyclic compound usually has 1-3 ring N atoms, especially 1 or 2 which usually has 5-7 ring atoms in each of 1 or 2 rings; imidazone and imidazoline rings are preferred.
  • the heterocyclic compound may have the aliphatic hydrocarbyl group on an N or preferably C atom in the ring; the ring may also have an amino- alkyl (e.g.
  • the long chain amine usually contains 8-24 carbons and preferably is an aliphatic primary amine, which is especially saturated or mono ethylenically unsaturated; an example is dodecylamine.
  • Mixtures of Additives (i) , (ii) or (iii) with more than one of the same type of any of (iv), (v) , (vi) , (vii) or (viii) may be used, but also mixtures with ones of different types (iii), (iv), (v) , (vi) , Vii) and/or (viii), especially mixtures of (i), (ii)or (iii) with (viii) and at least one of (iv), (v) , (vi) or (vii).
  • Mixtures of Additive (viii) and at least 2 of Additives (i), (iii), (v) and (ix) are preferred.
  • the mixtures may contain at least 1%, but preferably at least 10% and not more than 90% of each Additive, especially in the form of two component mixtures with 25-75; 75-25 ratios of the two components which are in particular mixtures of (i), (ii) or (iii) with (viii).
  • Such mixtures form another aspect of the invention, so there is also provided a blend which comprises a mixture of at least two Additives (i), (ii) , (iii), (iv), (v) , (vi) , (vii) and/or (viii), so long as it comprises at least one Additive (i), (ii) or (iii).
  • Such blends are primarily for use as gas hydrate inhibitors.
  • Additives (i-ix) for use as hydrate inhibitors are preferably water soluble, e.g. to at least 10 g/1 in water at 20 a C. They may be used undiluted, but preferably are in solution such as aqueous solution, for example, as a solution in brine, or preferably an alcohol, for example, a water miscible one such as methanol or ethanol. Preferably are used Additives i-ix, e.g. (i) with (iv)-(viii) an aqueous solution of which has a pH 1.5-12, e.g. 4-9, either naturally or after adjustment of the pH. Additives (viii) are preferably used in alcoholic solution.
  • the Additive(s) is suitably injected at concentrations in the range 10 to 20,000 ppm, e.g. 30 to 10,000 ppm, especially 50- 1200 ppm based on the total water volume in the medium, in which hydrate formation is to be inhibited, in particular at concentrations in the range 100-700 ppm.
  • the amount of methanol, ethanol, or mono, di or tri ethylene glycol added relative to the total water volume in the medium is usually less than 10%, e.g. less than 5% or 2%, but especially less than 10,000 ppm.
  • the inhibitors may be injected at normal ambient conditions of temperature and pressure.
  • blends of at least one Additive (i) (ii) or (iii) and (ix) a polymer of a polar ethylenically unsaturated compound can give synergistic results compared to the ingredients above, so that blends of at least one Additive (iii) and a polyvinyl pyrrolidone, had a gas hydrate inhibition time in a test very many more times than each individually, e.g. at least two times more than the sura of their individual times.
  • the Additives may thus also be used in formulations which also comprise a polymer of a polar ethylenically unsaturated compound; these Formulations constitute another aspect of the invention.
  • the polymer of the polar ethylenically unsaturated compound (ix) is usually water soluble (to at least 10 g/1 at 20 a C) and advantageously has a molecular weight of 1000-1500,000, e.g. 5000- 1,000,000, preferably 200,000-1,000,000 and especially 400,000- 900,000.
  • the ethylenically unsaturated compound is preferably a vinyl or methyl vinyl group, and the polar group may be an alcohol, carboxylic acid, sulphonic acid or N-heterocyclic group, especially pyrrolidone.
  • Preferred polar compounds are thus vinyl sulphonic acid, acrylic and methacrylic acids and N-vinyl pyrrolidone and "vinyl alcohol".
  • the polymers may be copolymers, but are preferably homopolymers of these polar compounds, especially polyvinyl alcohol (e.g. hydrolysed polyvinyl acetate), polyacrylates and polyvinyl pyrrolidone.
  • the amount of said polymer is usually 10-1000%, such as 50-300% or 90-250% based on the weight of the total of Additive(s) e.g. (i)-(iii) or (iv)- (vii) .
  • Blends of the colloid and at least one Additive (iv)-(vii) and/or a polymer of a polar ethylenically unsaturated compound can give synergistic results compared to the ingredients alone, so that blends of at least one Additive (iv)-(vii), the colloid and optionally a polyvinyl pyrrolidone, can have a gas hydrate inhibition time in a test very many more times than each individually, e.g. at least two times more than the sum of their individual times.
  • Formulations may be used in amount of 50-10,000 ppm, preferably 2000-5000 ppm or 150-2000 ppm, e.g.
  • the Formulations may also comprise at least one Additive (iv)-(viii). They may comprise the corrosion inhibitor (Additive (viii)) and the polymer (ix) as well as the Additive (i), (ii) or (iii), which are then preferably in the weight ratio 5-200:100-2000:100-2000, especially 10-100:400-800:150-800 or as percentages of the total formulation weight of corrosion inhibitor, polymer and Additive (i), (ii) or (iii) of 1-20%, 40-80% and 10-60% respectively, especially 1-10%, 40-70% and 20-50% respectively.
  • the Formulations may also comprise the hydrophilic colloid (i) and total Additive (iv)-(viii) in relative amounts of 1:99 to 99.9:0.1, especially 20:80 to 90:10, though the relative amounts of colloid to Additive (viii) are preferably 95:5 to 99:0.5.
  • the relative amounts of colloid (i) to polymer (ix) may be 1:99 to 99:1 such as 10:90 to 90:10 or 30:70 to 70:30.
  • the formulations may comprise (a) the corrosion inhibitor (Additive (viii)), and (b) the colloid (i) alone or with the polymer (ix) as well as the (c) Additive (iv)-(viii), which are then preferably in the weight ratio (a):(b):(c) of 1-200:100-2000:100-2000, especially 2- 100:200-800:150-500 or as percentages of the total formulation weight of (a), (b) and (c) of 0.1-20%, 40-80% and 10-50% respectively, especially 0.1-10%, 50-70% and 20-40% respectively.
  • Additive (viii) is usually present in an amount of 0.1-50% (by weight of the total of Additives (i), (ii) and
  • the Formulation may also contain another hydrate inhibitor and/or a water dispersant or surfactant, in particular an anionic one such as sodium dodecyl sulphonate or stearic acid and in amount of 1-10% of the Formulation weight and/or a biocide, e.g. formaldehyde, e.g. in amount of 10-10,000 ppm and/or a metal complexant such as citric acid (e.g. in amount of 10-10,000 ppm) all amounts being in relation to the total weight of the
  • the Formulations may be used to retard or inhibit hydrate formation in the same manner as the individual Additives, as described above.
  • the inhibitor Additives and Formulations of the present invention are suitable for use in media containing water and gas, in particular in the petroleum, natural gas and gas industries. In particular, they may be suitable for use during the transportation of fluids comprising gas and water. They may also be suitable for use in oil based drilling muds to inhibit hydrate formation during drilling operations.
  • the invention provides an oil based drilling mud, which comprises as hydrate inhibitor at least one Additive, as such or in a Formulation.
  • the inhibitors When used during the transportation of fluids, e.g. gases in pipelines the inhibitors may be injected continuously or batchwise into the pipeline upstream of conditions (e.g. the locus in siad pipeline) wherein hydrate formation may occur, which are often 20-
  • the inhibitors may be added to the drilling muds in the mud tank at the wellhead.
  • the hydrate inhibitor test apparatus consisted of a simple 316 stainless steel pressure cell, with a usable internal volume of 1000 cm--' with a thermostated cooling jacket, a sapphire window, an inlet and outlet and a platinum resistance thermometer.
  • the cell contained water which was stirred by a magnetic pellet. Temperature and pressure were monitored and the results provided on a computer data logger; gas hydrates were also detected visibly using a time lapse video recording system. Before each test the cell was cleaned thoroughly by soaking successively in 10% aqueous hydrochloric acid for 1 hour, 10% aqueous sodium hydroxide solution for 1 hour and then double distilled water.
  • HMW denotes High Molecular Weight (about 2 million) MMW MediumMolecular Weight (about 750,000) and LMW Low Molecular Weight (about 70,000).
  • Example 4 The process of Example 4 was repeated with a blend of the following composition Chitosan (HMW) (500ppm) , a polyvinyl pyrrolidone of Molecular Weight (Mw) of about 700,000 (from BDH Ltd) (600ppm) and an alkyl benzyl dimethyl ammonium chloride sold as a corrosion inhibitor by Hoechst under the Trade Mark DODIGEN 5462 (50ppm).
  • HMW Chitosan
  • Mw Polyvinyl pyrrolidone of Molecular Weight
  • Mw polyvinyl pyrrolidone of Molecular Weight
  • DODIGEN 5462 50ppm
  • the pH of the water containing the blend was 4.3.
  • the averaged inhibition time from several experiments was about 115mins. Examples 11-15
  • Example 4 The process of Example 4 was repeated with the Chitosan replaced by the Additives below. The results as follows:
  • Example 11 The process of Example 11 was repeated with a Formulation containing Additives as follows.
  • Additive (viii) C alkyl benzyldimethyl ammonium chloride sold by Hoechst under the Trade Mark DODIGEN 5462 as a corrosion inhibitor. The results were as follows, with an averaged inhibition time from several experiments.
  • Example 20 The process of Example 20 was repeated with a Formulation containing Additives (i) A gelatin (500 ppm) (v)B tris(hydroxymethyl) methyl ammonium chloride (700 ppm) and (viii)C the alkyl benzyl dimethyl ammonium chloride DODIGEN 5462, making a total of 1350 ppm Additives. The inhibition time was 154 minutes. The experiment was repeated with the same relative proportion of the Additives A, B and C, but a total amount of 1000 ppm and also 500 ppm, giving averaged inhibition times of 156 and 59 minutes respectively.

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Abstract

On inhibe ou on retarde la formation d'hydrate gazeux, tel que les hydrates cristallins provenant du gaz naturel, par l'addition dans un milieu sensible à celui-ci d'un additif étant au moins (i) un colloïde hydrophile, (ii) un composé cyclique avec au moins un groupe -(C=O)-O- dans un cycle et (iii) un aminocarbohydrate et, de préférence, au moins (iv) un aminoacide ou un dérivé de celui-ci, (v) un aminoalcool ou un dérivé de celui-ci, (vi) un glycoléther ou un dérivé de celui-ci, (vii) un hydroxyacide ou un dérivé de celui-ci, (viii) un inhibiteur de corrosion ou (ix) un polymère d'un composé éthyléniquement insaturé.
PCT/GB1994/000952 1993-05-04 1994-05-04 Inhibition de l'hydrate WO1994025727A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB939309132A GB9309132D0 (en) 1993-05-04 1993-05-04 Method for inhibiting hydrate formation
GB9309106.4 1993-05-04
GB939309106A GB9309106D0 (en) 1993-05-04 1993-05-04 Hydrate inhibition
GB9309132.0 1993-05-04
GB9322209.9 1993-10-28
GB939322209A GB9322209D0 (en) 1993-10-28 1993-10-28 Hydrate inhibition

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
WO1995032356A1 (fr) * 1994-05-25 1995-11-30 Colorado School Of Mines Additifs et procede de regulation d'hydrates de clathrate dans des systemes a fluides
WO1996038492A1 (fr) * 1995-06-02 1996-12-05 Nippon Shokubai Co., Ltd. Inhibiteur d'hydrates de clathrates et procede d'inhibition de la formation d'hydrates de clathrates l'utilisant
WO2003087532A1 (fr) * 2002-04-12 2003-10-23 Queen's University At Kingston Proteines antigel permettant d'inhiber la formation et la reformation d'hydrate de clathrate
WO2013053766A1 (fr) * 2011-10-11 2013-04-18 Eco Inhibitors As Procédé d'inhibition de la formation d'hydrates gazeux utilisant des amidines et des guanidines
CN104039918B (zh) * 2011-10-11 2016-11-30 Eco抑制剂公司 使用脒和胍抑制气体水合物形成的方法
WO2017087326A1 (fr) * 2015-11-16 2017-05-26 Gcp Applied Technologies Inc. Apparition reportée de l'hydratation de la chaux vive
CN114524944A (zh) * 2022-01-24 2022-05-24 成都昂赛福科技有限公司 一种叔胺封端的环保型超支化聚胺插层抑制剂的合成及水基钻井液

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EP0323307A1 (fr) * 1987-12-30 1989-07-05 Institut Français du Pétrole Procédé de transport d'un fluide formant des hydrates
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5639925A (en) * 1992-11-20 1997-06-17 Colorado School Of Mines Additives and method for controlling clathrate hydrates in fluid systems
WO1995032356A1 (fr) * 1994-05-25 1995-11-30 Colorado School Of Mines Additifs et procede de regulation d'hydrates de clathrate dans des systemes a fluides
GB2307244A (en) * 1994-05-25 1997-05-21 Colorado School Of Mines Additives and method for controlling clathrate hydrates in fluid systems
GB2307244B (en) * 1994-05-25 1998-12-30 Colorado School Of Mines Additives and method for controlling clathrate hydrates in fluid systems
WO1996038492A1 (fr) * 1995-06-02 1996-12-05 Nippon Shokubai Co., Ltd. Inhibiteur d'hydrates de clathrates et procede d'inhibition de la formation d'hydrates de clathrates l'utilisant
AU705814B2 (en) * 1995-06-02 1999-06-03 Nippon Shokubai Co., Ltd. Clathrate hydrate inhibitor and method of inhibiting the formation of clathrate hydrates using it
US6232273B1 (en) 1995-06-02 2001-05-15 Nippon Shokubai Co., Ltd. Clathrate hydrate inhibitor and method of inhibiting the formation of clathrate hydrates using it
WO2003087532A1 (fr) * 2002-04-12 2003-10-23 Queen's University At Kingston Proteines antigel permettant d'inhiber la formation et la reformation d'hydrate de clathrate
WO2013053766A1 (fr) * 2011-10-11 2013-04-18 Eco Inhibitors As Procédé d'inhibition de la formation d'hydrates gazeux utilisant des amidines et des guanidines
GB2509867A (en) * 2011-10-11 2014-07-16 Eco Inhibitors As Method of inhibiting the formation of gas hydrates using amidines and guanidines
CN104039918A (zh) * 2011-10-11 2014-09-10 Eco抑制剂公司 使用脒和胍抑制气体水合物形成的方法
US9303201B2 (en) 2011-10-11 2016-04-05 Eco Inhibitors As Method of inhibiting the formation of gas hydrates using amidines and guanidines
CN104039918B (zh) * 2011-10-11 2016-11-30 Eco抑制剂公司 使用脒和胍抑制气体水合物形成的方法
GB2509867B (en) * 2011-10-11 2020-05-06 Eco Inhibitors As Method of inhibiting the formation of gas hydrates using amidines and guanidines
WO2017087326A1 (fr) * 2015-11-16 2017-05-26 Gcp Applied Technologies Inc. Apparition reportée de l'hydratation de la chaux vive
US10597325B2 (en) 2015-11-16 2020-03-24 Gcp Applied Technologies Inc. Postponed onset of quicklime hydration
CN114524944A (zh) * 2022-01-24 2022-05-24 成都昂赛福科技有限公司 一种叔胺封端的环保型超支化聚胺插层抑制剂的合成及水基钻井液

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