CN102952023B - Star-shaped hydrate anti-agglomerant and its preparation method - Google Patents
Star-shaped hydrate anti-agglomerant and its preparation method Download PDFInfo
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- CN102952023B CN102952023B CN201110240506.6A CN201110240506A CN102952023B CN 102952023 B CN102952023 B CN 102952023B CN 201110240506 A CN201110240506 A CN 201110240506A CN 102952023 B CN102952023 B CN 102952023B
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Abstract
The invention discloses a star-shaped hydrate anti-agglomerant used for natural gas collection in gas fields and long-distance pipeline conveying production, and its preparation method, and relates to the technical fields of general methods in the organic chemistry, materials not put into other categories and not having other applications, and the petroleum industry. The star-shaped hydrate anti-agglomerant has a four-armed star-shaped structure, and each of single arms contains a quaternary cation composed of two R1 structures and a long hydrophobic chain, wherein the R1 structure is one selected from an n-butyl group, an n-pentyl group or an isopentyl group; the butyl group or the pentyl group penetrates cavities at the hydrate surface to delay the hydrate growth; the single long alkyl carbon chain structure is selected from C8-18 saturated alkyl groups; and the single long hydrophobic chain prevents the continuous hydrate surface growth. The star-shaped hydrate anti-agglomerant has the advantages of no super-cooling degree restriction, promotion of the water-in-oil emulsion formation of an oil-water solution, good hydrate dispersion effect, and greatest inhibition of the conglomeration of the generated hydrate.
Description
Technical field
The present invention is a kind of for star-like hydrate anticoagulant and preparation method thereof that natural gas field gathers and long-distance transportation through pipeline is produced, and relates to vitochemical general method, excludes material and the petroleum industry technical field of other application of do of other classification.
Background technology
Lower boiling methane be main lighter hydrocarbons and carbonic acid gas, hydrogen sulfide under certain temperature and pressure condition, easily form the seemingly solid hydrate of ice of cage shape with water molecules.In oil-gas mining course of conveying, owing to condensing on part water in-line wall in Sweet natural gas, easily cause medium flowing aperture in pipe to diminish, constricted flow, energy consumption increases, and just can cause the local ice of pipeline stifled when serious.How the generation of prevent and avoid hydrate ensures that the safe operation of gas transmission line has caused everybody very big concern.
At present, the method that inhibition hydrate generates mainly contains: evaporation, voltage drop method, heating method, interpolation chemical inhibitor method, wherein adding chemical inhibitor is the most frequently used and effective means.The alcohols of tradition use or electrolytes thermodynamics inhibitor are avoided and prevent that hydrate from generating by changing hydrate generation temperature and pressure condition.This thermodynamics inhibitor exists that consumption is large, content is high (generally accounting for the 10%-60% of water massfraction), high in cost of production shortcoming, and this type of inhibitor also exists the danger such as inflammable and explosive, poisonous, burn into contaminate environment, Oil and gas station safety in production and operating personnel are had a negative impact.From the nineties in 20th century, be devoted to research and develop low-dosage inhibitor both at home and abroad always and substitute thermodynamics inhibitor, it has, and add-on is little, successful, use cost are low, advantages of environment protection.Anti polymerizer is some tensio-active agents or low-molecular(weight)polymer, makes hydrate be molecule be suspended in fluid and flow by dissemination, and preventing being gathered into piece by hydrate crystal, to form ice stifled.
It is a kind of desirable anti polymerizer that Shell patent WO9517579 has mentioned quaternary ammonium surfactant, the ammonium salt that contains two or more normal-butyls has the performance of good delay hydrate crystal growth, adopt long hydrophobic chain to replace 1-2 little alkyl, there is better anti-poly-performance.
CN101376852 mentions a kind of four quaternary cationicses that contain long carbochain, and this inhibitor has two methyl and a butyl.In process of inhibition, methyl replaces methane component to participate in hydrate generation, and butyl replaces the above component participation of C4 hydrate to form, and the hydrate of generation can not be gathered into piece due to the existence of long normal carbon chain, play anti-poly-effect.
Hub-and-spoke configuration molecule has good space symmetr structure, easily generates spherocrystal as nucleus, and structure is dense, and dispersion effect is better.The present invention, on the mechanism of action basis that takes into full account gas hydrate anti polymerizer, in conjunction with the distinctive symmetrical structure of hub-and-spoke configuration molecule, has proposed a kind of efficient star-like hydrate anticoagulant, for hydrate inhibitor research provides a new thinking.
Summary of the invention
The object of the invention is to invent and a kind ofly there is the condensate depression of not being subject to restriction, impel oil solution to form the hydrate that water in oil milk sap, hydrate dispersion effect suppressed to generate better, to be to the full extent gathered into star-like hydrate anticoagulant of piece effect and preparation method thereof.
Gas hydrate anti polymerizer of the present invention has following feature: a) four arms asteroids; B) in single armed, all contain four quaternary ammonium salt cationics that formed by two R1 structures and single long hydrophobic group chain.
Described R1 structure is selected from the one in normal-butyl, n-pentyl or isopentyl; In the hole on butyl or amyl group water leaking-in compound surface, delay hydrate growth;
Described single long alkyl carbon chain structure is selected from C8-18 saturated alkyl; Single long hydrophobic group chain stops the continuous surface growth of hydrate.
These gas hydrate anti polymerizer is specifically: octadecyl bromide and dibutyl or amylamine obtain octadecyl dibutylamine or octadecyl amylamine for 0.8: 1 in molar ratio～1: 1; Tetramethylolmethane and SOCl
21: 4.1 in molar ratio～1: 5.0, obtain white crystal season penta tetrachloro; Season penta tetrachloro and octadecyl dibutyl or amylamine within 1.4: 1 in molar ratio～1.8: 1, obtain star-like hydrate anticoagulant.
Hub-and-spoke configuration provides good space symmetr structure, impels oil solution to form water in oil milk sap, and hydrate dispersion effect is better, and the hydrate that has suppressed to the full extent to generate is gathered into piece.
The preparation method of gas hydrate anti polymerizer of the present invention comprises three steps:
(1) at 30～100 DEG C, under base catalysis, octadecyl bromide is added drop-wise in dibutyl or amylamine, wherein bromine/amine mol ratio 0.8: 1～1: 1, reaction 2～6h, after filtration, obtain octadecyl dibutyl or amylamine after underpressure distillation;
(2) tetramethylolmethane/pyridine is added in the four-hole bottle that reflux condensing tube is housed, in 2h, drip SOCl
2, wherein alcohol/SOCl
2mol ratio 1: 4.1～1: 5.0, back flow reaction 20h at 100～140 DEG C; After overcooling, filtration, washing, dry, distillation procedure, obtain white crystal season penta tetrachloro;
(3) octadecyl dibutyl or amylamine/Virahol are joined in there-necked flask, season penta, tetrachloro slowly dropped in reactor, wherein chlorine/amine mol ratio 1.4: 1～1.8: 1,60～120 DEG C of reaction 2～6h obtain the star-like hydrate anticoagulant with long hydrophobic alkyl chain after underpressure distillation.
In gas hydrate anti polymerizer of the present invention, four quaternary ammonium salt cationics of hydrophilic compound have retrained hydrate particles, in the hole on butyl or amyl group water leaking-in compound surface, delay hydrate growth, long hydrophobic group chain stops the continuous surface growth of hydrate, hub-and-spoke configuration provides good space symmetr structure, impel oil solution to form water in oil milk sap, hydrate dispersion effect is better, and the hydrate that has suppressed to the full extent to generate is gathered into piece.
Star-like hydrate anticoagulant of the present invention is low as hydrate inhibitor working concentration in natural gas field collection and long-distance transportation through pipeline production, adds massfraction between 0.1%-2%, between working pressure 0.1-30Mpa.
Brief description of the drawings
The star-like hydrate anticoagulant molecular structure of Fig. 1
Embodiment
Embodiment. also the present invention is further illustrated with this example, the specific embodiment of the present invention to be described.
1) 10g dibutylamine is joined in there-necked flask, add 0.6g salt of wormwood to make catalyzer, solution is heated to 60 DEG C, 51.8g octadecyl bromide is slowly dropped in reactor, stopped reaction after 4h, after filtration, obtain octadecyl dibutylamine after underpressure distillation;
2) 13.6g tetramethylolmethane and 23.7g pyridine are added in the 250ml four-hole bottle that reflux condensing tube is housed, under agitation in 2h, drip 53.6gSOCl with constant pressure funnel
2(keeping system temperature at 65 DEG C), be slowly warming up to 120 DEG C, back flow reaction 20h.After overcooling, filtration, washing, dry, distillation procedure, obtain white crystal season penta tetrachloro;
3) 16.1g octadecyl dibutylamine is joined in there-necked flask, add 2.5g Virahol, solution be heated to 80 DEG C, by 16.8g season penta tetrachloro slowly drop in reactor, stopped reaction after 4h obtains the star-like hydrate anticoagulant with long hydrophobic alkyl chain after underpressure distillation.
The star-like hydrate anticoagulant that this example is made is low as hydrate inhibitor working concentration in natural gas field collection and long-distance transportation through pipeline production, adds massfraction between 0.1%-2%, between working pressure 0.1-30Mpa.
Claims (3)
1. a star-like hydrate anticoagulant, is characterized in that it has: a) four arms asteroids; B) in single armed, all contain four quaternary ammonium salt cationics that formed by two R1 structures and single long hydrophobic group chain;
Described R1 structure is selected from the one in normal-butyl, n-pentyl or isopentyl; In the hole on butyl or amyl group water leaking-in compound surface, delay hydrate growth;
Described single long alkyl carbon chain structure is selected from C8-18 saturated alkyl; Single long hydrophobic group chain stops the continuous surface growth of hydrate;
Described star-like hydrate anticoagulant molecular structure is:
2. the star-like hydrate anticoagulant of one according to claim 1, it is characterized in that octadecyl bromide and dibutyl or amylamine in molar ratio 0.8:1～1:1 obtain octadecyl dibutyl or amylamine; Tetramethylolmethane and SOCl
21:4.1～1:5.0 in molar ratio, obtains white crystal season penta tetrachloro; Season penta tetrachloro and octadecyl dibutyl or amylamine in molar ratio 1.4:1～1.8:1 obtain star-like hydrate anticoagulant.
3. a preparation method for star-like hydrate anticoagulant as claimed in claim 1, is characterized in that it comprises three steps:
(1) at 30～100 DEG C, under base catalysis, octadecyl bromide is added drop-wise in dibutyl or amylamine, wherein bromine/amine mol ratio 0.8:1～1:1, reaction 2～6h, after filtration, obtain octadecyl dibutyl or amylamine after underpressure distillation;
(2) tetramethylolmethane/pyridine is added in the four-hole bottle that reflux condensing tube is housed, in 2h, drip SOCl
2, wherein alcohol/SOCl
2mol ratio 1:4.1～1:5.0, back flow reaction 20h at 100～140 DEG C; After overcooling, filtration, washing, dry, distillation procedure, obtain white crystal season penta tetrachloro;
(3) octadecyl dibutyl or amylamine/Virahol are joined in there-necked flask, season penta, tetrachloro slowly dropped in reactor, wherein chlorine/amine mol ratio 1.4:1～1.8:1,60～120 DEG C of reaction 2～6h obtain the star-like hydrate anticoagulant with long hydrophobic alkyl chain after underpressure distillation.
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| CN104086436A (en) * | 2014-07-14 | 2014-10-08 | 山东省泰和水处理有限公司 | Synthetic method of star-shaped tetra-quaternary ammonium salt |
| CN104262184B (en) * | 2014-08-26 | 2016-06-08 | 中国石油天然气股份有限公司 | Gemini quaternary ammonium salt class anti polymerizer and synthetic method and suppression hydrate thereof build up method |
| CN105900979A (en) * | 2016-05-18 | 2016-08-31 | 大连和田科技有限公司 | Preparation method of multi-quaternary ammonium salt fungicide |
| CN106398664B (en) * | 2016-09-07 | 2020-01-14 | 中国石油大学(华东) | Clay stabilizer and preparation method thereof |
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| US2778826A (en) * | 1954-04-26 | 1957-01-22 | Rohm & Haas | Preparation of basic nitrogen compounds |
| US5460728A (en) * | 1993-12-21 | 1995-10-24 | Shell Oil Company | Method for inhibiting the plugging of conduits by gas hydrates |
| CN1580090B (en) * | 2004-05-20 | 2010-12-29 | 北京石油化工学院 | Multi-arm star-type thermoplastic elastomer synthesizing method |
| CN101376852A (en) * | 2008-10-10 | 2009-03-04 | 中国石油大学(华东) | Low dose hydrate inhibitor |
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Effective date of registration: 20211105 Address after: Room 08-10, 6 / F, block a, No. 5, Dongtucheng Road, Chaoyang District, Beijing 100013 Patentee after: National Petroleum and natural gas pipeline network Group Co.,Ltd. Address before: 100007 Oil Mansion, 9 North Avenue, Dongcheng District, Beijing, Dongzhimen Patentee before: PETROCHINA Co.,Ltd. |