Additive for preserving fluidity of fluids containing gaseous hydrates

FIELD: chemistry.

SUBSTANCE: anti-agglomerates are surface-active non-quaternary nitrogen-containing compounds with 1-5 nitrogen atoms, which have at least one hydrophobic group with 6-24 carbon atoms, and where the hydrophobic group is bonded to the remainder of the molecule by an amine moiety, an ether moiety or an amide moiety, provided that when the hydrophobic group is bonded by an amide moiety to the remainder of the molecule, the compounds must contain a total of at least two nitrogen atoms, and optionally contain 1-12 -CH2CH2O- groups and/or 1-6 hydroxyalkyl groups with 3-4 carbon atoms; and compounds having at least one C2-C3 acyl group and/or at least one hydroxyalkyl group with 3-4 carbon atoms; or a salt thereof. The method of inhibiting agglomeration of gaseous hydrates in a conduit, containing a fluid mixture which contains hydrocarbons with 1-4 carbon atoms and water, involves adding to the mixture said agglomerate in amount of 0.05-10% of the content of water in the fluid mixture. The composition contains said anti-agglomerate of gaseous hydrates, a corrosion inhibitor and/or a paraffin deposition inhibitor.

EFFECT: high efficiency of the anti-agglomerate for gaseous hydrates and biodegradability thereof.

9 cl, 2 ex, 2 tbl

 

The present invention relates to the use of group alkoxysilane and/or acylated nekaterih nitrogen-containing compounds as protivoelektrodom for gas hydrates.

When low molecular weight hydrocarbon gases such as methane, ethane, propane, butane and isobutane, is subjected to high pressure in the presence of water, may form a special type of ice, the so-called gas hydrate. The maximum temperature for education will depend on the gas pressure. At a sufficiently high pressure of the gas hydrate may be resistant to +25°C.

The formation of gas hydrates has important practical significance in the oil and gas production, particularly for transportation of natural gas in offshore pipelines, dominated by high pressure and low temperature. If you do not take any measures, the pipeline is easily blocked by the formation of gas hydrates.

Adding or methanol, or ethylene glycol to the gas/water or gas/water/oil flow for lowering the freezing point of the gas/water mixture for a long time has been the common practice. This method, which is called thermodynamic inhibition prevents the initial formation of gas hydrates. However, it requires adding 10-60% of the amount of water present in the fluid, depending on the pace of atory and gas pressure. This high level of addition will also make the necessary return of the additive to the destination. In General, it makes thermodynamic inhibition rather expensive operation.

The foregoing, in turn, led to the search for additives that can be used in much lower doses, and this search led to two fundamentally different modes of action, kinetic inhibition and dispersion. In both cases, the normal dosage of the additive is 1-3% water, presented at the gas/water or gas/water/oil flow.

Kinetic inhibition of the formation of gas hydrates

Kinetic inhibitors are products that delaying the initial nucleation of gas hydrates. Kinetic inhibitors, therefore, are effective for only a limited period of time, which is inconvenient. These products are usually polymers, and several classes of polymers suitable as kinetic inhibitors, have been described in WO 93/25798.

Dispersion of gas hydrates

When using the dispersant, the formation of small crystals of gas hydrates, but the agglomeration of these crystals prevent. This, as mainly it is assumed to be due to adsorption of the dispersant on the surface of the original is correctly formed crystals of gas hydrate. Dispersers are typically surface-active agents, i.e. they contain at least one hydrophilic (polar) and at least one hydrophobic (nonpolar, oleophilic) group. The dispersant is adsorbed its polar end toward the gas crystal hydrate, turning his non-polar hydrocarbon end out. The crystals thus obtained oleophilic and can be easily dispersed in the liquid hydrocarbon phase. Dispersers, thus, are effective only when such liquid oil phase is present. This will normally take place in the pipeline from the production well to the first processing station, when the liquid stream contains both gas and oil as well as water. Adsorbed layer of dispersant on the crystals will also hinder their growth together into larger agglomerates, which otherwise can cause complete blockage of the pipeline. This property dispersant has led to what is usually called protivogelmintny, and this term will be used everywhere in the application.

In the US 4915176 disclosed method of transportation hydrate forming fluid, in which the additive is introduced into the fluid to reduce the tendency of agglomerating hydrate to obtain hydrates in dispersed form. Additives used in the work ol the measures are diethanolamide fatty acids with different length alkyl chains, dioctylsulfosuccinate sodium and sorbitanoleat.

In WO 96/34177 described surfactants based on Quaternary ammonium compounds, in which at least two butylene, Pintilie or isopentyl group attached to the nitrogen atom which bears one or two long alkylpyridine chain. Some products with this configuration showed that they are good antiglomerular gas hydrates. Their main drawback is that they do not fully bioresource. The production process of these types of compounds also includes several stages, and thus it takes a lot of time.

WO 03/008757 reveals alkoxysilane of Quaternary ammonium compounds containing ester groups, as protivoelektrodom. These compounds are also not fully bioresource.

In the US 6331508 disclosed a method of controlling the formation of crystals of gas hydrates in a fluid mixture, where polyoxyalkylene added to the mixture in an amount effective to prevent and/or inhibit the growth of crystals. Preferred compounds have the General formula

where R is an alkyl group having 1-20 carbon atoms, x=1-4, n=2 or 3 and b+f+g=3-30, predpochtitel is about 20-30. In the working example used Ethoduomeen T/25 (ex Akzo Nobel). This compound is N-(oil alkyl)Propylenediamine, which interacts with 15 moles of ethylene oxide; thus it is a compound according to the formula above, where x is 3, n is 2 and b+f+g=15. It was also suggested propoxycarbonyl connection with b+f+g=30. However propoxycarbonyl products containing large quantities of units of propylene oxide, will show a high logPow(see further, below the definition logPowas the solubility in water is quite low and the ability to decomposition by microorganisms is insufficient.

In the US 4973775 disclosed process delays of education and/or reduce the tendency of agglomeration of gas hydrates, where the use hydroxycarbamide and polyhydroxyamide. The proposed compounds are described by the General formula (1), (2) and (3)

where R-C=O is a radical of carboxylic acid and contains 4-28 carbon atoms, R', R" and R"' are hydroxycarbazole, and R"" is alkilinity radical type CnH2nand n is an integer equal to at least 1. Disclosed only compounds according to the formula (2) types of coconut diethanolamide, ethoxylated coconut diethanolamide, rape diethanolamide or diethanolamide from other acids.

Despite the fact that offer the SJ different ways, to overcome the problem of agglomeration, still there is a need for improved protivougonnye for gas hydrates.

The present invention is to find new protivogelmintny for gas hydrates, which are effective in sea water, brackish, and/or fresh water, and have a better ability to decomposition by microorganisms, and are more economically attractive than the previous known connections.

The present invention unexpectedly found that the surface-active nitrogen-containing compound with 1-5, preferably 1-4, more preferably 1-3 and most preferably 1 or 2 nitrogen atoms, a compound that has at least one hydrophobic group with 6-24, preferably 8-22, and most preferably 8-18 carbon atoms, and in which a hydrophobic group linked to the remainder of the molecule of amine part, essential part, or amide part, provided that, when a hydrophobic group linked through an amide portion with the remainder of the molecule, the compound must contain a total of at least 2 nitrogen atom;

the compound, which optionally contains 1 to 12, preferably 2-10-CH2CH2O - groups and/or 1-6 hydroxyalkyl group with 3-4 carbon atoms; and

the compound which has at least one C2-C3 preferably C2-acyl group and/or at least one hydroxyalkyl group with 3-4 carbon atoms, preferably 3 carbon atoms; a compound which is selected from the group below, consisting of compounds IA, IB, IC, II and III or their salts;

an effective protivoelektrodom for gas hydrates in salt and in fresh water and at the same time has the best ability to biodegrade than compounds of the prior art. An additional advantage is that these compounds also have the ability to act as corrosion inhibitors. According to unsubstantiated theory assumes that the main acyl, hydroxiproline and hydroxybutylidene groups have improved adhesion to the surface of gas hydrate and, thus, facilitate the dispersion and prevent agglomeration.

Surface-active nicetitties nitrogen-containing compound selected from the group nekaterih nitrogen-containing compounds having the following General formulas IA, IB, IC, II and III, ie,

where R is a C6-C24preferably8-C22and most preferably8-C18hidrocarburos group; m is 2 or 3, preferably 3; a=0-4, preferably 0-3, and most preferably 0 or 1; b is at least 1 in each paragraph is the situation; Σb value on average is 2 to 12, preferably 2 to 10; c is 0 or 1; d the average is 0-5, preferably 0; each A is independently selected from H, -C(=O)CH3, -C(=O)CH2CH3C1-C3alkyl groups,- (CH2CH(X)O]eN -[CH2CH(X)O]e-C(=O)CH3where X is-CH3or-CH2CH3preferably-CH3e is equal to 1-3, and the sum of all e in the molecule is at most 6 average; provided that at least one of the groups A is- (CH2CH(X)O]eH, -CH2CH(X)O]e-C(=O)CH3, -C(=O)CH3or-C(=O)CH2CH3;

where B is independently chosen from- (CH2CH(X)O]eH,- (CH2CH(X)O]e-C(=O)CH3or H; each D is independently selected from H, hidrocarburos group with 1-24 carbon atoms, preferably 1-3 carbon atoms,- (CH2CH(X)O]eN or -[CH2CH(X)O]e-C(=O)CH3; provided that at least one group D or group B is

- (CH2CH(X)O]eH or- (CH2CH(X)O]e-C(=O)CH3;

m, a, c, e, Σe and X are defined as for IA; and R is hidrocarburos group with 6-24 carbon atoms, preferably 6 to 18 and most preferably 6 to 15 carbon atoms, provided that when all D and B are the group- (CH2CH(X)O]eH, c=0, m=3 and a=1-4, then logPowfor a molecule is at most 3;

where R is hidrocarburos group having 6-24, preferably 8-22, and most preferably 8-18 carbon atoms; m is 2 or 3, preferably 3; a=0-4, preferably 0-3, and most preferably 1, E is C1-C3by alkyl, -C(=O)CH3or-C(=O)CH2CH3and F is-C(=O)CH3or-C(=O)CH2CH3;

where R is C(=O)- is an acyl group with 6-24, preferably 8-22, and most preferably 8-18 carbon atoms; o=0-3, preferably 1-2; p=0-3, preferably 0-2; Σ(o+p) average of 0-6, preferably 1-4; and m is 2 or 3, preferably 2; and each A is independently selected from H,- (CH2CH(X)O]eH,- (CH2CH(X)O]e-C(=O)CH3, -C(=O)CH3, -C(=O)CH2CH3and C1-C3-alkyl groups; provided that at least one of the groups A is- (CH2CH(X)O]eH,- (CH2CH(X)O]e-C(=O)CH3, -C(=O)CH3or-C(=O)CH2CH3where X, e and Σe are the same value as for IA; and

where r and s are independently equal to 0 to 2, provided that Σr+s=0-2; and j is 0 or 1, provided that when j=1, then c=0 and R"=R', and when j=0, then R=R, and provided that at least one of A is- (CH2CH(X)O]eH,- (CH2CH(X)O]e-C(=O)CH3, -C(=O)CH3or-C(=O)CH2CH3where X, e and Σe are the same value is s, as for IA; R, c, d, b, σb value, m and A are defined as for IA, and R C(=O)- defined as for (II);

or salt of any of the compounds IA, IB, IC, II or III; or any combination thereof.

The preferred structures of the formula IA are those where all groups are A-CH2CH(CH3HE, or those where all group A is-C(=O)CH3.

Thus, one implementation of the invention provides compounds of formula

where R is hidrocarburos group 6-24, preferably 8-22, and most preferably 8-18 carbon atoms, m is 2 or 3, preferably 3, and is 0 or 1, the sum of b average of 2-6, and the sum of e is equal to 2 or 3, and

where R is hidrocarburos group of 6-24, preferably 8-22, and most preferably 8-18 carbon atoms, m is 2 or 3, a is 0 or 1 and the sum of b is equal to 2-6.

Another implementation includes compounds having formula IB, where R is a C6-C15hidrocarburos group, c is 0, m is 3, a is 1, B and D independently are selected from the groups- (CH2CH(X)O]eH and- (CH2CH(X)O]e-C(=O)CH3and the amount e average of 3-6.

The preferred structures of the formula IC are those in which a=1, group F is-C(=O)CH3and group E is C1-C3the alkyl or-C(=O)CH3.

Thus, the further implementation of the invention including the AET connection those having the formula :

where R is an alkyl group having 6-24, preferably 8-22, and most preferably 8-18 carbon atoms, m is 2 or 3, preferably 3, and E is C1-C3by alkyl, preferably by stands or-C(O)CH3.

Preferred surface-active nezatertye nitrogen-containing compounds of formula II are selected from the group of compounds having the following General formula

where n is at least 1 in each position and Σn average is 2-4, m is 2 or 3, preferably 2, R'(C=O)- and A is defined as for II, except that X is-CH3provided that at least one of A is- (CH2CH(CH3)O]eH,- (CH2CH(CH3)O]e-C(=O)CH3or-C(O)CH3where e and Σe is defined as for II;

and

where m is 2 or 3, preferably 2; R'(C=O)- and A is defined as for II, except that X is-CH3provided that at least one of A is- (CH2CH(CH3)O]eH,- (CH2CH(CH3)O]e-C(=O)CH3or-C(O)CH3; where X, e and Σe are the same value as for IA;

and salts of any compounds of IIA and IIB.

Thus, still another implementation of the invention contains compounds IIA having the formula

where R'(C=O)- is an acyl group having 6-24, preferably 8-22, and most preferably 8-18 carbon atoms and m is 2 or 3, preferably 2;

and compound IIB having the formula

where R'(C=O)- is an acyl group having 6-24, preferably 8-22, and most preferably 8-18 carbon atoms and m is 2 or 3, preferably 2.

Preferred surface-active nezatertye nitrogen-containing compounds of formula III have the formula

where r and s are independently equal to 0 to 1, and preferably r and s are 0; R, b, σb value, m and A are defined as for IA, except that X is-CH3provided that at least one of A is- (CH2CH(CH3)O]eH,- (CH2CH(CH3)O]e-C(=O)CH3or-C(O)CH3where e and Σe are defined for both IA; or a salt IIIA.

Can also be used with any combination of IA, IB, IC, IIA, IIB and IIIA or their salts. Compounds having the formulas or their salts, have been found as effective biodegradable protivogelmintny for gas hydrates.

In the further implementation of protivoallergic has a low logPow(=logKow), preferably ≤3, more preferably 2 or less, so as substances with logPowhigher than 3 are prone to bioaccumulation. This value can be either experimentally izmerenii theoretically calculated and obtained from the separation of the connection between these two phases of n-octanol and water. The partition coefficient (P) is defined as the ratio of the equilibrium concentrations of a dissolved substance in a two-phase system consisting of two largely immiscible solvents; in the case of n-octanol and water Powvalue (=the octanol-water distribution coefficient) connection is:

Pow=(Cn-octanol/Cwater), where Cn-octanoland Cwaterare the equilibrium concentrations of the compounds in octanone and water phases, respectively. Due to the emulsifying properties of many surfactants for these kinds of products usually theoretically calculated logPow. For introduction into the calculation of Powsee Annex to the OECD Guideline for Testing of Chemicals 117 and references there. For compounds IB is essential that logPowequal to at most 3.

The above-mentioned compounds obtained by methods known from the prior art. The compounds of formula IA receive the first ethoxycarbonyl appropriate alkylamine, alkylamine, alkylpyridine or alkylamidoamines, such as pre-selected (fatty alkyl)monoamin, (fatty alkyl)aminopropyl, 3-[(fatty alkyl)oxy]Propylamine or N-[3-(fatty alkyl)oxy]-1,3-propandiamine and then propoxycarbonyl and/or butoxycarbonyl and/or acetylated ethoxylated product. The number of moles of ethylene oxide, which interacts with the amine compound, should not be the ü integer and represents the number average degree of polymerization of ethylene oxide in the product (see Nonionic Surfactants: Organic Chemistry in Surfactant Science Series Volume 72, 1998, p 1ff, edited Nico M. van Os; Marcel Dekker, Inc). The products of formula IA can be added to the aqueous phase by themselves or as a salt with an acid, preferably as they are salt of carboxylic acid. Any lower salt of carboxylic acid is suitable, and salts of acetic acid are particularly preferred. May, accordingly, be used salts of IA with mineral acids, such as chlorides, sulphates and phosphates.

The compounds of formula IB are propoxycarbonyl and/or butoxycarbonyl appropriate alkylamine, alkylamine or alkylpyridine. The product is preferably added as a salt of carboxylic acids, but the salts with mineral acids are also suitable for use.

The compounds of formula IC is obtained by acetylation of N-(fatty alkyl)-1,3-propanediamine or N-(fatty alkyl), N-(C1-3alkyl)-1,3-Propylenediamine.

The compounds of formula IIA get, producing amide of a fatty acid and aminoethylethanolamine or aminopropyldimethylamine ethoxycarbonyl amide and then propoxycarbonyl and/or acetylation ethoxylated amide.

The compounds of formula IIB get, producing amide of a fatty acid and aminoethylethanolamine or aminopropyldimethylamine and then directly propoxycarbonyl and/or acetylase what W amide. For IIA and IIB product is preferably added as salt.

The compounds of formula IIIA get the first ethoxycarbonyl suitable alkylamine containing tertiary mono(fatty alkyl)amino group and then propoxycarbonyl and/or acetylation ethoxylated product. The product is preferably added as salt.

Suitable alkylamines followed and acylpolyamines that can be used as starting compounds for the compounds of formulas IA and IB, are (fatty alkyl)monoamines according to the formula R1NH2where R1 is an aliphatic group with 6-24 carbon atoms; (fatty alkyl)diamines according to the formula R2NHCH2CH2CH2NH2where R2 is an aliphatic group with 6-24 carbon atoms (also suitable as starting substances for IC); and linear (fatty alkyl)triamine according to the formula R3NHCH2CH2CH2NHCH2CH2CH2NH2where R3 is an aliphatic group with 6-24 carbon atoms.

Suitable alkylpyridine or alkylamidoamines that can be used as starting compounds for the compounds of formulas IA and IB, are alkylpyridine according to the formula R4O(CH2CH2CH2)NH2and alkylamidoamines according to the formula R5O(CH2CH2CH2)NH(CH2CH2CH2)NH2, is de R4 and R5 are aliphatic groups, having 6-24 carbon atoms.

Suitable acylpolyamines that can be used as starting compounds for the compounds of formulas III and IIIA are branched (fatty alkyl)triamine (Y-triamine) formula R6N(CH2CH2CH2NH2)2where R6 is an aliphatic group with 6-24, preferably 8-22 carbon atoms or a branched (fatty alkyl)pentamine formula R7N(CH2CH2CH2NHCH2CH2CH2NH2)2where R7 is an aliphatic group with 6-24, preferably 8-22 carbon atoms.

Suitable alkylamidoamines that can be used as starting compounds for the compounds of formula III are those of the formula R8O(CH2CH2CH2)N(CH2CH2CH2NH2)2in which R8 is an aliphatic group with 6-24, preferably 8-22 carbon atoms.

Examples of suitable fatty amines for use as starting compounds for the compounds of formulas IA and IB are n-hexylamine, 2-ethylhexylamine, n-octylamine, 2-propylheptyl, n-decylamine, n-dodecylamine, (Coco alkyl)amine, n-tetradecyl, n-hexadecylamine, n-octadecylamine, oleylamine, (oil alkyl)amine, (rapeseed alkyl)amine, (soya alkyl)amine, aracelly amine, N-(n-decyl)trimethylenediamine, N-(n-dodecyl)trimethylenediamine, N-(what olsowy alkyl)trimethylenediamine, N-(rapeseed alkyl)trimethylenediamine, N-(soya alkyl)trimethylenediamine, N-(oil alkyl)trimethylenediamine, N-arazilerinden, N-(n-decyl)-N'-(3-aminopropyl)-1,3-propandiamine, N-(n-dodecyl)-N'-(3-aminopropyl)-1,3-propandiamine, N-(coconut alkyl)-N'-(3-aminopropyl)-1,3-propandiamine, N-(rapeseed alkyl)-N'-(3-aminopropyl)-1,3-propandiamine, N-(soya alkyl)-N'-(3-aminopropyl)-1,3-propandiamine, N-oleyl-N'-(3-aminopropyl)-1,3-propandiamine, N-(oil alkyl)-N'-(3-aminopropyl)-1,3-propandiamine, N-erucyl-N'-(3-aminopropyl)-1,3-propandiamine, N-(3-aminopropyl)-N'-[3-(9-decylamine)propyl]-1,3-propandiamine N-(3-aminopropyl)-N'-[3-(9-dodecylamino)propyl]-1,3-propandiamine, N-(3-aminopropyl)-N'-[3-(9-(coconut alkyl)amino)propyl]-1,3-propandiamine, N-(3-aminopropyl)-N'-[3-(9-(rapeseed alkyl)amino)propyl]-1,3-propandiamine, N-(3-aminopropyl)-N'-[3-(9-(soya alkyl)amino)propyl]-1,3-propandiamine, N-(3-aminopropyl)-N'-[3-(9-octadecylamino)propyl]-1,3-propandiamine, N-(3-aminopropyl)-N'-[3-(9-(oil alkyl)amino)propyl]-1,3-propandiamine and N-(3-aminopropyl)-N'-[3-(9-Arellano)propyl]-1,3-propandiamine.

Examples of suitable fatty diamines for use as starting compounds for the compounds of formula IC are N-(2-ethylhexyl)trimethylenediamine, N-(n-octyl)trimethylenediamine, N-(n-decyl)trimethylenediamine, N-(n-dodecyl)trimethylenediamine, N-(n-tetradecyl)trimethylenediamine, N-(coconut alkyl)trimethylindium is, N-(n-hexadecyl)trimethylenediamine, N-alertsemergencies, N-(rapeseed alkyl)trimethylenediamine, N-(soya alkyl)trimethylenediamine, N-(oil alkyl)trimethylenediamine, N-arazilerinden, N-(n-octyl)-N-methylaminopropane, N-(2-ethylhexyl)-N-methylaminopropane, N-(n-decyl)-N-methylaminopropane, N-(n-dodecyl)-N-methylaminopropane, N-(coconut alkyl)-N-methylaminopropyl, N-(n-tetradecyl)-N-methylaminopropane, N-oleyl-N-methylaminopropane, N-(rapeseed alkyl)-N-methylaminopropane, N-(soya alkyl)-N-methylaminopropyl and N-(oil alkyl)-N-methylaminopropyl.

Examples of suitable alkylamino and alkylamidoamines for use as starting compounds for the compounds of formulas IA and IB are 3-(n-octyloxy)Propylamine, 3-[2-(ethylhexyl)oxy]Propylamine, 3-(n-decyloxy)Propylamine, 3-[2-(propylheptyl)oxy]Propylamine, 3-(dodecyloxy)Propylamine, 3-[(coconut alkyl)oxy]Propylamine, 3-[(rapeseed alkyl)oxy]Propylamine, 3-[(soya alkyl)oxy]Propylamine, 3-(octadecanoyloxy)Propylamine, 3-[(oil alkyl)oxy]Propylamine, 3-(eruzione)Propylamine, N-[3-(2-(ethylhexyl)oxy)propyl]-1,3-propandiamine, N-[3-(n-octyloxy)propyl]-1,3-propandiamine, N-[3-(n-decyloxy)propyl]-1,3-propandiamine, N-[3-(2-(propylheptyl)oxy)propyl]-1,3-propandiamine, N-[3-(tridecylamine)propyl]-1,3-propandiamine and ether mono - and diamines, based on C6-C alcohols that were ethoxycarbonyl 5 moles of ethylene oxide.

Examples of fatty acids for use as starting substances for the amides of the compounds of formulas II, IIA, IIB and III are hexanoic acid, 2-atelophobia acid, n-Caprylic acid, n-cekanova acid, n-dodecanoyl acid, coconut fatty acid, oleic acid, rapeseed fatty acid, soya fatty acid oil fatty acid, fatty acid of tall oil and erucic acid.

Examples (fatty alkyl)polyamines that can be used as starting compounds for the compounds of formulas III and IIIA are N,N-bis(3-aminopropyl)hexylamine, N,N-bis(3-aminopropyl)(2-ethylhexyl)amine, N,N-bis(3-aminopropyl)-n-octylamine, N,N-bis(3-aminopropyl)decylamine, N,N-bis(3-aminopropyl)(2-propylheptyl)amine, N,N-bis(3-aminopropyl)dodecylamine, N,N-bis(3-aminopropyl)-(Coco alkyl)amine, N,N-bis(3-aminopropyl)tetradecanamide, N,N-bis(3-aminopropyl)hexadecylamine, N,N-bis(3-aminopropyl)stearylamine, N,N-bis(3-aminopropyl)(rapeseed alkyl)amine, N,N-bis(3-aminopropyl)(oil alkyl)amine, N,N-bis(3-aminopropyl)(soya alkyl)amine, N,N-bis(3-aminopropyl)oleylamine and N,N-bis(3-aminopropyl)arulsamy.

Examples (fatty alkyl)epicontinental that can be used as starting compounds for the compounds of formula III are N-[3-(n-octyloxy)propyl]-N,N-bis(-aminopropyl)amine, N-[3-(n-dodecyloxy)propyl]-N,N-bis(3-aminopropyl)amine, N-[3-(tridecylamine)propyl]-N,N-bis(3-aminopropyl)amine, N-[3-[(oil alkyl)oxy)]propyl]-N,N-bis(3-aminopropyl)amine and N-[3-(octadecanoyloxy)propyl]-N,N-bis(3-aminopropyl)amine.

The acylation reaction can be carried out with acid, acid anhydride or acylchlorides. The acylation reaction is most conveniently carried out with acetic anhydride, but also, for example, can be used acetic acid or acetyl chloride. Reaction amoxilonline and propoxycarbonyl known from the prior art. Usually all primary and secondary amine groups are alkoxycarbonyl the first stage in the absence of any catalyst, to obtain amino groups, which are fully substituted hydroxyalkyl groups, i.e. usually on the nitrogen atoms leaving no hydrogens. If you then add the oxide alkylene typically use an alkali metal hydroxide as catalyst, preferably KOH. However, the choice of catalyst is not critical and there are many catalysts known to the person skilled in the technical field, which can be used equally well. Anywhere in the description, when discussing the degree of alkoxysilane mentioned numbers are the average numbers of moles.

The present invention also relates to a method for inhibiting the agglomeration of gas is o hydrates in the pipeline, where the pipe contains a fluid mixture containing a hydrocarbon with 1 to 4 carbon atoms, and water and where the hydrates formed from hydrocarbons and water, the method involves the following stages:

a) adding to the mixture of protivopokazana defined in formulas IA, IB, IC, II and III, in an amount that is effective for inhibiting the agglomeration of hydrates at the prevailing temperature and pressure in the piping;

b) for mixtures containing protivoallergic through the pipeline.

Concentration protivoelektrodom be at least 0,05%, preferably at least 0.5% wt. the aqueous phase, and at most 10%, preferably at most 5% and most preferably at most 3% of the mass. the aqueous phase. The exact number of protivopokazana, which is used depends, among other things, on the structure of protivopokazana, water quality, applied pressure and the actual composition of the gas and/or oil. Protivogelmintny of the invention in addition to their dispersal ability also have other useful properties, such as the ability to inhibit corrosion. Protivogelmintny preferably added to the wellhead in the composition, which may also contain other corrosion inhibitors and inhibitors of the formation of paraffin deposits in the pipes. This composition respectively contains

a) 1 mass cha is th protivopokazana gas hydrate as defined in formula IA, IB, IC, II and III, and

b) is 0.0001 to 0.1, preferably of 0.001 to 0.05 mass parts of a corrosion inhibitor and/or an inhibitor of the formation of paraffin deposits in the pipes.

In the final implementation of the invention use this protivoallergic in combination with other compounds used in compositions where gas hydrates are potentially formed, such as corrosion inhibitors and other additives. Examples of suitable corrosion inhibitors are oil amines, N-(oil alkyl)trimethylenediamine, imidazoline and Quaternary amines, and examples of suitable inhibitors of the formation of paraffin deposits in pipes are alcohol esters of alpha-olefin maleic anhydride copolymers, ethylene vinyl acetate copolymers, and alcohol esters of polyacrylic acid. Other additives that may be present in the compositions are the foam depressors, such as containing silicon compounds, glycols and polyglycols, kinetic inhibitors, such as polymers or copolymers of N-vinyl-2-pyrrolidone, described in WO 1993/025798, biocides, metalcomplexes, such as citric acid, solubilizing agents, and additives for the stabilization of the dispersion, as well as other dispersants.

The following exercise will illustrate the invention and should not be considered as limiting its capabilities.

EXAMPLES

About the s

Technique used to estimate protivoelektrodom, described in detail in "New Technique for Evaluating Antiagglomerate Gas-Hydrate Inhibitors in Oilfield Applications", SPE 93075, 2005 SPE International Symposium on Oilfield Chemistry, Houston, TX, Feb. 2-4.

Basis: Full multicell system consists of a pressure vessel containing multiple test unit, cooling unit, the agitator with drive unit sensor interface and the computer system. The pressure vessel is connected with two gas cylinders containing compressed hydrocarbon gas (87,9% methane, 7.7% of ethane, 3.1% of propane and 1,3% of isobutane) and nitrogen. Thus, in the experimental run, each test cell will be subjected to the same gas mixture, temperature and pressure. Each cell has a magnetic slab stirrer, and the rotation of the agitator and check register sensor. When gas hydrate crystals in the cell is formed, there will be a change in viscosity or the flow behavior and will change in the delay of the bar stirrer. Each time the magnetic beam passes a certain point, record the optical pulse. The delay is measured as the difference between the position of the lower magnets of the motor and the agitator in the cell. When the viscosity becomes too high, which occurs when formed large aggregates of gas hydrates, magnetic stirrer or the fully stop in this case, the signal will be zero or will begin to "slip"that will create unstable/random signal, and it will be shown in the registration column.

Each cell is also equipped with a temperature sensor.

In the tables of examples 1 and 2 below were used following notes.

SW = ethylenoxy unit

RO = propionoxy unit

0 = the connection is not working as protivopokazana,

1 = connection initially works as protivoallergic, but not during the whole test

2 = the connection works as protivopokazana throughout the test (for notes 0, 1, and 2, see further explanation in example 2),

- = test not performed.

Example 1

Table 1 contains the results ofmultiple screeningsome protivoelektrodom.

Cells loaded with 1 ml of a mixture water/inhibitor and 2.5 ml of condensate read (= crude oil obtained from the read oil Statoil). Nitrogen is first used to remove most of the air and then let hydrocarbon gas as long as there is a constant pressure of 100 bar.

Throughout the test mixture was continuously mixed at 120 rpm, the Temperature was first lowered from approximately 20 to 4°C after approximately 1.5 hours, then maintained at 4°C for approximately two hours and Nakane is, re-raised again to 20°C after approximately 1.5 hours. When the mixer is working all the time, it is considered that the connection works well as protivoallergic, whereas if the bar stirrer is stopped, it is considered that the connection does not work as protivoallergic under the prevailing conditions. Tests were performed in sea water and in fresh water, and at various concentrations of protivoelektrodom.

2
Table 1
Testing multiple screening
ConnectionSea waterFresh water
1,0%1,5%1,5%2,5%
A. Oleylamine + EO + RO, stereoselectivity CH3Cl (comparison)-20-
Century (Coco alkyl)amine + EO (comparison)00--
C. (Coco alkyl)amine + EO; salt acetic acid (cf the ranking) 00--
D. Oleyl Amin + EO; salt acetic acid (comparison)0---
1. Oleylamine + EO + RO; salt of acetic acid-2--
2. Arulsamy + EO + RO; salt of acetic acid-22-
3. (Coco alkyl)amine + EO + RO; salt of acetic acid22--
4. N-(n-octyl)trimethylenediamine + 3RO; salt acetic acid (logPow=0,84)*-2--
5. Oleylamine + EO, complex fluids with acetic acid, salt of acetic acid020 0
6. N-alertsemergencies + EO, createrepository acetic anhydride; salt of acetic acid-2-2
7. Monoamide oleic acid and aminoethylethanolamine + EO, datarepository acetic anhydride; salt of acetic acid2---
8. Monoamide oleic acid and aminoethylethanolamine, aminirovanie acetic anhydride222-
9. N,N-bis(3-aminopropyl)(oil alkyl)amine, deliciously acetic anhydride02--
10. N-alertsemergencies, deliciously acetic anhydride-2--
11. N-(n-octyl)trimethylenediamine, deliciously acetic anhydride---
12. N-(coconut alkyl)trimethylenediamine, deliciously acetic anhydride-2--
13. N-(oil alkyl)-N-methylaminopropyl, monolithically acetic anhydride-2--
*Values of logPowin tables 1 and 2 were calculated using the model from the U.S. EPA Office of Pollutions Prevention and Toxics and Syracuse Research Corporation (U.S. EPA (United States Environmental Protection Agency). 2004. Estimation Program Interface (EPI) Suite (EPISuite™) Version 3.12, August 17, 2004).

The products according to the invention are at least good or better protivogelmintny screening test than links A, B, C and D, and at the same time more easily biodegradable than A. Note also that references B and C, which are (coconut alkyl)aminocarboxylate, in this test are not effective as protivoelektrodom for gas hydrates, whereas the product 3, which is (Coco alkyl)amine, which was first amoxillian and then propoxylated, works perfectly as protivoallergic.

p> Example 2

Table 2 contains the results of some protivoelektrodom ofmultiple modes private wells and re-run. This test is more affected than the test in example 1.

Cells loaded in the same way as above, but the hydrocarbon gas is admitted as long as there is a constant set pressure.

In this experiment, a test cell was stirred at 120 rpm./min for one hour at 20°C and the prescribed pressure. The stirring was then stopped and the autoclave cooled to 4°C in approximately 1.5 hours. Cells were maintained at 4°C for at least twelve hours before moving the magnets were re-run at 120 rpm supported Them working for about two hours at 4°C before the cells were re-heated to 20°C after approximately 1.5 hours.

Then there could be three different events:

- Mixing did not start at all until the temperature was not increased so much, that gas hydrate melted, which usually happened at approximately 15°C.

It is marked as 0 in the table.

The stirring was started, but stopped again after a short period. It is marked as 1 in the tables.

The stirring was started and continued to run continuously. This is tocino as 2 tables.

Table 2
Testing multiple modes private wells
ConnectionSea water (70 bar)Fresh water (70 bar)
1,5%2,5%2,0%2,5%
1. Oleylamine + EO + RO; salt of acetic acid2**111
3. (Coco alkyl)amine + EO + RO; salt of acetic acid012-
6. N-alertsemergencies + EO, createrepository acetic anhydride; salt of acetic acid01-2
10. N-alertsemergencies, deliciously acetic anhydride02-2
14. N-(2-ethylhexyl)trimethylenediamine, deliciously acetic anhydride00-2
15. N-(2-ethylhexyl)trimethylenediamine + 3RO; salt acetic acid (logPow*= 0,77)-2-1
*Values of logPowin tables 1 and 2 were calculated using the model from the U.S. EPA Office of Pollutions Prevention and Toxics and Syracuse Research Corporation (U.S. EPA (United States Environmental Protection Agency). 2004. Estimation Program Interface (EPI) Suite (EPISuite™) Version 3.12, August 17, 2004).
**Measured at 100 bars.

Protivogelmintny according to the invention have significant protivogelmintny effect in marine, brackish, and/or fresh water and at the same time are more easily biodegradable.

1. The use of surface-active nicetitties nitrogen-containing compounds selected from the group of compounds having the following General formulas IA, IB, IC, II and III, i.e

where R is a C6-C24hidrocarburos group; m is 2 or 3; a=0-4; b is at least 1 in each position; σb value on average is 2 to 12; C is 0 or 1; d is on average 0-5; each And independently selected the play from H, -C(=O)CH3-C(=O)CH2CH3C1-C3alkyl groups, -[CH2CH(X)O]eN -[CH2CH(X)O]e-C(=O)CH3where X is-CH3or-CH2CH3e is 1-3, and the sum of all e in the molecule is at most 6 average; provided that at least one of the groups And are selected from the group consisting of -[CH2CH(X)O]eH, -CH2CH(X)O]e-C(=O)CH3-C(=O)CH3and-C(=O)CH2CH3;

where independently selected from -[CH2CH(X)O]eN -[CH2CH(X)O]e-C(=O)CH3or N; each D is independently selected from the group consisting of N, hidrocarburos group with 1-24 carbon atoms, -[CH2CH(X)O]eN -[CH2CH(X)O]e-C(=O)CH3; and R, m, a, C, e, Σ and X are defined as for IA;
provided that at least one group D or group is
-[CH2CH(X)O]eN or -[CH2CH(X)O]e-C(=O)CH3;
and provided that when all D and b are group -[CH2CH(X)O]eH, C=0, m=3 and a=1-4, then logPowwhere Powis the distribution coefficient octanol - water, for a molecule equal to at most 3;

where R has the meaning as in IA, preferably R is hidrocarburos group with 8-22 and most preferably 8-18 carbon atoms, m R the VNO 2 or 3, preferably 3, a=0-4, preferably 0-3, and most preferably 1, E is C1-C3by alkyl, -C(=O)CH3or-C(=O)CH2CH3and F is-C(=O)CH3or-C(O)CH2CH3;

where R is C(=O)- is an acyl group with 6-24 carbon atoms; o=0-3, p=0-3, Σ(o+R) average of 0-6; m is 2 or 3, and each And independently selected from H,
-[CH2CH(X)O]eN -[CH2CH(X)O]e-C(=O)CH3-C(=O)CH3-C(=O)CH2CH3and C1-C3alkyl groups; provided that at least one of the groups And is
-[CH2CH(X)O]eN -[CH2CH(X)O]e-C(=O)CH3-C(=O)CH3or-C(=O)CH2CH3where X, e and Σ have value for IA; and

where r and s are independently equal to 0 to 2, provided that Σr+s=0-2; j is 0 or 1, provided that when j=1, then C=0 and R"=R', and when j=0, then R=R; and provided that at least one of the groups And are selected from the group consisting of
-[CH2CH(X)O]eN -[CH2CH(X)O]e-C(=O)CH3-C(=O)CH3and-C(=O)CH2CH3where X, e and Σe are important for both IA; R, C, d, b, σb value, m and a are defined as for IA and R is C(=O)- defined as for (II);
or salt of any of the compounds IA, IB, IC, II or III, or any combination thereof; as protivoelektrodom for gas hydrates.

p> 2. The use of surface-active nicetitties nitrogen-containing compounds according to claim 1, selected from the group of compounds having the General formulas IA, IB, IC, IIA, IIB, IIIA, where IA, IB and IC are defined as in claim 1, has the formula IIA

where n is at least 1 in each position and Σn average is 2-4, m is 2 or 3, R(C=O)and As defined for II, except that X is-CH3provided that at least one of And is
-[CH2CH(CH3)O]eN -[CH2CH(CH3)O]e-C(=O)CH3or-C(=O)CH3where e and Σ defined as for II;
IIB has the formula

where m is 2 or 3; R(C=O)and As defined for II, except that X is-CH3provided that at least one of And is
-[CH2CH(CH3)O]eN -[CH2CH(CH3)O]e-C(=O)CH3or-C(=O)CH3where e and Σ defined as for II;
and has the formula IIIA

where r and s are independently equal to 0 to 1; R, b, σb value, m and a are defined as for IA, except that X is-CH3provided that at least one of And is -[CH2CH(CH3)O]eH,- (CH2CH(CH3)O]e-C(=O)CH3or-C(=O)CH3where e and Σ defined for IA; or a salt of any of the compounds IA, IB, IC, IIA, IIB Il the IIIA or any combination thereof.

3. The use according to claims 1 and 2, where protivoallergic is the product of the formula IA, where R is a C8-C18hidrocarburos group; and a is 0 or 1; m is 3; C is 0; the sum of b on average is 2 to 6 and all are any -[CH2CH(CH3)O]eN, where the sum of all e in the molecule is 2 or 3, or-C(=O)CH3.

4. The use according to claim 3, where σb value averages 2-3.

5. The use according to claims 1 and 2, where protivoallergic is IC, where m is equal to 3 and E is-C(=O)CH3.

6. The use according to claims 1 and 2, where protivoallergic is IB, where R is a C6-C15hidrocarburos group, C is 0, m is 3, a is 1, b and D independently are selected from the groups-CH2CH(X)O]eN -[CH2CH(X)O]e-C(=O)CH3and the sum of e averages 3-6.

7. Method of inhibiting agglomeration of gas hydrates in the pipeline, where the pipeline contains a fluid mixture containing a hydrocarbon with 1 to 4 carbon atoms and water, and where hydrates are formed from hydrocarbons and water; the method involves the following stages:
a) adding to the mixture of protivopokazana as defined in any of the preceding paragraphs, in the amount of 0.05-10%, preferably 0.5 to 5% and most preferably 0.5 to 3 wt.%, based on the water content of the mixture of the hydrocarbon/water
b) for mixtures containing protivoallergic through the pipeline.

8. The method according to claim 7, where the corrosion inhibitor and/and and inhibitor of deposition of paraffin is added to the mixture of the hydrocarbon/water.

9. Composition containing
a) 1 parts by weight of protivopokazana gas hydrate as defined in claims 1 to 6, and
b) is 0.0001 to 0.1 parts by weight of a corrosion inhibitor and/or an inhibitor of the formation of paraffin deposits.



 

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EFFECT: raised temperature of combustion of thermal source composition facilitating more deep heating and melting deposits of bottomhole zone of a reservoir, which plug channels and pores, while maintaining level of strength for compression of composition material.

FIELD: production and exploratory well drilling, particularly foaming drilling fluids used during penetration through incompetent rock intervals and during primary productive oil and gas deposit opening in the case of abnormally low formation pressure.

SUBSTANCE: foam composition comprises surfactant, foam stabilizer, water, water hardness control additive and lubricant. The water hardness control additive is sodium silicate. The lubricant is VNIINP-117 emulsion. The foam stabilizer is polyacrylamide, the surfactant is sulphonole. All above components are taken in the following amounts (% by weight): sulphonole - 0.8-1.5, sodium silicate - 0.2-0.5, polyacrylamide - 0.1-0.5, VNIINP-117 - 0.5-2, remainder is water.

EFFECT: reduced power inputs for well drilling, as well as reduced coefficient of friction between drilling tool and well wall.

1 tbl

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