CN106336480B - For improving the additive of high-content wax viscous crude low temperature fluidity - Google Patents

For improving the additive of high-content wax viscous crude low temperature fluidity Download PDF

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CN106336480B
CN106336480B CN201610705111.1A CN201610705111A CN106336480B CN 106336480 B CN106336480 B CN 106336480B CN 201610705111 A CN201610705111 A CN 201610705111A CN 106336480 B CN106336480 B CN 106336480B
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additive
viscous crude
low temperature
improving
dosage
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CN106336480A (en
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马爱青
郑万刚
孙克己
盖平原
隋旭强
翟勇
徐鹏
陈连喜
何旭
贺文媛
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China Petroleum and Chemical Corp
Sinopec Research Institute of Petroleum Engineering Shengli Co
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China Petroleum and Chemical Corp
Sinopec Research Institute of Petroleum Engineering Shengli Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2368—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0453—Petroleum or natural waxes, e.g. paraffin waxes, asphaltenes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Lubricants (AREA)

Abstract

The invention discloses a kind of for improving the additive of high-content wax viscous crude low temperature fluidity, belong to macromolecule material preparation area.The additive is 1 according to molar ratio by maleic anhydride, acrylamide and 2 vinyl imidazoles:0.05~5:Then 0.5~6 ratio copolymerization adds in straight-chain fatty amine and reacts, 6000~50000g/mol of molecular weight.The additive temperature-resistant anti-salt performance of the present invention is good, and for heatproof up to 140 DEG C, resistance to salinity reaches 220000mg/L；Depression effeCt is good simultaneously, and dosage is low, under the conditions of dosage is 100ppm, the solidification point that paraffin content is 30~40% viscous crude can be made to reduce by 7 DEG C or more.Therefore, present invention is generally applicable in the pour point depression field test of high-content wax heavy oil wells.

Description

For improving the additive of high-content wax viscous crude low temperature fluidity
Technical field
The invention belongs to field of polymer material preparing technology, more particularly to a kind of to be used to improve high-content wax viscous crude low temperature stream The additive of dynamic performance.
Background technology
Height coagulates the special oil property of the high-content wax of oil, high-solidification point so that the solidifying oil of height reservoir exploitation, wellbore lift with And heat tracing technique is needed in later stage transmission process.Generally, crude oil temperature, on condensation point, the mobile performance that height coagulates oil is preferable； Temperature is less than crude oil solidification point, and wax can be precipitated, and forms tridimensional network, increases so as to cause viscosity, and resistance also increases therewith. When viscosity increases to a certain extent, crude oil loses flowability.The solution of generally use is both at home and abroad：(1) mixing light oil method； (2) water emulsifying method；(3) heating；(4) pour-point depressant method is added.At present, pour-point depressant can effectively realize crude oil with high solidifying point in the defeated pipe of length Road conveys, it is considered to be one of state-of-the-art crude pipeline transportation method in the world.
High-content wax viscous crude not only has a large amount of wax, the also labyrinths such as light hydrocarbon component, colloid, asphalitine, these structures The poor fluidity of viscous crude is not only caused, but also is easy to corrode oil pipe, mesh containing some acidic materials in colloid, structure of asphaltene Preceding oil-soluble pour-point depressant function both domestic and external is more single, and application effect is undesirable in terms of content of wax thickened oil recovery, pour point depression Rate is low, and universality is poor, and stability is poor.Most of conveying that content of wax viscous crude is only used for as flow ability modifying agent；Meanwhile these are dropped Solidifying agent is mainly influenced by complex formation condition, there are resistance to mild salt resistant character it is poor the problem of.
By literature search, the patent No. " ZL90105871.8 ", patent name " fluidity improver for crude oil containing wax ", application Number " ZL201510428058.0 ", title " a kind of high wax viscous crude pour-point depressant and preparation method thereof " and the patent No. " ZL201310653034.6 ", title " a kind of preparation method of waxy crude oil pour-point depressant ", these types of pour point depression agent prescription only carries The pour-point depressant of single side chain lengths has been supplied, due to the complexity of waxy crude oil component, a variety of side chains are added in pour point depression agent molecule Group is easier to be formed with wax crystalline substance interaction of molecules, obstruction wax crystalline substance tridimensional network；Meanwhile the pour point depression of above-mentioned waxy crude oil Agent heat-resistant salt-resistant poor-performing, adaptability is poor, is unfavorable for field popularization application.
Invention content
The present invention is for currently used for high-content wax viscous crude pour-point depressant, application effect is undesirable in terms of content of wax thickened oil recovery, drop The problems such as solidifying viscosity break ratio is low, bad adaptability, heat-resistant salt-resistant poor performance, and it is thick for improving high-content wax to provide a kind of resisting high temperature, high salt The additive of oily low temperature fluidity, 140 DEG C of the additive heatproof, resistance to salinity reach 220000mg/L, and suitable paraffin content is less than 40% viscous crude is a kind of pour-point depressant of the good high-content wax viscous crude of efficient heat-resistant salt-resistant performance, is 100ppm conditions in dosage Under, the solidification point that paraffin content is 30~40% viscous crude can be made to reduce by 7 DEG C or more, effectively solve high temperature and high salt high-content wax heavy crude reservoir Exploitation and lifting problem.
Provided by the present invention for improving the additive of high-content wax viscous crude low temperature fluidity, the additive is by maleic acid Acid anhydride, acrylamide and 2- vinyl imidazoles are copolymerized, 6000~50000g/mol of molecular weight, and general structure is：
In formula, in formula, R CxH2x+1Normal chain alkyl, 12≤X≤20；
M=40~340, preferably 60~90；
N=2~250, preferably 30~45；
P=20~300, preferably 120~180.
Maleic anhydride, acrylamide and the 2- vinyl imidazoles molar ratio is 1: 0.05~5: 0.5~6, preferably 1 ∶0.5∶2。
Preferably, the additive molecule amount is 20000~30000g/mol.
The preparation method of the additive of the present invention for being used to improve high-content wax viscous crude low temperature fluidity, the system Preparation Method specifically includes following steps：
(1) solvent and 2- vinyl imidazols are added in four-hole boiling flask, are passed through N2Protection, and with 100~200rpm rates 10~20min is stirred, is heated to 30~40 DEG C, secondly, adds in maleic anhydride, 2~10min is stirred with 50~100rpm rates, Obtain mixture A；
(2) acrylamide of aforementioned proportion is dissolved into n,N-dimethylacetamide, be subsequently poured into mixture A, it will Initiator is dissolved into toluene, and toluene dosage is 0.1~0.3 times of monomer gross mass, is placed into constant pressure funnel, is controlled Drop velocity is 3~5 drops/min；Being subsequently agitated for rate increases to 300~500rpm, and temperature rises to 50~90 DEG C, isothermal reaction 2 ~6h adds in hydroquinone of polymerization retarder after reaction, stirs 30~40min, obtains product B；
(3) product B temperature is reduced to 40~50 DEG C or so, adds in mixing straight-chain fatty amine stirring and dissolving, mix straight chain Fatty amine addition is 1: 0.5~1 for the molar ratio with maleic anhydride, then adds in catalyst p-methyl benzenesulfonic acid, and catalyst is used Amount is the 0.75~4.5% of monomer gross mass, then raises temperature to 80~90 DEG C, and stir speed (S.S.) is 200~300rpm, constant temperature 1~ After 1.5h, 110~150 DEG C are warming up to, stir speed (S.S.) is 100~500rpm, and mixing time is 2~7min, is cooled to room temperature, so Vacuum distillation removes solvent afterwards, obtains product C；
(4) by product C first with mass concentration in 5% sodium carbonate liquor and remaining acid, then with 10% aqueous sodium chloride Liquid is washed till neutrality, and precipitation filters, and is finally dried under vacuum to constant weight, obtains this additive.
Wherein, the solvent is toluene or dimethylbenzene, and dosage is 0.8~1.2 times of monomer gross mass, the N, N- Dimethylacetylamide dosage is 0.1~0.5 times of monomer gross mass, and the initiator is different for benzoyl peroxide or azo two Butyronitrile, dosage are the 0.5~3.5% of monomer gross mass, and the hydroquinone of polymerization retarder, dosage is the 0.5 of monomer gross mass ~3%.
The mixing straight-chain fatty amine is two kinds in lauryl amine, tetradecy lamine, cetylamine, octadecylamine and 20 amine, Dosage is that molar ratio is 1: 1.
Provided by the present invention for improving the additive of high-content wax viscous crude low temperature fluidity, using MOLECULE DESIGN thought. According to polymer molecule pendant alkyl group length with viscous crude wax hydrocarbon average carbon number more close, the better principle of depression effeCt, this hair It is bright that a variety of amine side-chains are introduced in additive molecule, to adapt to the self-condition of high wax viscous crude.Each monomer is equal in the molecule Nitrogen is introduced, improves stability and dispersibility of the additive in components such as crude oil wax, resin and asphalts.Designed adds Adding has primary amine group in agent molecule so that polymer molecule has alkalescent, can reduce the corrosivity of viscous crude；Increase in polymer The content of nitrogen-atoms, improves the polarity of additive, increases the repulsive interaction for the additive for being covered in wax surface, effectively hinders The formation of wax tridimensional network is hindered, so as to fulfill better pour-viscosity reduction effect；Imidazole ring is introduced in macromolecule, effectively Improve the high temperature stability performance of polymer.
The present invention has the following advantages that compared with prior art and advantageous effect：
(1) raw material sources of additive of the invention are extensive, and synthesis technology is simple, and process cleans are pollution-free, and product is easy to It obtains and transport preserves；
(2) additive of the invention is adaptable, and dosage is few, easy to use, alternative Wax removing agent, reduces Wax removing agent Dosage, remarkable in economical benefits；
(3) additive temperature-resistant anti-salt performance of the invention is good, and for heatproof up to 140 DEG C, resistance to salinity reaches 220000mg/L, overcomes The shortcomings that previous pour-point depressant temperature-resistant anti-salt performance is poor；
(4) additive of the invention has depression effeCt good, make under the conditions of additive amount is 100ppm paraffin content be 30~ The solidification point of 40% viscous crude reduces by 7 DEG C or more, improves high-content wax viscous crude mobility, meets wellbore lift requirement.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment, and with reference to data.It should be understood that these embodiments Solely for the purpose of illustration the present invention rather than limit the scope of the invention in any way.
Embodiment 1：Additive L1And preparation method thereof
(1) additive L1Composition and component are as follows：
Maleic anhydride 0.2mol (19.61g)
Acrylamide 0.01mol (0.71g)
2- vinyl imidazoles 0.1mol (9.4g)
(2) additive L1Preparation method is as follows：
1. 23.78g toluene and 9.4g 2- vinyl imidazols are added in four-hole boiling flask, it is passed through N2Protection, and with 100rpm Rate stirs 10min, is heated to 30 DEG C, then, adds in 19.61g maleic anhydrides, stirs 2min with 50rpm rates, is mixed Object A.
2. 0.71g acrylamides are dissolved into 2.97g n,N-dimethylacetamide, it is subsequently poured into mixture A, it will 0.15g benzoyl peroxides are dissolved into 2.97g toluene, are placed into constant pressure funnel, control drop velocity for 3 drop/ min；Being subsequently agitated for rate increases to 300rpm, and temperature rises to 50 DEG C, isothermal reaction 2h, adds in 0.15g inhibitions after reaction Agent hydroquinone stirs 30min, obtains product B.
3. product B temperature is reduced to 40 DEG C or so, 20 amine stirring and dissolving of 18.54g lauryl amines and 29.76g is added in, so 0.22g p-methyl benzenesulfonic acid is added in afterwards, after then raising temperature to 80 DEG C, stir speed (S.S.) 200rpm, constant temperature 1h, is warming up to 110 DEG C, is stirred Rate is mixed as 100rpm, mixing time 2min is cooled to room temperature, and then vacuum distillation removes solvent, obtains product C.
4. it by product C mass concentrations in 5% sodium carbonate liquor and remaining acid, then is washed with 10% sodium-chloride water solution To neutrality, precipitation filters, and is finally dried under vacuum to constant weight, obtains this additive L1。
Embodiment 2：Additive L2And preparation method thereof
(1) additive L2Composition and component are as follows：
Maleic anhydride 0.2mol (19.61g)
Acrylamide 1.0mol (71.08g)
2- vinyl imidazoles 1.2mol (112.8g)
(2) additive L2Preparation method is as follows：
1. 244.19g dimethylbenzene and 112.8g 2- vinyl imidazols are added in four-hole boiling flask, it is passed through N2Protection, and with 200rpm rates stir 20min, are heated to 40 DEG C, then, add in 19.61g maleic anhydrides, and 10min is stirred with 100rpm rates, Obtain mixture A.
2. 71.08g acrylamides are dissolved into 101.75g n,N-dimethylacetamide, it is subsequently poured into four-hole boiling flask In, 7.12g azodiisobutyronitriles are dissolved into 61.0g toluene, are placed into constant pressure funnel, control drop velocity is 5 Drop/min；Being subsequently agitated for rate increases to 500rpm, and temperature rises to 90 DEG C, isothermal reaction 6h, adds in 6.10g resistances after reaction Poly- agent hydroquinone stirs 40min, obtains product B.
3. product B temperature is reduced to 50 DEG C or so, 53.9g octadecylamines and 42.7g tetradecy lamine stirring and dissolvings are added in, then 9.16g p-methyl benzenesulfonic acid is added in, after then raising temperature to 90 DEG C, stir speed (S.S.) 300rpm, constant temperature 1.5h, 150 DEG C is warming up to, stirs Rate is mixed as 500rpm, mixing time 7min is cooled to room temperature, and then vacuum distillation removes solvent, obtains product C.
4. it by product C mass concentrations in 5% sodium carbonate liquor and remaining acid, then is washed with 10% sodium-chloride water solution To neutrality, precipitation filters, and is finally dried under vacuum to constant weight, obtains this additive L2。
Embodiment 3：Additive L3And preparation method thereof
(1) additive L3Composition and component are as follows：
Maleic anhydride 0.2mol (19.61g)
Acrylamide 0.1mol (7.11g)
2- vinyl imidazoles 1.2mol (112.8g)
(2) additive L3Preparation method is as follows：
1. 125.57g dimethylbenzene and 112.8g 2- vinyl imidazols are added in four-hole boiling flask, it is passed through N2Protection, and with 150rpm rates stir 20min, are heated to 35 DEG C, then, add in 19.61g maleic anhydrides, stir 6min with 70rpm rates, obtain To mixture A.
2. 7.11g acrylamides are dissolved into 55.81g n,N-dimethylacetamide, it is subsequently poured into mixture A, it will 2.09g benzoyl peroxides are dissolved into 27.90g toluene, are placed into constant pressure funnel, control drop velocity for 4 drop/ min；Being subsequently agitated for rate increases to 400rpm, and temperature rises to 70 DEG C, isothermal reaction 4h, adds in 2.09g inhibitions after reaction Agent hydroquinone stirs 35min, obtains product B.
3. product B temperature is reduced to 45 DEG C or so, 20 amine stirring and dissolving of 24.15g cetylamines and 29.76g is added in, so 1.05g p-methyl benzenesulfonic acid is added in afterwards, after then raising temperature to 80 DEG C, stir speed (S.S.) 200rpm, constant temperature 1h, is warming up to 140 DEG C, is stirred Rate is mixed as 400rpm, mixing time 5min is cooled to room temperature, and then vacuum distillation removes solvent, obtains product C.
4. it by product C mass concentrations in 5% sodium carbonate liquor and remaining acid, then is washed till with 10% sodium-chloride water solution Neutrality, precipitation filter, and are finally dried under vacuum to constant weight, obtain this additive L3。
Embodiment 4：Additive L4And preparation method thereof
(1) additive L4Composition and component are as follows：
Maleic anhydride 0.2mol (19.61g)
Acrylamide 0.1mol (7.11g)
2- vinyl imidazoles 0.4mol (37.6g)
(2) additive L4Preparation method is as follows：
1. 70.75g toluene and 37.6g 2- vinyl imidazols are added in four-hole boiling flask, it is passed through N2Protection, and with 200rpm rates stir 10min, are heated to 30 DEG C, then, add in 19.61g maleic anhydrides, and 4min is stirred with 100rpm rates, Obtain mixture A.
2. 7.11g acrylamides are dissolved into 32.16g n,N-dimethylacetamide, it is subsequently poured into mixture A, it will 0.96g benzoyl peroxides are dissolved into 19.30g toluene, are placed into constant pressure funnel, control drop velocity for 5 drop/ min；Being subsequently agitated for rate increases to 400rpm, and temperature rises to 70 DEG C, isothermal reaction 4h, adds in 0.64g inhibitions after reaction Agent hydroquinone stirs 30min, obtains product B.
3. product B temperature is reduced to 40 DEG C or so, 36.22g cetylamines and 40.43g octadecylamine stirring and dissolvings are added in, so 1.29g p-methyl benzenesulfonic acid is added in afterwards, after then raising temperature to 85 DEG C, stir speed (S.S.) 300rpm, constant temperature 1h, is warming up to 125 DEG C, is stirred Rate is mixed as 350rpm, mixing time 7min is cooled to room temperature, and then vacuum distillation removes solvent, obtains product C.
4. it by product C mass concentrations in 5% sodium carbonate liquor and remaining acid, then is washed with 10% sodium-chloride water solution To neutrality, precipitation filters, and is finally dried under vacuum to constant weight, obtains this pour-point depressant L4。
Embodiment 5：Additive L5And preparation method thereof
(1) additive L5Composition and component are as follows：
Maleic anhydride 0.2mol (19.61g)
Acrylamide 0.5mol (35.54g)
2- vinyl imidazoles 1.2mol (112.8g)
(2) additive L5Preparation method is as follows：
1. 184.75g dimethylbenzene and 112.8g 2- vinyl imidazols are added in four-hole boiling flask, it is passed through N2Protection, and with 100rpm rates stir 20min, are heated to 40 DEG C, then, add in 19.61g maleic anhydrides, stir 4min with 50rpm rates, obtain To mixture A.
2. 35.54g acrylamides are dissolved into 33.59g n,N-dimethylacetamide, it is subsequently poured into mixture A, 2.52g azodiisobutyronitriles are dissolved into 33.59g toluene, are placed into constant pressure funnel, control drop velocity for 4 drop/ min；Being subsequently agitated for rate increases to 400rpm, and temperature rises to 80 DEG C, isothermal reaction 5h, adds in 2.52g inhibitions after reaction Agent hydroquinone stirs 40min, obtains product B.
3. product B temperature is reduced to 45 DEG C or so, 21.34g tetradecy lamines and 24.15g cetylamine stirring and dissolvings are added in, so 3.36g p-methyl benzenesulfonic acid is added in afterwards, after then raising temperature to 90 DEG C, stir speed (S.S.) 200rpm, constant temperature 1.4h, is warming up to 140 DEG C, Stir speed (S.S.) is 300rpm, and mixing time 5min is cooled to room temperature, and then vacuum distillation removes solvent, obtains product C.
4. it by product C mass concentrations in 5% sodium carbonate liquor and remaining acid, then is washed with 10% sodium-chloride water solution To neutrality, precipitation filters, and is finally dried under vacuum to constant weight, obtains this additive L5。
Embodiment 6：Additive L6And preparation method thereof
(1) additive L6Composition and component are as follows：
Maleic anhydride 0.2mol (19.61g)
Acrylamide 0.5mol (35.54g)
2- vinyl imidazoles 0.4mol (37.6g)
(2) additive L6Preparation method is as follows：
1. 111.3g dimethylbenzene and 37.6g 2- vinyl imidazols are added in four-hole boiling flask, it is passed through N2Protection, and with 170rpm rates stir 10min, are heated to 30 DEG C, then, add in 19.61g maleic anhydrides, stir 8min with 80rpm rates, obtain To mixture A.
2. 35.54g acrylamides are dissolved into 37.1g n,N-dimethylacetamide, it is subsequently poured into mixture A, it will 1.39g benzoyl peroxides are dissolved into 9.28g toluene, are placed into constant pressure funnel, control drop velocity for 5 drop/ min；Being subsequently agitated for rate increases to 500rpm, and temperature rises to 70 DEG C, isothermal reaction 5h, adds in 1.39g inhibitions after reaction Agent hydroquinone stirs 35min, obtains product B.
3. product B temperature is reduced to 50 DEG C or so, 20 amine stirring and dissolving of 26.95g octadecylamines and 29.76g is added in, so 1.39g p-methyl benzenesulfonic acid is added in afterwards, after then raising temperature to 90 DEG C, stir speed (S.S.) 300rpm, constant temperature 1.2h, is warming up to 140 DEG C, Stir speed (S.S.) is 400rpm, and mixing time 5min is cooled to room temperature, and then vacuum distillation removes solvent, obtain product C.
4. it by product C mass concentrations in 5% sodium carbonate liquor and remaining acid, then is washed with 10% sodium-chloride water solution To neutrality, precipitation filters, and is finally dried under vacuum to constant weight, obtains this additive L6。
Embodiment 7
To verify effect of the present invention, by the additive L of the present invention1、L2、L3、L4、L5、L6Applied to two kinds of Shengli Oil Field height Content of wax viscous crude.The basic parameter of Shengli Oil Field high-content wax viscous crude H is as follows：Solidification point is in 55 DEG C, paraffin content 35.7%, viscosity (50 DEG C) 34.52 × 104mPas, density 936.2kg/m3, moisture content 21.56%.Shengli Oil Field high-content wax viscous crude M's Basic parameter is as follows：Solidification point is in 43 DEG C, paraffin content 31.4%, and viscosity is (50 DEG C) 1092mPas, density is 960.9kg/m3, moisture content 18.36%.Tables 1 and 2 is respectively the additive L that the present invention synthesizes1、L2、L3、L4、L5、L6It is right In the pour point depression experimental result of Shengli Oil Field high-content wax viscous crude H and M.
The additive that 1 present invention of table synthesizes is for the pour point depression experimental result of Shengli Oil Field high-content wax viscous crude H
2 synthetic additive of the present invention of table is for the pour point depression experimental result of Shengli Oil Field high-content wax viscous crude M
It can be seen from Tables 1 and 2 under the conditions of additive additive amount is 100ppm, the present invention can make high-content wax viscous crude H The solidification point minimum of (paraffin content 35.7%) reduces by 9 DEG C, can drop the solidification point minimum of high-content wax viscous crude M (paraffin content 31.4%) Low 8 DEG C.The synthetic method of the additive is simple, and dosage is few, easy to use, has preferable pour point depression to imitate to different content of wax viscous crude Fruit meets wellbore lift requirement, remarkable in economical benefits.

Claims (8)

1. a kind of for improving the additive of high-content wax viscous crude low temperature fluidity, the additive is by maleic anhydride, acrylamide With 2- vinyl imidazoles according to molar ratio be 1:0.05~5:0.5~6 ratio copolymerization, then add in straight-chain fatty amine reaction and Into, 6000~50000g/mol of molecular weight, general structure is：
In formula, in formula, R CxH2x+1Normal chain alkyl, 12≤X≤20；
M=40~340；
N=2~250；
P=20~300.
2. the additive according to claim 1 for being used to improve high-content wax viscous crude low temperature fluidity, which is characterized in that institute The additive stated is 1 according to molar ratio by maleic anhydride, acrylamide and 2- vinyl imidazoles:0.5:2 ratio copolymerization, then Straight-chain fatty amine is added in react.
3. it is according to claim 1 or 2 for improving the preparation method of the additive of high-content wax viscous crude low temperature fluidity, It is characterized in that, the preparation method specifically includes following steps：
(1) solvent and 2- vinyl imidazoles are added in four-hole boiling flask, are passed through N2Protection, and stirred with 100~200rpm rates 10~20min is heated to 30~40 DEG C, secondly, adds in maleic anhydride, stirs 2~10min with 50~100rpm rates, obtains Mixture A；
(2) acrylamide of aforementioned proportion is dissolved into n,N-dimethylacetamide, be subsequently poured into mixture A, will caused Agent is dissolved into toluene, and toluene dosage is 0.1~0.3 times of monomer gross mass, is placed into constant pressure funnel, controls dropping liquid Rate is 3~5 drops/min；Being subsequently agitated for rate increases to 300~500rpm, and temperature rises to 50~90 DEG C, and isothermal reaction 2~ 6h adds in hydroquinone of polymerization retarder after reaction, stirs 30~40min, obtains product B；
(3) product B temperature is reduced to 40~50 DEG C, adds in mixing straight-chain fatty amine stirring and dissolving, mixing straight-chain fatty amine adds It is 1 to enter amount for the molar ratio with maleic anhydride:0.5~1, catalyst p-methyl benzenesulfonic acid is then added in, catalyst amount is monomer The 0.75~4.5% of gross mass, then raises temperature to 80~90 DEG C, and stir speed (S.S.) is 200~300rpm, after 1~1.5h of constant temperature, rises For temperature to 110~150 DEG C, stir speed (S.S.) is 100~500rpm, and mixing time is 2~7min, is cooled to room temperature, and then decompression is steamed Solvent is removed in distillation, obtains product C；
(4) product C is first washed with mass concentration in 5% sodium carbonate liquor and remaining acid, then with 10% sodium-chloride water solution To neutrality, precipitation filters, and is finally dried under vacuum to constant weight, obtains this additive.
4. it is according to claim 3 for improving the preparation method of the additive of high-content wax viscous crude low temperature fluidity, It is characterized in that, the solvent is toluene or dimethylbenzene, and dosage is 0.8~1.2 times of monomer gross mass.
5. it is according to claim 3 or 4 for improving the preparation method of the additive of high-content wax viscous crude low temperature fluidity, It is characterized in that, the n,N-dimethylacetamide dosage is 0.1~0.5 times of monomer gross mass.
6. it is according to claim 3 for improving the preparation method of the additive of high-content wax viscous crude low temperature fluidity, Be characterized in that, the initiator be benzoyl peroxide or azodiisobutyronitrile, dosage for monomer gross mass 0.5~ 3.5%.
7. it is according to claim 3 or 4 for improving the preparation method of the additive of high-content wax viscous crude low temperature fluidity, It is characterized in that, the hydroquinone of polymerization retarder, dosage is the 0.5~3% of monomer gross mass.
8. it is according to claim 7 for improving the preparation method of the additive of high-content wax viscous crude low temperature fluidity, It being characterized in that, the mixing straight-chain fatty amine is two kinds in lauryl amine, tetradecy lamine, cetylamine, octadecylamine and 20 amine, Dosage is that molar ratio is 1:1.
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CN1059157A (en) * 1990-08-18 1992-03-04 成都科技大学 The waxy crude oil fluidity improver
CN104693352A (en) * 2013-12-05 2015-06-10 青岛惠城石化科技有限公司 Preparation method of wax-containing crude oil pour-point depressant
CN105175629A (en) * 2015-07-20 2015-12-23 山东大学 High-wax thick oil pour point depressant and preparation method thereof

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FR2826015A1 (en) * 2001-06-18 2002-12-20 Schlumberger Services Petrol Shear viscosifying or gelling fluid for well drilling operations, comprises polymer containing hydrosoluble non-ionic, ionic and hydrophobic or low critical solution temperature functional groups

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CN104693352A (en) * 2013-12-05 2015-06-10 青岛惠城石化科技有限公司 Preparation method of wax-containing crude oil pour-point depressant
CN105175629A (en) * 2015-07-20 2015-12-23 山东大学 High-wax thick oil pour point depressant and preparation method thereof

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