Asymmetrically substituted diamido ammonium dicarboxylic acid salts and their use for antiagglomerating gas hydrates
阅读说明：本技术 不对称取代的二羧酸二酰氨基铵盐及其用于气体水合物抗附聚的用途 (Asymmetrically substituted diamido ammonium dicarboxylic acid salts and their use for antiagglomerating gas hydrates ) 是由 N·普尔卡亚斯塔 Z·T·沃德 F·施奈德 D·莱因韦贝尔 M·克鲁尔 J·怀尔德 于 2019-09-11 设计创作，主要内容包括：本发明涉及包含由式(I)表示的N-烷基-N’-(N”,N”-二烷基铵烷基)二羧酸二酰胺盐的气体水合物抑制剂其中：R是含8-22个碳原子的烷基或烯基,R～1是氢、C-1-C-(22)烷基或C-3-C-(22)烯基,R～2和R～3各自独立地是含1-10个碳原子的烷基或一起形成具有5-10个环原子的非必要取代的环,其中所述环可以携带至多3个取代基,R～4是氢,A是含1-18个碳原子的非必要取代的烃基,B是含2-6个碳原子的亚烷基,Y是NR～5,R～5是氢、C-1-C-(22)烷基或C-3-C-(22)烯基,和M～-是阴离子,根据式(I)的化合物的制备方法,式(I)的N-烷基-N’-(N”,N”-二烷基铵烷基)二羧酸二酰胺盐作为气体水合物抗附聚剂的用途和抑制气体水合物附聚的方法,所述方法包括将式(I)的N-烷基-N’-(N”,N”-二烷基铵烷基)二羧酸二酰胺盐添加到含有气体和水的流体中。(The present invention relates to gas hydrate inhibitors comprising N-alkyl-N ' - (N ', N ' -dialkylammonioalkyl) dicarboxylic acid diamide salts represented by formula (I) Wherein: r is an alkyl or alkenyl group having 8 to 22 carbon atoms, R is 1 Is hydrogen, C 1 ‑C 22 Alkyl or C 3 ‑C 22 Alkenyl radical, R 2 And R 3 Each independently an alkyl group having 1 to 10 carbon atomsOr together form an optionally substituted ring having 5 to 10 ring atoms, wherein the ring may carry up to 3 substituents, R 4 Is hydrogen, A is an optionally substituted hydrocarbon radical having from 1 to 18 carbon atoms, B is an alkylene radical having from 2 to 6 carbon atoms, Y is NR 5 ，R 5 Is hydrogen, C 1 ‑C 22 Alkyl or C 3 ‑C 22 Alkenyl, and M ‑ Is an anion, use of an N-alkyl-N '- (N ", N" -dialkylammoniumalkyl) dicarboxylic acid diamide salt of formula (I) as a gas hydrate antiagglomerating agent and a method of inhibiting agglomeration of gas hydrates, the method comprising adding an N-alkyl-N' - (N ", N" -dialkylammoniumalkyl) dicarboxylic acid diamide salt of formula (I) to a fluid containing gas and water.)
1. Gas hydrate inhibitor comprising N-alkyl-N ' - (N ', N ' -dialkylammonioalkyl) dicarboxylic acid diamide salt represented by formula (I)
Wherein:
r is an alkyl or alkenyl group having 8 to 22 carbon atoms,
R1is hydrogen, C1-C22Alkyl or C3-C22An alkenyl group, which is a radical of an alkenyl group,
R2and R3Each independently of the other being an alkyl radical having from 1 to 10 carbon atoms or together forming an optionally substituted ring having from 5 to 10 ring atoms, where the ring may carry up to 3 substituents,
R4is a hydrogen atom, and is,
a is an optionally substituted hydrocarbon radical having from 1 to 18 carbon atoms,
b is an alkylene group having 2 to 6 carbon atoms,
y is NR5，
R5Is hydrogen, C1-C22Alkyl or C3-C22Alkenyl, and
M-is an anion.
2. A gas hydrate inhibitor according to claim 1, wherein R1Is hydrogen or methyl.
3. A gas hydrate inhibitor according to claim 1 and/or 2, wherein R1Is hydrogen.
4. A gas hydrate inhibitor according to one or more of claims 1-3, wherein R2And R3Each independently an alkyl group having 1 or 6 carbon atoms.
5. A gas hydrate inhibitor according to one or more of claims 1-4, wherein R2And R3Each independently an alkyl group having 4 or 5 carbon atoms.
6. A gas hydrate inhibitor according to one or more of claims 1-5, wherein R2And R3Each independently is a linear alkyl group.
7. A gas hydrate inhibitor according to one or more of claims 1-6, wherein R2And R3Are the same.
8. A gas hydrate inhibitor according to one or more of claims 1-7, wherein R5Is hydrogen.
9. A gas hydrate inhibitor according to one or more of claims 1-8, wherein R is an alkyl or alkenyl group containing 10-18 carbon atoms, preferably 12-14 carbon atoms.
10. A gas hydrate inhibitor according to one or more of claims 1-9, wherein a is an alkylene group containing 2-6 carbon atoms.
11. A gas hydrate inhibitor according to one or more of claims 1-10, wherein a is an aromatic radical containing 6-12 carbon atoms.
12. A gas hydrate inhibitor according to one or more of claims 1-11, wherein B is an alkylene group containing 2, 3 or 4 carbon atoms.
13. A gas hydrate inhibitor according to one or more of claims 1-12, wherein B is of formula-CH2-CH2Ethylene of the formula-or having the formula-CH2-CH2-CH2-propylene group.
14. A gas hydrate inhibitor according to one or more of claims 1-13, wherein M-Selected from the group consisting of sulfate, carbonate, bicarbonate, nitrate, halide, and carboxylate.
15. A gas hydrate inhibitor according to one or more of claims 1-14, wherein M-Is a carboxylate anion.
16. A gas hydrate inhibitor according to one or more of claims 1-15, wherein M-Is an anion of a monocarboxylic acid having 1 to 22 carbon atoms.
17. The gas hydrate inhibitor according to one or more of claims 1, 4-9, 12-16, wherein the gas hydrate inhibitor corresponds to formula (Ib)
18. A gas hydrate inhibitor according to one or more of claims 1, 4-7, 9, 14-16, wherein the gas hydrate inhibitor corresponds to formula (Ic)
19. A gas hydrate inhibitor according to one or more of claims 1, 9, 14-16, wherein the gas hydrate inhibitor corresponds to formula (Id)
20. A gas hydrate inhibitor according to one or more of claims 1 or 9, wherein the gas hydrate inhibitor corresponds to formula (If)
21. A gas hydrate inhibitor according to one or more of claims 1-20, wherein the gas hydrate inhibitor comprises both an N-alkyl-N '- (N ", N" -dialkylaminoalkyl) dicarboxylic acid diamide salt according to formula (I) and a corresponding base thereof, which is an N-alkyl-N' - (N ", N" -dialkylaminoalkyl) dicarboxylic acid diamide according to formula (II)
Wherein:
r is an alkyl or alkenyl group having 8 to 22 carbon atoms,
R1is hydrogen, C1-C22Alkyl or C3-C22An alkenyl group, which is a radical of an alkenyl group,
R2and R3Each independently of the other being an alkyl radical having from 1 to 10 carbon atoms or together forming an optionally substituted ring having from 5 to 10 ring atoms, where the ring may carry up to 3 substituents,
a is an optionally substituted hydrocarbon radical having from 1 to 18 carbon atoms,
b is an alkylene group having 2 to 6 carbon atoms,
y is NR5And are and
R5is hydrogen, C1-C22Alkyl or C3-C22An alkenyl group.
22. A gas hydrate inhibitor according to one or more of claims 1-21, wherein the gas hydrate inhibitor contains an organic solvent.
23. A method of synthesis of a compound according to one or more of claims 1-22, wherein the method comprises:
i) condensing a dicarboxylic acid with an aliphatic amine to form a cyclic imide intermediate according to formula (III)
Wherein A and R1Having the meaning given above, it is preferred that,
II) subjecting the cyclic imide intermediate of formula (III) to a ring-opening reaction with an N, N-dialkylaminoalkyleneamine to form an N-alkyl-N' - (N ", N" -dialkylaminoalkyl) dicarboxylic acid diamide represented by formula (II), and
iii) reacting (II) with an acid to form an N-alkyl-N' - (N ", N" -dialkylammonioalkyl) dicarboxylic acid diamide salt represented by formula (I).
24. A method of synthesis of a compound according to one or more of claims 1-22, wherein the method comprises:
i) condensing a dicarboxylic acid with an N, N-dialkylaminoalkyleneamine to form the corresponding mono-and/or dicarboxamides and/or cyclic dicarboximides,
II) carrying out a ring-opening reaction of said mono-and/or dicarboxamide and/or cyclic dicarboximide with a fatty amine to form an N-alkyl-N' - (N ", N" -dialkylaminoalkyl) dicarboxylic diamide represented by formula (II), and
iii) reacting (II) with an acid to form an N-alkyl-N' - (N ", N" -dialkylammonioalkyl) dicarboxylic acid diamide salt represented by formula (I).
25. A method of synthesizing a compound according to one or more of claims 23 or 24, wherein the dicarboxylic acid has the formula:
HOOC-A-COOH (III)
wherein A is an optionally substituted hydrocarbyl group containing 1 to 18 carbon atoms.
26. A method of synthesizing a compound according to one or more of claims 23-25, wherein the fatty amine is a primary or secondary amine of the formula:
HNRR1,
wherein:
r is an alkyl or alkenyl group having 8 to 22 carbon atoms, and
R1is hydrogen, C1-C22Alkyl or C3-C22An alkenyl group.
27. The method of claim 26, wherein R1Is hydrogen.
28. The process of one or more of claims 23-27, wherein the N, N-dialkylaminoalkyleneamine corresponds to (IV)
Wherein:
R2and R3Each independently of the other being an alkyl radical having from 1 to 10 carbon atoms or together forming an optionally substituted ring having from 5 to 10 ring atoms, where the ring may carry up to 3 substituents,
b is an alkylene group having 2 to 6 carbon atoms,
y is NR5Wherein R is5Is hydrogen, C1-C22Alkyl or C3-C22An alkenyl group.
29. The method according to one or more of claims 28, wherein R5Is hydrogen.
30. The method of one or more of claims 23-29, wherein the acid is an organic acid.
31. The method of one or more of claims 23-30, wherein the acid is a carboxylic acid containing 1-22 carbon atoms.
32. Use of a compound according to one or more of claims 1 to 22 as antiagglomerating agent for gas hydrates.
33. Use according to claim 32, wherein the dosage rate of the compound according to one or more of claims 1 to 22 is from 0.01 to 5% by volume (based on the volume of the aqueous phase).
34. A method of inhibiting gas hydrate agglomeration comprising adding a compound according to one or more of claims 1-22 to a fluid comprising a gas and water.
35. The method according to claim 34 wherein the dosage rate of the compound according to one or more of claims 1 to 22 is from 0.01 to 5% by volume (based on the volume of the aqueous phase).
36. Fluid containing a gas, water and oil and an N-alkyl-N' - (N ", N" -dialkylammonioalkyl) dicarboxylic acid diamide salt of formula (I) according to any one of claims 1 to 22.
Examples
The general process for preparing N-alkyl-N' - (N ", N" -dialkylaminoalkyl) dicarboxylic acid diamides starts with a dicarboxylic acid:
the amounts of dicarboxylic acid, aliphatic amine and optionally solvent given in the reaction protocol below were charged to a five-necked flask equipped with a distillation condenser or optionally a Dean-Stark trap connected to a reflux condenser, overhead stirrer, internal thermometer and nitrogen inlet. The temperature of the mixture was increased to 130 ℃ while stirring gently. As the temperature approaches 130 ℃, the mixture slowly melts into a tan liquid. Heating and stirring were continued with continuous removal of water from the reaction mixture.
The progress of the reaction was monitored by potentiometric amine number titration (potentiometric amine number titration) by titrating an aliquot of the reaction mixture with perchloric acid. The amine number is abbreviated AN. Determined by potentiometric titration of the sample with perchloric acid after dilution of the sample with acetic acid. When titration showed AN ≦ 1mmol/g, the formation of the cyclic imide intermediate was considered complete. Cyclic imide products by1H-NMR Spectroscopy (CDCl)3δ 2.67ppm, 4H singlet).
The reaction mixture was cooled to 80 ℃ and equimolar amounts of the diaminoalkanes given in the corresponding protocol were added to the reaction mixture. The reaction mixture was heated to 120-130 ℃ for up to 18 hours with stirring. By passing1The H-NMR spectrum followed the progress of the reaction. When in1When four symmetrical cyclic hydrogen signals of the cyclic imide structure at δ 2.67ppm in the H-NMR spectrum are no longer visible, the reaction is stopped. By passing1H-NMR confirmed the asymmetric diamide structure.
Example 1: N-dodecyl-N' - [3- (dimethylamino) propyl ] -succinic acid diamide
Using 100g (0.85mol) succinic acid, 156.96g (0.85mol) dodecylamine and 86.85g (0.85mol) N, N-dimethylpropane-1, 3-diamine, 298g of N-dodecyl-N' - [3- (dimethylamino) propyl ] -succinic acid diamide were obtained as a brown solid.
Example 2: N-dodecyl-N' - [6- (dimethylamino) hexyl ] -succinic acid diamide
Using 100g (0.85mol) succinic acid, 156.96g (0.85mol) dodecylamine and 122.62g (0.85mol) N, N-dimethyl-hexane-1, 6-diamine, 330g of N-dodecyl-N' - [6- (dimethylamino) hexyl ] -succinic acid diamide were obtained as a brown solid.
Example 3: N-dodecyl-N' - [3- (dibutylamino) propyl ] -succinic acid diamide
Using 100g (0.85mol) succinic acid, 156.96g (0.85mol) dodecylamine and 158.40g (0.85mol) N, N-dibutyl-propane-1, 3-diamine, 379g of N-dodecyl-N' - [3- (dibutylamino) propyl ] -succinic acid diamide were obtained as a brown solid.
Example 4: N-Cocoyl (cocoyl) -N' - [3- (dibutylamino) propyl ] -succinic acid diamide
Using 100g (0.85mol) succinic acid, 166.14g (0.85mol) cocoamine (cocoylamine) (AN 287.15mg koh/g) and 158.40g (0.85mol) N, N-dibutylpropane-1, 3-diamine yielded 374g of N-cocoyl-N' - [3- (dibutylamino) propyl ] -succinic diamide as a brown solid.
Example 5: N-dodecyl-N' - [3- (dibutylamino) propyl ] -malic acid diamide
Using 114g (0.85mol) malic acid, 156.96g (0.85mol) dodecylamine and 158.40g (0.85mol) N, N-dibutyl-propane-1, 3-diamine gave 392g of N-dodecyl-N' - [3- (dibutylamino) propyl ] -malic acid diamide as a brown solid.
Example 6: N-cocoyl-N' - [3- (dibutylamino) propyl ] -malic acid diamide
Using 114g (0.85mol) malic acid, 166.14g (0.85mol) cocoamine (AN 287.15mg koh/g) and 158.40g (0.85mol) N, N-dibutylpropane-1, 3-diamine gave 397g of N-cocoyl-N' - [3- (dibutylamino) propyl ] -malic acid diamide as a brown solid.
Example 7: N-dodecyl-N' - [3- (dibutylamino) propyl ] -tartaric acid diamide
Using 127.58g (0.85mol) tartaric acid, 156.96g (0.85mol) dodecylamine and 158.40g (0.85mol) N, N-dibutyl-propane-1, 3-diamine, 408g of N-dodecyl-N' - [3- (dibutylamino) propyl ] -tartaric acid diamide were obtained as a brown solid.
Example 8: N-cocoyl-N '- [3- (dibutylamino) propyl ] -tartaric acid diamide using 127.58g (0.85mol) tartaric acid, 166.14g (0.85mol) cocoamine (AN ═ 287.15mg koh/g) and 158.40g (0.85mol) N, N-dibutylpropane-1, 3-diamine gave 400g of N-cocoyl-N' - [3- (dibutylamino) propyl ] -tartaric acid diamide as a brown solid.
Example 9: N-dodecyl-N' - [4- (dibutylamino) butyl ] -succinic acid diamide
Using 100g (0.85mol) succinic acid, 156.96g (0.85mol) dodecylamine and 170.31g (0.85mol) N, N-dibutyl-butane-1, 4-diamine, 401g of N-dodecyl-N' - [4- (dibutylamino) butyl ] -succinic acid diamide were obtained as a brown solid.
Example 10: N-dodecyl-N' - [2- (dibutylamino) ethyl ] -succinic acid diamide
Using 100g (0.85mol) succinic acid, 156.96g (0.85mol) dodecylamine and 146.48g (0.85mol) N, N-dibutyl-ethane-1, 2-diamine, 363g of N-dodecyl-N' - [2- (dibutylamino) ethyl ] -succinic acid diamide were obtained as a brown solid.
Example 11: N-dodecyl-N' - [3- (dibutylamino) propyl ] -phthalic acid diamide
141.21g (0.85mol) phthalic acid, 156.96g (0.85mol) dodecylamine and 158.40g (0.85mol) N, N-dibutyl-propane-1, 3-diamine were used to obtain 407g of N-dodecyl-N' - [3- (dibutylamino) propyl ] -phthalic acid diamide as a brown solid.
Example 12: N-dodecyl-N' - [3- (1-piperidinyl) propyl ] -succinic acid diamide
Using 100g (0.85mol) succinic acid, 156.96g (0.85mol) dodecylamine and 167.34g (0.85mol) 3-piperidinylpropylamine, 301g of N-dodecyl-N' - [3- (1-piperidinyl) propyl ] -succinic acid diamide were obtained as a brown solid.
Example 13: N-dodecyl-N' - [3- (4-methylpiperazin-1-yl) ] -succinic acid diamide
Using 100g (0.85mol) of succinic acid, 156.96g (0.85mol) of dodecylamine and 185.00g (0.85mol) of 3- (4-methylpiperazin-1-yl) propylamine, 301g of N-dodecyl-N' - [3- (4-methylpiperazin-1-yl) ] -succinic acid diamide were obtained as a brown solid.
Example 14: N-dodecyl-N-methyl-N' - [3- (dibutylamino) propyl ] -succinic acid diamide
Using 100g (0.85mol) succinic acid, 169.47g (0.85mol) N-methyldodecylamine and 158.40g (0.85mol) N, N-dibutyl-propane-1, 3-diamine, 390g of N-dodecyl-N-methyl-N' - [3- (dibutylamino) propyl ] -succinic acid diamide were obtained as a brown solid.
Example 15: N-dodecyl-N' - [3- (dibutylamino) propyl ] -malonic acid diamide
Using 100g (0.96mol) of malonic acid, 177.94g (0.96mol) of dodecylamine and 178.88g (0.96mol) of N, N-dibutyl-propane-1, 3-diamine, 450g of N-dodecyl-N' - [3- (dibutylamino) propyl ] -malonic acid diamide were obtained as a brown solid.
Example 16: n- [3- (dibutylamino) -propyl ] -N' -dodecyl-succinamide; preparation in xylene
100g (0.85mol) succinic acid, 156.96g (0.85mol) dodecylamine, xylene 415g and 158.40g (0.85mol) N, N-dibutyl-propane-1, 3-diamine were used to obtain 379g of a 50% active solution of N- [3- (dibutylamino) -propyl ] -N' -dodecyl-succinamide in xylene.
General procedure for the preparation of N-alkyl-N' - (N ", N" -dialkylaminoalkyl) dicarboxylic acid diamide salts:
to a reaction flask equipped with an overhead stirrer, reflux condenser and thermometer were added equimolar amounts of the N-alkyl-N' - (N ", N" -dialkylaminoalkyl) dicarboxylic acid diamide synthesized in examples 1-16, the solvent and the acid given in examples 17-35. The temperature of the apparatus was raised to 50 ℃ and the mixture was gently stirred for 2 hours.
Example 17: acrylic acid N-dodecyl-N' - [3- (dibutylammonium) propyl ] -succinic acid diamide
Using 100g (0.22mol) of N-dodecyl-N '- [3- (dibutylamino) propyl ] -succinic acid diamide according to example 3, 15.66g (0.22mol) of acrylic acid and 115.66g of methanol, 231.32g of a 50% active solution of N-dodecyl-N' - [3- (dibutylammonium) propyl ] -succinic acid diamide acrylate in methanol were obtained.
Example 18: acetic acid N-dodecyl-N' - [3- (dibutylammonium) propyl ] -succinic acid diamide
Using 100g (0.22mol) of N-dodecyl-N '- [3- (dibutylamino) propyl ] -succinic acid diamide according to example 3, 12.99g (0.22mol) of acetic acid and 112.99g of methanol, 126g of a 50% active solution of acetic acid N-dodecyl-N' - [3- (dibutylammonium) propyl ] -succinic acid diamide in methanol were obtained.
Example 19: dodecanoic acid N-dodecyl-N' - [3- (dibutylammonium) propyl ] -succinic acid diamide
Using 100g (0.22mol) of N-dodecyl-N '- [3- (dibutylamino) propyl ] -succinic acid diamide according to example 3, 44.07g (0.22mol) of dodecanoic acid and 144.07g of methanol, 288.14g of a 50% active solution of dodecanoic acid N-dodecyl-N' - [3- (dibutylammonium) propyl ] -succinic acid diamide in methanol was obtained.
Example 20: coco oil acid N-dodecyl-N' - [3- (dibutylammonium) propyl ] -succinic acid diamide
Using 100g (0.22mol) of N-dodecyl-N '- [3- (dibutylamino) propyl ] -succinic acid diamide according to example 3, 48.04g (0.22mol) of coconut oil fatty acid and 148.04g of methanol, 296.08g of a 50% active solution of coconut oil N-dodecyl-N' - [3- (dibutylammonium) propyl ] -succinic acid diamide in methanol was obtained.
Example 21: acrylic acid N-cocoyl-N' - [3- (dibutylammonium) propyl ] -succinic acid diamide
Using 100g (0.21mol) of N-cocoyl-N '- [3- (dibutylamino) propyl ] -succinic diamide according to example 4, 15.13g (0.21mol) of acrylic acid and 115.13g of methanol, 130.26g of a 50% active solution of acrylic acid N-cocoyl-N' - [3- (dibutylammonium) propyl ] -succinic diamide in methanol were obtained.
Example 22: acrylic acid N-dodecyl-N' - [3- (dibutylammonium) propyl ] -succinic acid diamide
Using 100g (0.11mol) of a 50% active solution of N-dodecyl-N '- [3- (dibutylamino) propyl ] -succinic acid diamide according to example 15 and 7.83g (0.11mol) of acrylic acid, 107.83g of a 50% active solution of N-dodecyl-N' - [3- (dibutylammonium) propyl ] -succinic acid diamide acrylate in xylene were obtained.
Example 23: acrylic acid N-dodecyl-N' - [3- (dibutylammonium) propyl ] -malic acid diamide
Using 100g (0.21mol) of N-dodecyl-N '- [3- (dibutylamino) propyl ] -malic acid diamide according to example 5, 15.34g (0.21mol) of acrylic acid and 115.34g of methanol, 230.68g of a 50% active solution of N-dodecyl-N' - [3- (dibutylammonium) propyl ] -malic acid diamide acrylate in methanol were obtained.
Example 24: acrylic acid N-cocoyl-N' - [3- (dibutylammonium) propyl ] -malic acid diamide
Using 100g (0.22mol) of N-cocoyl-N '- [3- (dibutylamino) propyl ] -malic acid diamide according to example 6, 15.85g (0.22mol) of acrylic acid and 115.85g of methanol, 231.7g of a 50% active solution of N-cocoyl-N' - [3- (dibutylammonium) propyl ] -malic acid diamide acrylate in methanol were obtained.
Example 25: acrylic acid N-dodecyl-N' - [3- (dibutylammonium) propyl ] -tartaric acid diamide
Using 100g (0.21mol) of N-dodecyl-N '- [3- (dibutylamino) propyl ] -tartaric acid diamide according to example 7, 15.34g (0.21mol) of acrylic acid and 115.34g of methanol, 230.68g of a 50% active solution of N-dodecyl-N' - [3- (dibutylammonium) propyl ] -tartaric acid diamide acrylate in methanol were obtained.
Example 26: acrylic acid N-cocoyl-N' - [3- (dibutylammonium) propyl ] -tartaric acid diamide
Using 100g (0.23mol) of N-cocoyl-N '- [3- (dibutylamino) propyl ] -tartaric acid diamide according to example 8, 16.57g (0.23mol) of acrylic acid and 116.57g of methanol, 233.14g of a 50% active solution of N-cocoyl-N' - [3- (dibutylammonium) propyl ] -tartaric acid diamide acrylate in methanol were obtained.
Example 27: acrylic acid N-dodecyl-N' - [4- (dibutylammonium) butyl ] -succinic acid diamide
Using 100g (0.26mol) of N-dodecyl-N '- [4- (dibutylamino) butyl ] -succinic acid diamide according to example 9, 18.72g (0.26mol) of acrylic acid and 118.72g of methanol 237.44g of a 50% active solution of N-dodecyl-N' - [4- (dibutylammonium) butyl ] -succinic acid diamide acrylate in methanol were obtained.
Example 28: acrylic acid N-dodecyl-N' - [2- (dibutylammonium) ethyl ] -succinic acid diamide
Using 100g (0.23mol) of N-dodecyl-N '- [2- (dibutylamino) ethyl ] -succinic acid diamide according to example 10, 16.38g (0.23mol) of acrylic acid and 116.38g of methanol, 232.77g of a 50% active solution of N-dodecyl-N' - [2- (dibutylammonium) ethyl ] -succinic acid diamide acrylate in methanol were obtained.
Example 29: acrylic acid N-dodecyl-N' - [3- (dimethylammonium) propyl ] -succinic acid diamide
Using 100g (0.27mol) of N-dodecyl-N '- [3- (dimethylamino) propyl ] -succinic acid diamide according to example 1, 19.48g (0.23mol) of acrylic acid and 119.48g of methanol, 238.96g of a 50% active solution of N-dodecyl-N' - [3- (dimethylammonium) propyl ] -succinic acid diamide acrylate in methanol were obtained.
Example 30: acrylic acid N-dodecyl-N' - [6- (dimethylammonium) hexyl ] -succinic acid diamide
Using 100g (0.25mol) of N-dodecyl-N '- [6- (dimethylamino) hexyl ] -succinic acid diamide according to example 2, 17.50g (0.23mol) of acrylic acid and 117.50g of methanol, 235g of a 50% active solution of N-dodecyl-N' - [6- (dimethylammonium) hexyl ] -succinic acid diamide of acrylic acid in methanol were obtained.
Example 31: acrylic acid N-dodecyl-N' - [3- (1-piperidine) propyl ] -succinic acid diamide
100g (0.24mol) of N-dodecyl-N' - [3- (1-piperidinyl) propyl ] according to example 12 are used]Succinic acid diamide, 17.58g (0.24mol) of acrylic acid and 117.58g of methanol to yield 235.16g of N-dodecyl-N' - [3- (1-piperidine) acrylate) Propyl radical]-50% active solution of succinic acid diamide in methanol.
Example 32: acrylic acid N-dodecyl-N' - [3- (4-methylpiperazin-1-yl) ] -succinic acid diamide
100g (0.23mol) of N-dodecyl-N' - [3- (4-methylpiperazin-1-yl) according to example 13 were used]Succinic acid diamide, 16.56g (0.23mol) of acrylic acid and 116.56g of methanol to obtain 233.12g of N-dodecyl-N' - [3- (4-methylpiperazin-1-yl) acrylate)]-50% active solution of succinic acid diamide in methanol.
Example 33: acrylic acid N-dodecyl-N' - [3- (dibutylammonium) propyl ] -phthalic acid diamide
Using 100g (0.20mol) of N-dodecyl-N '- [3- (dibutylamino) propyl ] -phthalic acid diamide according to example 11, 14.40g (0.20mol) of acrylic acid and 114.40g of methanol, 228.8g of a 50% active solution of N-dodecyl-N' - [3- (dibutylammonium) propyl ] -phthalic acid diamide acrylate in methanol were obtained.
Example 34: acrylic acid N-dodecyl-N-methyl-N' - [3- (dibutylammonium) propyl ] -succinic acid diamide
Using 100g (0.21mol) of N-dodecyl-N-methyl-N '- [3- (dibutylamino) propyl ] -succinic acid diamide according to example 14, 15.39g (0.21mol) of acrylic acid and 115.39g of methanol, 130.78g of a 50% active solution of N-dodecyl-N-methyl-N' - [3- (dibutylammonium) propyl ] -succinic acid diamide acrylate in methanol were obtained.
Example 35: acrylic acid N-dodecyl-N' - [3- (dibutylammonium) propyl ] -malonic acid diamide
Using 100g (0.22mol) of N-dodecyl-N '- [3- (dibutylamino) propyl ] -malonic acid diamide according to example 15, 16.37g (0.22mol) of acrylic acid and 116.37g of methanol, 232.74g of a 50% active solution of N-dodecyl-N' - [3- (dibutylammonium) propyl ] -malonic acid diamide acrylate in methanol were obtained.
Table 1: characterization of the inhibitors tested
To evaluate the performance of the disclosed N-alkyl-N' - (N ", N" -dialkylammoniumalkyl) dicarboxylic acid diamide salt (I) as a low dose gas hydrate inhibitor, a rocking cell test (a rocking cell test) was used. The rocking tank test is a common test used in the art to evaluate the performance of anti-agglomerant chemicals. Briefly, additives were evaluated based on their ability to effectively minimize the size of hydrate particle agglomerates, and then disperse those particles into the hydrocarbon phase. The results were classified as either "pass" or "drop" depending on whether hydrate blockage was detected. Performance was evaluated by determining the Minimum Effective Dose (MED) required to register as a "pass" in the rocking cell assay. The effective dose (MED) was screened at 50 and 60 vol% moisture and 138 bar at 4 ℃ for 5.0 wt% NaCl brine, respectively.
The rocking trough device ("rack") is constructed of a plurality of sapphire tubes, each of which is placed within a stainless steel support cage. Each assembled sapphire tube and steel cage (referred to herein as a wobble groove) typically contains a fluid containing a hydrocarbon fluid phase and a brine phase, and stainless steel balls for mixing. The rocking trough can withstand pressures up to 200 bar (2900 psi). Once filled with fluid, the rocking cell is mounted on a frame and gas injection and pressure monitoring is performed. During the test, as the gas cooled and hydrates formed, the consumed gas was replaced by a high pressure syringe pump to maintain a constant pressure in the system.
The frame is provided with 10 swing grooves (2 is groove width, 5 is groove height) which are arranged in 2 x 5. The central position on the frame (between the two slots) is fixed and allowed to rotate while the outer position on the frame moves vertically up and down. This vertical movement rotates the rocking slot to either a positive or negative angular position. The steel ball, which is swung within the sapphire tube, moves from one end of the trough to the other during the rocking process. The frame oscillates up and down at a rate of about 5 complete cycles (up and down) per minute. The racks are also housed in temperature control baths attached to coolers controlled at-10 ℃ to 60 ℃.
The rocking trough is filled with three components: hydrocarbon, aqueous phase and gas. First, each rocking sapphire tube was filled with 5mL dodecane and 5mL 5% NaCl brine (50% water by volume) and 4mL dodecane and 6mL 5% NaCl brine (60% water by volume), respectively, with a total liquid loading of 50% of the total subvolume (20 mL total). The inhibitor was added as a 50 wt% active solution at a dosage rate in percent by volume (vol%) of water. Green Canyon gas was used for this test, the composition of which is given in table 2.
Table 2: green Canyon gas composition
ComponentsName (name)Balance
TransformingLearning symbolNumber (C)
Measurement of
(mol-％)
Nitrogen is present inQi (Qi)
N2
0.14
IIOxygen gasTransformingCarbon (C)
CO2
0
First of allAlkane (I) and its preparation method
C1
87.56
Second stepAlkane (I) and its preparation method
C2
7.6
C3Alkane (I) and its preparation method
C3
3
Chinese medicinal compositionAlkane (I) and its preparation method
i-C4
0.5
Is justT-shirtAlkane (I) and its preparation method
n-C4
0.8
Isoprene (I)Alkane (I) and its preparation method
i-C5
0.2
Is justWu Ying (five-element)Alkane (I) and its preparation method
n-C5
0.2
Rocking bath test procedure:
A. the method comprises the following steps: once the swing tank containing hydrocarbon fluid and brine is loaded on the rack, the swing tank is evacuated for 15-20 minutes with a vacuum pump. Simultaneously with the evacuation, the bath temperature was raised to the initial test temperature of 49 ℃. Once the bath temperature reached 49 ℃, the tank and syringe pump were pressurized to 138 bar with Green Canyon gas and the syringe pump was turned on to maintain the pressure during the initial saturation.
B. A saturation step: the apparatus was set to rock at a rate of 5 oscillations per minute for 2 hours to ensure that the hydrocarbon fluids and brine loaded in the tank had been saturated with gas. The test was carried out at constant pressure, and in the rest of the test the syringe pump was kept open and set at 138 bar.
C, cooling: the system was cooled from 49 ℃ to 4 ℃ over 6 hours while maintaining a rocking speed of 5 oscillations per minute.
D. Steady state mixing step before shutdown (Shut-in): the apparatus was rocked at 5 oscillations per minute for 12 hours at a constant temperature of 4 ℃ to ensure complete hydrate formation.
E. Shutdown step: the apparatus was set to stop rocking and the slot position was set to horizontal and held at a constant temperature of 4 ℃ for 12 hours.
F. Steady state mixing after shutdown: at the end of the shutdown period, the device was restarted at a constant temperature of 4 ℃ for 4 hours at a rate of 5 swings per minute.
G. And (3) completing the test: at the end of the experiment, the apparatus was set to stop rocking and the grooves were set to a negative inclination to allow the fluid to exit the gas injection port. The cooler bath temperature was set to 49 ℃ to melt any hydrates formed and to depressurize and clean.
To determine the relative performance of each inhibitor or the dose rate of the inhibitor, visual observations were made during shutdown and correlated with the time required for the ball in the tank to move between the two magnetic sensors. Each experiment was repeated to confirm reproducibility. Table 3 below shows the results of some rocking cell tests.
For comparison, the following substances according to the prior art were tested.
C1 acrylic acid N- [3- (dibutylammonium) propyl ] -cocamide according to WO 2005/042675
C2 reaction product of N- (3-dibutylamino-propyl) -N' -octadecyl-propionamide with acrylic acid according to WO 2016/069987
C3N- (2-dibutyl-2-methylammonium-ethyl) -tetrapropylenesuccinate methylsulfate according to example 5 of U.S. Pat. No. 5, 2004/163306
Table 3: as a result of the test of the anti-agglomerating agent, the water content was 50% by volume
Test of
Restraining deviceSystem for makingAgent for treating cancer
MED (vol%)
T1
Practice ofExample (b)
17
0.2％
T2
Practice ofExample (b)
18
0.4％
T3
Practice ofExample (b)
19
0.3％
T4
Practice ofExample (b)
20
0.3％
T5
Practice ofExample (b)
21
0.3％
T6
Practice ofExample (b)
22
0.6％
T7
Practice ofExample (b)
23
0.6％
T8
Practice ofExample (b)
24
0.6％
T9
Practice ofExample (b)
25
0.6％
T10
Practice ofExample (b)
26
0.6％
T11
Practice ofExample (b)
27
0.4％
T12
Practice ofExample (b)
28
0.4％
T13
Practice ofExample (b)
29
0.6％
T14
Practice ofExample (b)
30
0.6％
T15
Practice ofExample (b)
31
0.4％
T16
Practice ofExample (b)
32
0.5％
T17
Practice ofExample (b)
33
0.6％
T18
Practice ofExample (b)
34
0.4％
T19
Practice ofExample (b)
35
0.5％
T20 (comparison)
)
Practice ofExample (b)
C1
0.7％
T21 (comparison)
)
Practice ofExample (b)
C2
0.8％
T22 (comparison)
)
Practice ofExample (b)
C3
0.9％
MED is the lowest effective dose; comparative example, not according to the invention.
Table 4: as a result of the test of the anti-agglomerating agent, the water content was 60% by volume
Test of
Restraining deviceSystem for makingAgent for treating cancer
MED (vol%)
T23
Practice ofExample (b)
17
0.3％
T24
Practice ofExample (b)
18
0.5％
T25
Practice ofExample (b)
19
0.5％
T26
Practice ofExample (b)
20
0.4％
T27
Practice ofExample (b)
21
0.4％
T28
Practice ofExample (b)
22
0.7％
T29
Practice ofExample (b)
23
0.7％
T30
Practice ofExample (b)
24
0.8％
T31
Practice ofExample (b)
25
0.8％
T32
Practice ofExample (b)
26
0.7％
T33
Practice ofExample (b)
27
0.5％
T34
Practice ofExample (b)
28
0.6％
T35
Practice ofExample (b)
29
0.9％
T36
Practice ofExample (b)
30
0.8％
T37
Practice ofExample (b)
31
0.5％
T38
Practice ofExample (b)
32
0.7％
T39
Practice ofExample (b)
33
0.7％
T40
Practice ofExample (b)
34
0.6％
T41
Practice ofExample (b)
35
0.7％
T42 (comparison)
)
Practice ofExample (b)
C1
1.1％
T43 (comparison)
)
Practice ofExample (b)
C2
1.2％
T44 (comparison)
)
Practice ofExample (b)
C3
1.5％
MED is the lowest effective dose; comparative example, not according to the invention.
In another set of experiments, the temperature was set to 4 ℃ and the time (hours) for hydrate formation was measured under isobaric conditions using the same dose rate (induction time) of 0.6 vol.% for all products.
Table 5: induction time at 4 deg.C
From the above test results it can be seen that the product according to the invention shows improved properties compared to gas hydrate inhibitors according to the prior art. They require lower dose rates even with increased water cut and allow longer shut down times.