# US 11,898,091 B2 · Synergistic blends of anti-agglomerant gas hydrate inhibitors with quaternary benzyl ammonium compounds

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- Number: US 11,898,091 B2
- Document ID: US11898091B2
- Status: Granted
- Kind: B2
- Application number: 17/099,233
- Filed: 2020-11-16
- Published: 2021-06-17
- Granted: 2024-02-13
- Earliest claimed: 2019-12-11
- Assignees: Clariant International Ltd.
- Applicants: Clariant International, Ltd.
- Inventors: Dirk Leinweber; Zachary Thomas Ward; Felix Hoevelmann; Jonathan James Wylde; Matthias Krull
- Web page: https://patentgrep.com/patent/US11898091B2

## CPC

- C09K 8/035: Organic additives
- C09K 8/52: Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C07D 207/404: with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
- C09K 8/524: organic depositions, e.g. paraffins or asphaltenes
- C10L 1/2222: {(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates (C10L1/221 takes precedence)}
- C10L 3/107: {Limiting or prohibiting hydrate formation}
- C09K 2208/22: Hydrates inhibition by using well treatment fluids containing inhibitors of hydrate formers
- C10L 2200/0259: Nitrogen containing compounds
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C10L: FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS

## Abstract

Disclosed is a gas hydrate inhibitor composition comprising an amphiphile by a linking moiety, the amphiphile having of the general formula (1) [R5-L-N(R1)(R2)(R3)]+X− (1) wherein each of R1 and R2 is an alkyl group having from 1 to 5 carbon atoms; or wherein the nitrogen atom and the R1 and R2 groups together form a heterocyclic group; R3 is present or not as hydrogen or an alkyl group having from 1 to 8 carbon atoms L is a linking moiety comprising a hydrocarbyl group having at least 2 adjacent carbon atoms, at least one heteroatom selected from nitrogen and oxygen, R5 is a hydrocarbyl group having from 6 to 22 carbon atoms; and X− is present as an anion when R3 is present; and a cationic surfactant which is selected from quaternary benzyl ammonium salts and a method of using the gas hydrate inhibitor composition.

## Claims

### Claim 1

A method for inhibiting the formation of gas hydrate agglomerates and plugs, the method comprising bringing a system containing hydrocarbons and water susceptible to gas hydrate formation into contact with a composition comprising
A) from 5 to 95 weight % of an amphiphile having a hydrophobic tail, R5, linked to a hydrophilic head group —N(R1)(R2) or —[N(R1)(R2)(R3)]+X−by a linking moiety, L,
the amphiphile having the general formula (1)
[R5-L-N(R1)(R2)(R3)]+X− (1)
wherein each of R1 and R2 is independently an alkyl group having from 1 to 5 carbon atoms; or the nitrogen atom and the R1 and R2 groups together form a substituted or unsubstituted heterocyclic group;
R3 is optionally present; when present, R3 is hydrogen or an alkyl group having from 1 to 8 carbon atoms which optionally bears a hydroxy group or a carboxy group at the 2-position;
L comprises an optionally substituted hydrocarbyl group having at least 2 adjacent carbon atoms, at least one heteroatom selected from nitrogen and oxygen, and optionally one or more further heteroatoms;
R5 is a hydrocarbyl group having from 6 to 22 carbon atoms;
X− is present as an anion when R3 is present; and
B) from 5 to 95 weight-% of a cationic surfactant which is selected from the group consisting of quaternary benzyl ammonium salts having, in addition to the benzyl group, at least one C8-C18-alkyl group bound to the nitrogen atom.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the pressure during contacting is at or greater than atmospheric pressure.

### Claim 3 (depends on 1)

The method according to claim 1, wherein the hydrocarbon is a naturally produced gas with the major part of the gas being C1-C5 hydrocarbons.

### Claim 4 (depends on 1)

The method according to claim 1, wherein R1 and R2 independently are alkyl groups having from 3 to 5 carbon atoms.

### Claim 5 (depends on 1)

The method according to claim 1, wherein R5 is an alkyl or alkenyl group having between 8 and 20 carbon atoms.

### Claim 6 (depends on 1)

The method according to claim 1, wherein R3 is present as hydrogen or as a methyl group.

### Claim 7 (depends on 1)

The method according to claim 1, wherein X− is selected from the group consisting of hydroxide, carboxylate, halide, sulphate, nitrite, nitrate, organic sulfonate, phosphate, organic phosphonate and combinations thereof.

### Claim 8 (depends on 1)

The method according to claim 1, wherein X− is a carboxylate anion.

### Claim 9 (depends on 8)

The method according to claim 8, wherein the carboxylate anion is selected from the group consisting of formate, acetate, propionate, acrylate, methacrylate and any combination thereof.

### Claim 10 (depends on 1)

The method according to claim 1, wherein the linking moiety L contains a connecting chain that directly connects the hydrophilic head group to the hydrophobic tail, the connecting chain comprising: at least 2 adjacent carbon atoms, at least one heteroatom selected from nitrogen and oxygen, and, optionally, one or more additional heteroatoms, wherein the carbon atoms and heteroatoms are optionally substituted.

### Claim 11 (depends on 10)

The method according to claim 10, wherein the connecting chain is an optionally substituted heteroaliphatic chain comprising at least one heteroatom selected from the group consisting of nitrogen and oxygen.

### Claim 12 (depends on 11)

The method according to claim 11, wherein the at least one heteroatom is nitrogen.

### Claim 13 (depends on 10)

The method according to claim 10, wherein the connecting chain is a heteroaliphatic chain wherein one or more non-adjacent CH2 groups are replaced by a heteroatom selected from the group consisting of nitrogen and oxygen and optionally by one or more further heteroatom(s) which are part of a functional group selected from the group consisting of —C(═O)—O—, —O—C(═O)—, —C(═O)—NR6—, —NR7—C(═O), —NR6—, —R7 N—, —O—, —S—, —(SO)— or —(SO2)—, wherein R6 is hydrogen or an alkyl group having from 1 to 5 carbon atoms, and R7 is hydrogen or an organic moiety having from 1 to 20 carbon atoms.

### Claim 14 (depends on 10)

The method according to claim 10, wherein the connecting chain comprises one or more aliphatic groups having 2 to 10 adjacent carbon atoms, connected
a) to each other;
b) to the hydrophobic tail; or
c) to both a) and b)
by a heteroatom, wherein the heteroatom may be part of a functional group selected from the group consisting of —C(═O)—O—, —O—C(═O)—, —C(═O)—N(R6)—, —N(R7)—C(═O)—, —N(R6)—, —(R7)N—, —O—, —S—, —(SO)— of and —(SO2)—, wherein R6 is hydrogen or an alkyl group having from 1 to 5 carbon atoms and R7 is hydrogen or an organic moiety having from 1 to 20 carbon atoms.

### Claim 15 (depends on 1)

The method according to claim 1, wherein the structure of the linking moiety L corresponds to one out of formulae (2) to (12b)
—C(═O)—N(R6)—(CH2)t— (2)
—N(R7)—C(═O)—(CH2)t— (3)
—N(R7)—(CH2)2—C(═O)—NH—(CH2)t— (4)
—N(R7)—C(═O)—(CH2)2—N(R6)—(CH2)t— (5)
—CH(OH)—CH2—N(R6)—(CH2)t— (6)
—CH(COOH)—CH2—C(═O)—N(R6)—(CH2)t— (7a)
—CH(CH2—COOH)—C(═O)—N(R6)—(CH2)t— (7b)
—CH(COOH)—CH2—C(═O)[O—(CH2)t]v— (8a)
—CH(CH2—COOH)—C(═O)[O—(CH2)t]v— (8b)
—N(R7)—C(═O)—(CH2)2—C(═O)—N(R6)—(CH2)t— (9)
—N(R7)—C(═O)—CH2—CH(OH)—C(═O)—N(R6)—(CH2)t— (10a)
—N(R7)—C(═O)—CH(OH)—CH2—C(═O)—N(R6)—(CH2)t— (10b)
—N(R7)—C(═O)—CH(OH)—CH(OH)—C(═O)—N(R6)—(CH2)t— (11)
—N(R7)—C(═O)—C(OH)(CH2COOH)—CH2—C(═O)—N(R6)—(CH2)t— (12a)
—N(R7)—C(═O)—CH2—C(OH)(CH(COOH)—C(═O)—N(R6)—(CH2)t— (12b)
wherein
t is 2, 3 or 4:
v is an integer between 1 and 30
R6 is hydrogen or an alkyl group having from 1 to 5 carbon atoms; and
R7 is hydrogen or an organic moiety having from 1 to 20 carbon atoms.

### Claim 16 (depends on 1)

The method according to claim 1, wherein the amphiphile is an amido amine according to the general formula (13)
wherein
R1, R2, R3, R5 and X− have the general meanings given above for formula (1);
R4 is selected from the group consisting of —(CH2)—, —[(CH2—CHR10)]—, —(CH2—CHR10O)u(CH2)t— and combinations thereof;
R6 is hydrogen or an alkyl group having from 1 to 5 carbon atoms;
R7 is hydrogen or an organic moiety having from 1 to 20 carbon atoms;
R8 is present or not as hydrogen or an alkyl group having from 1 to 5 carbon atoms; with the proviso that when m=0, R8 is not present;
R9 is present or not as hydrogen or an alkyl group having from 1 to 5 carbon atoms; with the proviso that when o=0, R9 is not present;
R10 is an alkyl group having 1 to 4 carbon atoms;
m is 0 or 2,
n is 0 or 1,
o is 0 or 2,
p is 0 or an integer between 1 and 5;
q is 0 or an integer between 1 and 6, but is not more than the sum of n+p
n+p is an integer between 1 and 6;
s is 1, 2 or 3;
t is 2, 3 or 4; and
u is an integer between 1 and 100.

### Claim 17 (depends on 1)

The method according to claim 1, wherein the amphiphile is an amido amine according to the general formula (14)
wherein
R1,R2, R3, R5 and X− have the general meanings given above;
R4 is selected from the group consisting of —(CH2)t— and —[(CH2—CHR10)s]—;
R6 is hydrogen or an alkyl group having from 1 to 5 carbon atoms;
R10 is an alkyl group having 1 to 4 carbon atoms;
p is an integer between 1 and 5;
s is 1, 2 or 3;
t is 2, 3 or 4;
q is 0 when R3 is absent, or q is 1 when R3 is present.

### Claim 18 (depends on 17)

The method according to claim 17, wherein the compound according to formula (14) is the reaction product of an N,N-dialkyl-aminoalkylamine of formula HN(R6)—R4—N(R1)(R2) with a fatty acid, a fatty acid ester or a glyceride.

### Claim 19 (depends on 17)

The method according to claim 17, wherein the compound according to formula (14) includes a product prepared by the reaction of an amine selected from the group consisting of (3-dialkylamino)propylamine and (3-dialkylamino)ethylamine with a vegetable oil or tallow oil, followed by either neutralization with an acid selected from the group consisting of mineral acids and carboxylic acids having from 1 to 20 carbon atoms, or followed by quaternization with an alkylating agent selected from the group consisting of an organic halide, dimethyl sulfate, diethyl sulfate and C2-C4 alkylene oxides, and wherein the dialkyl amino group of the (3-dialkylamino)propylamine includes two alkyl groups independently selected from the group consisting of methyl, ethyl, propyl, butyl, and combinations thereof or, wherein R1 and R2 together with the nitrogen atom to which they are attached form a substituted or unsubstituted heterocyclic group having 5 or 6 atoms in the ring.

### Claim 20 (depends on 1)

The method according to claim 1, wherein the amphiphile is an amido amine according to one or more of formulae (15), (16) and (17):
wherein
R1,R2, R3, R5 and X− have the meanings given above for formula (1);
R4 is —(CH2)t—;
R6 is hydrogen or an alkyl group having from 1 to 5 carbon atoms;
R7 is hydrogen or an organic moiety having 1 to 20 carbon atoms;
R8 and R9 independently is present or not as hydrogen or an alkyl group having from 1 to 5 carbon atoms;
q is 0 when R3, R8 and R9 are absent; and q is 1, 2 or 3 depending on the presence of one or more of R3, R8 and R9; and
t is 2, 3 or 4.

### Claim 21 (depends on 1)

The method according to claim 1, wherein the cationic surfactant is a benzyl ammonium compound of the formula (19):
wherein
R11 is an alkyl group having 8 to 18 carbon atoms,
R12 is an alkyl group having from 1 to 5 carbon atoms,
R19 is an alkyl group having from 1 to 18 carbon atoms, and
Y− is an anion.

### Claim 22 (depends on 21)

The method according to claim 21, wherein R12 and R19 are methyl groups.

### Claim 23 (depends on 21)

The method according to claim 21, wherein Y− is selected from the group consisting of, chloride, bromide, hydroxide, methosulfate, ethosulfate and combinations thereof.

### Claim 24 (depends on 1)

The method according to claim 1, wherein the portion of the cationic surfactant is between 10 and 85 wt. % based on the combined weights of the amphiphile and the cationic surfactant.

### Claim 25 (depends on 1)

The method according to claim 1, wherein the weight ratio between the amphiphile and the cationic surfactant is between 20:1 and 1:20.

### Claim 26 (depends on 1)

The method according to claim 1, additionally containing up to 30 wt. % of a further surfactant being different from the amphiphile and the cationic surfactant, based on the combined masses of the amphiphile and the cationic surfactant.

### Claim 27 (depends on 1)

The method according to claim 1, containing 1 to 30 wt. % of at least one further surfactant being different from the amphiphile and the cationic surfactant, wherein the at least one further surfactant is selected from the group consisting of anionic, nonionic, amphoteric and/or cationic surfactants.

### Claim 28 (depends on 26)

The method according to claim 26, wherein the composition further comprises at least one kinetic gas hydrate inhibitor being different from the amphiphile, the cationic surfactant, and the at least one further surfactant.

### Claim 29 (depends on 1)

The method according to claim 1, wherein the composition further comprises at least one diluent.

### Claim 30 (depends on 29)

The method according to claim 29, wherein the diluent is selected from the group consisting of monohydric lower alcohols, glycols, ether solvents, ketonic solvents, esters, acetonitrile, water, aliphatic, aromatic, alkylaromatic solvents, and mixtures thereof.

### Claim 31 (depends on 28)

The method according to claim 28, wherein the composition further comprises at least one diluent and wherein the diluent is present in the range from 0.1 wt. % to 95 wt. %, based on the combined weight of the amphiphile, the cationic surfactant, the at least one further surfactant and the diluent.