Synergistic blends of anti-agglomerant gas hydrate inhibitors with quaternary benzyl ammonium compounds

Patent metadata

Field	Value
Publication number	US-11898091-B2
Application number	US-202017099233-A
Country	US
Kind code	B2
Filing date	Nov 16, 2020
Priority date	Dec 11, 2019
Publication date	Feb 13, 2024
Grant date	Feb 13, 2024

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)whereineach 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 atomsL 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; andX− 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.

First claim

The invention claimed is:

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, R 5 , linked to a hydrophilic head group —N(R 1 )(R 2 ) or —[N(R 1 )(R 2 )(R 3 )] + X − by a linking moiety, L,
the amphiphile having the general formula (1)
[R 5 -L-N(R 1 )(R 2 )(R 3 )] + X −   (1)

wherein each of R 1 and R 2 is independently an alkyl group having from 1 to 5 carbon atoms; or the nitrogen atom and the R 1 and R 2 groups together form a substituted or unsubstituted heterocyclic group;
R 3 is optionally present; when present, R 3 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;
R 5 is a hydrocarbyl group having from 6 to 22 carbon atoms;
X− is present as an anion when R 3 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 C 8 -C 18 -alkyl group bound to the nitrogen atom.

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

3. The method according to claim 1 , wherein the hydrocarbon is a naturally produced gas with the major part of the gas being C 1 -C 5 hydrocarbons.

4. The method according to claim 1 , wherein R 1 and R 2 independently are alkyl groups having from 3 to 5 carbon atoms.

5. The method according to claim 1 , wherein R 5 is an alkyl or alkenyl group having between 8 and 20 carbon atoms.

6. The method according to claim 1 , wherein R 3 is present as hydrogen or as a methyl group.

7. 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.

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

9. 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.

10. 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.

11. 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.

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

13. The method according to claim 10 , wherein the connecting chain is a heteroaliphatic chain wherein one or more non-adjacent CH 2 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)—NR 6 —, —NR 7 —C(═O), —NR 6 —, —R 7 N—, —O—, —S—, —(SO)— or —(SO 2 )—, wherein R 6 is hydrogen or an alkyl group having from 1 to 5 carbon atoms, and R 7 is hydrogen or an organic moiety having from 1 to 20 carbon atoms.

14. 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(R 6 )—, —N(R 7 )—C(═O)—, —N(R 6 )—, —(R 7 )N—, —O—, —S—, —(SO)— of and —(SO 2 )—, wherein R 6 is hydrogen or an alkyl group having from 1 to 5 carbon atoms and R 7 is hydrogen or an organic moiety having from 1 to 20 carbon atoms.

15. 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(R 6 )—(CH 2 ) t —  (2)

—N(R 7 )—C(═O)—(CH 2 ) t —  (3)

—N(R 7 )—(CH 2 ) 2 —C(═O)—NH—(CH 2 ) t —  (4)

—N(R 7 )—C(═O)—(CH 2 )2—N(R 6 )—(CH 2 ) t —  (5)

—CH(OH)—CH 2 —N(R 6 )—(CH 2 ) t —  (6)

—CH(COOH)—CH 2 —C(═O)—N(R 6 )—(CH 2 ) t —  (7a)

—CH(CH 2 —COOH)—C(═O)—N(R 6 )—(CH 2 ) t —  (7b)

—CH(COOH)—CH 2 —C(═O)[O—(CH 2 ) t ] v —  (8a)

—CH(CH 2 —COOH)—C(═O)[O—(CH 2 ) t ] v —  (8b)

—N(R 7 )—C(═O)—(CH 2 ) 2 —C(═O)—N(R 6 )—(CH 2 ) t —  (9)

—N(R 7 )—C(═O)—CH 2 —CH(OH)—C(═O)—N(R 6 )—(CH 2 ) t —  (10a)

—N(R 7 )—C(═O)—CH(OH)—CH 2 —C(═O)—N(R 6 )—(CH 2 ) t —  (10b)

—N(R 7 )—C(═O)—CH(OH)—CH(OH)—C(═O)—N(R 6 )—(CH 2 ) t —  (11)

—N(R 7 )—C(═O)—C(OH)(CH 2 COOH)—CH 2 —C(═O)—N(R 6 )—(CH 2 ) t —  (12a)

—N(R 7 )—C(═O)—CH 2 —C(OH)(CH(COOH)—C(═O)—N(R 6 )—(CH 2 ) t —  (12b)

wherein
t is 2, 3 or 4:
v is an integer between 1 and 30
R 6 is hydrogen or an alkyl group having from 1 to 5 carbon atoms; and
R 7 is hydrogen or an organic moiety having from 1 to 20 carbon atoms.

16. The method according to claim 1 , wherein the amphiphile is an amido amine according to the general formula (13)

wherein
R 1 , R 2 , R 3 , R 5 and X− have the general meanings given above for formula (1);
R 4 is selected from the group consisting of —(CH 2 )—, —[(CH 2 —CHR 10 )]—, —(CH 2 —CHR 10 O) u (CH 2 ) t — and combinations thereof;
R 6 is hydrogen or an alkyl group having from 1 to 5 carbon atoms;
R 7 is hydrogen or an organic moiety having from 1 to 20 carbon atoms;
R 8 is present or not as hydrogen or an alkyl group having from 1 to 5 carbon atoms; with the proviso that when m=0, R 8 is not present;
R 9 is present or not as hydrogen or an alkyl group having from 1 to 5 carbon atoms; with the proviso that when o=0, R 9 is not present;
R 10 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.

17. The method according to claim 1 , wherein the amphiphile is an amido amine according to the general formula (14)

wherein
R 1 ,R 2 , R 3 , R 5 and X− have the general meanings given above;
R 4 is selected from the group consisting of —(CH 2 ) t — and —[(CH 2 —CHR 10 ) s ]—;

R 6 is hydrogen or an alkyl group having from 1 to 5 carbon atoms;
R 10 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 R 3 is absent, or q is 1 when R 3 is present.

Assignees

• Clariant Int Ltd

Inventors

• Leinweber Dirk
• Ward Zachary Thomas
• Hoevelmann Felix
• WYLDE Jonathan James
• Krull Matthias

Classifications

• C09K8/52 Primary

  Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning · CPC title

• C07D207/404 Primary

  with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide · CPC title

• C10L1/2222

  (cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates (C10L1/221 takes precedence) · CPC title

• C10L3/107

  Limiting or prohibiting hydrate formation · CPC title

• C09K2208/22

  Hydrates inhibition by using well treatment fluids containing inhibitors of hydrate formers · CPC title