CN106336480A - Additive for improving low temperature flow performance of heavy oil with high wax content - Google Patents

Additive for improving low temperature flow performance of heavy oil with high wax content Download PDF

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Publication number
CN106336480A
CN106336480A CN201610705111.1A CN201610705111A CN106336480A CN 106336480 A CN106336480 A CN 106336480A CN 201610705111 A CN201610705111 A CN 201610705111A CN 106336480 A CN106336480 A CN 106336480A
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additive
low temperature
viscous crude
preparation
speed
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CN106336480B (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)
  • Health & Medical Sciences (AREA)
  • 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 an additive for improving low temperature flow performance of heavy oil with high wax content, and belongs to the field of polymer material preparation. The additive is prepared by copolymerization of maleic anhydride, acrylamide and 2-vinyl imidazole in the mol ratio of 1: 0.05 to 5: 0.5 to 6, and the molecular weight is 6000-50000g/mol. The additive has the advantages of good temperature resistance and salt tolerance, and can resist temperature up to 140 DEG C, resistance to salinity reaches to 220000mg/L; at the same time, pour point depression effect is good, dosage is low, and the solidifying point of heavy oil with the wax content of 30-40% can be reduced by more than 7 DEG C under the condition of the dosage of 100ppm, so that the additive can be widely used in pour point depression field tests of heavy oil wells with high wax content.

Description

For improving the additive of high-content wax viscous crude low temperature flowability
Technical field
The invention belongs to field of polymer material preparing technology, it is used for improving high-content wax viscous crude low temperature stream particularly to one kind The additive of dynamic performance.
Background technology
The high solidifying high-content wax of oil, the special oil property of high-solidification point so that high solidifying oil reservoir exploitation, wellbore lift with And in later stage course of conveying, need heat tracing technique.General, on condensation point, the mobile performance of high solidifying oil is preferable for crude oil temperature； Temperature is less than crude oil freezing point, and wax can separate out, and forms tridimensional network, thus leading to viscosity to increase, resistance also increases therewith. When viscosity raises to a certain extent, crude oil loses flowability.The solution generally adopting both at home and abroad is: (1) mixing light oil method； (2) water emulsifying method；(3) heating；(4) add pour-point depressant method.At present, pour-point depressant can effectively realize crude oil with high solidifying point in long defeated pipe Road conveying is it is considered to be one of state-of-the-art crude pipeline transportation method in the world.
High-content wax viscous crude does not only have substantial amounts of wax, the also labyrinth such as light hydrocarbon component, colloid, asphalitine, these structures Not only cause the poor fluidity of viscous crude, and contain some acidic materials in colloid, structure of asphaltene it is easy to corrode oil pipe, mesh Front oil-soluble pour-point depressant function both domestic and external is all more single, and in terms of content of wax thickened oil recovery, application effect is all undesirable, pour point depression Rate is low, and universality is poor, and stability is poor.Major part is only used as flow ability modifying agent for the conveying of content of wax viscous crude；Meanwhile, these falls Solidifying agent is mainly affected by complex formation condition, there is a problem of that resistance to gentle salt resistant character is poor.
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 ", this several pour point depression agent prescription all only carries Supply the pour-point depressant of single side chain lengths, due to the complexity of waxy crude oil component, pour point depression agent molecule has added multiple side chains Group is easier to and wax crystalline substance interaction of molecules, hinders wax crystalline substance tridimensional network to be formed；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.
Content of the invention
In terms of content of wax thickened oil recovery, application effect is undesirable for currently used for high-content wax viscous crude pour-point depressant for the present invention, drops Solidifying viscosity break ratio is low, bad adaptability, the problems such as heat-resistant salt-resistant poor performance, and provide a kind of resisting high temperature, high salt be used for improving high-content wax thick The additive of oily low temperature flowability, 140 DEG C of this additive heatproof, resistance to salinity reaches 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 condition in consumption Under, the freezing point that paraffin content is 30～40% viscous crude can be made to reduce by more than 7 DEG C, effectively solving high temperature and high salt high-content wax heavy crude reservoir Exploitation and a lifting difficult problem.
Provided by the present invention for improving the additive of high-content wax viscous crude low temperature flowability, this additive is by maleic acid Acid anhydride, acrylamide and 2- vinyl imidazole copolymerization form, molecular weight 6000～50000g/mol, and its general structure is:
In formula, in formula, r is 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.
Described maleic anhydride, acrylamide and 2- vinyl imidazole mol ratio are 1: 0.05～5: 0.5～6, preferably 1 ∶0.5∶2.
Preferably, described additive molecule amount is 20000～30000g/mol.
The preparation method of the additive for improving high-content wax viscous crude low temperature flowability of the present invention, described system Preparation Method specifically includes following steps:
(1) solvent and 2- vinyl imidazol are added in four-hole boiling flask, are passed through n2Protection, and with 100～200rpm speed Stirring 10～20min, is heated to 30～40 DEG C, secondly, adds maleic anhydride, stirs 2～10min with 50～100rpm speed, Obtain mixture a；
(2) acrylamide of aforementioned proportion is dissolved into n, in n- dimethyl acetylamide, is subsequently poured in mixture a, will Initiator is dissolved in toluene, and toluene consumption is 0.1～0.3 times of monomer gross mass, is placed in constant pressure funnel, controls Drop velocity is 3～5/min；Being subsequently agitated for speed increases to 300～500rpm, and temperature rises to 50～90 DEG C, isothermal reaction 2 ～6h, reaction adds hydroquinone of polymerization retarder after terminating, and stirs 30～40min, obtains product b；
(3) product b temperature is reduced to 40～50 DEG C about, adds mixing straight-chain fatty amine stirring and dissolving, mix straight chain Fatty amine addition is to be 1: 0.5～1 with the mol ratio of maleic anhydride, is subsequently adding catalyst p-methyl benzenesulfonic acid, 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, it is warming up to 110～150 DEG C, stir speed (S.S.) is 100～500rpm, mixing time is 2～7min, is cooled to room temperature, so Vacuum distillation removes solvent afterwards, obtains product c；
(4) product c is first used mass concentration be in 5% sodium carbonate liquor and remaining acid, then use 10% aqueous sodium chloride Liquid is washed till neutrality, precipitation, sucking filtration, is finally dried under vacuum to constant weight, obtains this additive.
Wherein, described solvent is toluene or dimethylbenzene, and consumption is 0.8～1.2 times of monomer gross mass, described n, n- Dimethyl acetylamide consumption is 0.1～0.5 times of monomer gross mass, and described initiator is benzoyl peroxide or azo two is different Butyronitrile, consumption is the 0.5～3.5% of monomer gross mass, described hydroquinone of polymerization retarder, and consumption is the 0.5 of monomer gross mass ～3%.
Described mixing straight-chain fatty amine is two kinds in lauryl amine, tetradecy lamine, cetylamine, 18-amine. and 20 amine, its Consumption is 1: 1 for mol ratio.
Provided by the present invention for improving the additive of high-content wax viscous crude low temperature flowability, using MOLECULE DESIGN thought. , its depression effeCt better principle more close with viscous crude wax hydrocarbon average carbon number according to polymer molecule pendant alkyl group length, this Bright introduce multiple amine side-chain in additive molecule, to adapt to the self-condition of high wax viscous crude.Each monomer is equal in the molecule Introduce nitrogen, improve additive in the stability of the components such as crude oil wax, resin and asphalt and dispersibility.Designed adds Plus have primary amine group in agent molecule so that polymer molecule has alkalescence, it is possible to decrease the corrosivity of viscous crude；Increase in polymer The content of nitrogen-atoms, improves the polarity of additive, increases the repulsive interaction of the additive being covered in wax surface, effectively hinders Hinder the formation of wax tridimensional network, thus realizing more preferable pour-viscosity reduction effect；Imidazole ring is introduced, effectively in macromolecule Improve the high temperature stability performance of polymer.
The present invention compared with prior art has the advantage that and beneficial effect:
(1) extensively, synthesis technique is simple, and process cleans are pollution-free, and product is easy to for the raw material sources of the additive of the present invention Obtain and transport preserves；
(2) the additive strong adaptability of the present invention, consumption is few, easy to use, alternative Wax removing agent, reduces Wax removing agent Consumption, remarkable in economical benefits；
(3) the additive temperature-resistant anti-salt performance of the present invention is good, and heatproof reaches 140 DEG C, and resistance to salinity reaches 220000mg/l, overcomes The shortcoming of conventional pour-point depressant temperature-resistant anti-salt performance difference；
(4) to have a depression effeCt good for the additive of the present invention, make under the conditions of addition is for 100ppm paraffin content be 30～ The freezing point of 40% viscous crude reduces by more than 7 DEG C, improves high-content wax viscous crude mobility, meets wellbore lift requirement.
Specific embodiment
With reference to specific embodiment, and with reference to data, the present invention is described in further detail.It should be understood that these embodiments The present invention solely for the purpose of illustration, rather than limit the scope of the present invention by 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 imidazole 0.1mol (9.4g)
(2) additive l1Preparation method is as follows:
1. 23.78g toluene and 9.4g 2- vinyl imidazol are added in four-hole boiling flask, are passed through n2Protection, and with 100rpm speed Rate stirs 10min, is heated to 30 DEG C, subsequently, adds 19.61g maleic anhydride, stirs 2min with 50rpm speed, obtain mixture a.
2. 0.71g acrylamide is dissolved into 2.97g n, in n- dimethyl acetylamide, is subsequently poured in mixture a, will 0.15g benzoyl peroxide is dissolved in 2.97g toluene, is placed in constant pressure funnel, control drop velocity be 3/ min；Being subsequently agitated for speed increases to 300rpm, and temperature rises to 50 DEG C, isothermal reaction 2h, and reaction adds 0.15g inhibition after terminating Agent hydroquinone, stirs 30min, obtains product b.
3. product b temperature is reduced to 40 DEG C about, adds 18.54g lauryl amine and 29.76g 20 amine stirring and dissolving, so Add 0.22g p-methyl benzenesulfonic acid afterwards, then raise temperature to 80 DEG C, stir speed (S.S.) is 200rpm, after constant temperature 1h, is warming up to 110 DEG C, stirs Mixing speed is 100rpm, and mixing time is 2min, is cooled to room temperature, and then vacuum distillation removes solvent, obtains product c.
4. product c mass concentration is in 5% sodium carbonate liquor and remaining acid, then washed with 10% sodium-chloride water solution To neutral, precipitation, sucking filtration, finally it is 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 imidazole 1.2mol (112.8g)
(2) additive l2Preparation method is as follows:
1. 244.19g dimethylbenzene and 112.8g 2- vinyl imidazol are added in four-hole boiling flask, are passed through n2Protection, and with 200rpm speed stirs 20min, is heated to 40 DEG C, subsequently, adds 19.61g maleic anhydride, stirs 10min with 100rpm speed, Obtain mixture a.
2. 71.08g acrylamide is dissolved into 101.75g n, in n- dimethyl acetylamide, is subsequently poured into four-hole boiling flask In, 7.12g azodiisobutyronitrile is dissolved in 61.0g toluene, is placed in constant pressure funnel, control drop velocity to be 5 Drip/min；Being subsequently agitated for speed increases to 500rpm, and temperature rises to 90 DEG C, isothermal reaction 6h, and reaction adds 6.10g resistance after terminating Poly- agent hydroquinone, stirs 40min, obtains product b.
3. product b temperature is reduced to 50 DEG C about, adds 53.9g 18-amine. and 42.7g tetradecy lamine stirring and dissolving, then Add 9.16g p-methyl benzenesulfonic acid, then raise temperature to 90 DEG C, stir speed (S.S.) is 300rpm, after constant temperature 1.5h, is warming up to 150 DEG C, stirs Mixing speed is 500rpm, and mixing time is 7min, is cooled to room temperature, and then vacuum distillation removes solvent, obtains product c.
4. product c mass concentration is in 5% sodium carbonate liquor and remaining acid, then washed with 10% sodium-chloride water solution To neutral, precipitation, sucking filtration, finally it is 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 imidazole 1.2mol (112.8g)
(2) additive l3Preparation method is as follows:
1. 125.57g dimethylbenzene and 112.8g 2- vinyl imidazol are added in four-hole boiling flask, are passed through n2Protection, and with 150rpm speed stirs 20min, is heated to 35 DEG C, subsequently, adds 19.61g maleic anhydride, stirs 6min with 70rpm speed, obtain To mixture a.
2. 7.11g acrylamide is dissolved into 55.81g n, in n- dimethyl acetylamide, is subsequently poured in mixture a, will 2.09g benzoyl peroxide is dissolved in 27.90g toluene, is placed in constant pressure funnel, control drop velocity be 4/ min；Being subsequently agitated for speed increases to 400rpm, and temperature rises to 70 DEG C, isothermal reaction 4h, and reaction adds 2.09g inhibition after terminating Agent hydroquinone, stirs 35min, obtains product b.
3. product b temperature is reduced to 45 DEG C about, adds 24.15g cetylamine and 29.76g 20 amine stirring and dissolving, so Add 1.05g p-methyl benzenesulfonic acid afterwards, then raise temperature to 80 DEG C, stir speed (S.S.) is 200rpm, after constant temperature 1h, is warming up to 140 DEG C, stirs Mixing speed is 400rpm, and mixing time is 5min, is cooled to room temperature, and then vacuum distillation removes solvent, obtains product c.
4. product c mass concentration is in 5% sodium carbonate liquor and remaining acid, then is washed till with 10% sodium-chloride water solution Neutrality, precipitation, sucking filtration, finally it is 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 imidazole 0.4mol (37.6g)
(2) additive l4Preparation method is as follows:
1. 70.75g toluene and 37.6g 2- vinyl imidazol are added in four-hole boiling flask, are passed through n2Protection, and with 200rpm speed stirs 10min, is heated to 30 DEG C, subsequently, adds 19.61g maleic anhydride, stirs 4min with 100rpm speed, Obtain mixture a.
2. 7.11g acrylamide is dissolved into 32.16g n, in n- dimethyl acetylamide, is subsequently poured in mixture a, will 0.96g benzoyl peroxide is dissolved in 19.30g toluene, is placed in constant pressure funnel, control drop velocity be 5/ min；Being subsequently agitated for speed increases to 400rpm, and temperature rises to 70 DEG C, isothermal reaction 4h, and reaction adds 0.64g inhibition after terminating Agent hydroquinone, stirs 30min, obtains product b.
3. product b temperature is reduced to 40 DEG C about, adds 36.22g cetylamine and 40.43g 18-amine. stirring and dissolving, so Add 1.29g p-methyl benzenesulfonic acid afterwards, then raise temperature to 85 DEG C, stir speed (S.S.) is 300rpm, after constant temperature 1h, is warming up to 125 DEG C, stirs Mixing speed is 350rpm, and mixing time is 7min, is cooled to room temperature, and then vacuum distillation removes solvent, obtains product c.
4. product c mass concentration is in 5% sodium carbonate liquor and remaining acid, then washed with 10% sodium-chloride water solution To neutral, precipitation, sucking filtration, finally it is 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 imidazole 1.2mol (112.8g)
(2) additive l5Preparation method is as follows:
1. 184.75g dimethylbenzene and 112.8g 2- vinyl imidazol are added in four-hole boiling flask, are passed through n2Protection, and with 100rpm speed stirs 20min, is heated to 40 DEG C, subsequently, adds 19.61g maleic anhydride, stirs 4min with 50rpm speed, obtain To mixture a.
2. 35.54g acrylamide is dissolved into 33.59g n, in n- dimethyl acetylamide, is subsequently poured in mixture a, 2.52g azodiisobutyronitrile is dissolved in 33.59g toluene, is placed in constant pressure funnel, control drop velocity be 4/ min；Being subsequently agitated for speed increases to 400rpm, and temperature rises to 80 DEG C, isothermal reaction 5h, and reaction adds 2.52g inhibition after terminating Agent hydroquinone, stirs 40min, obtains product b.
3. product b temperature is reduced to 45 DEG C about, adds 21.34g tetradecy lamine and 24.15g cetylamine stirring and dissolving, so Add 3.36g p-methyl benzenesulfonic acid afterwards, then raise temperature to 90 DEG C, stir speed (S.S.) is 200rpm, after constant temperature 1.4h, is warming up to 140 DEG C, Stir speed (S.S.) is 300rpm, and mixing time is 5min, is cooled to room temperature, and then vacuum distillation removes solvent, obtains product c.
4. product c mass concentration is in 5% sodium carbonate liquor and remaining acid, then washed with 10% sodium-chloride water solution To neutral, precipitation, sucking filtration, finally it is 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 imidazole 0.4mol (37.6g)
(2) additive l6Preparation method is as follows:
1. 111.3g dimethylbenzene and 37.6g 2- vinyl imidazol are added in four-hole boiling flask, are passed through n2Protection, and with 170rpm speed stirs 10min, is heated to 30 DEG C, subsequently, adds 19.61g maleic anhydride, stirs 8min with 80rpm speed, obtain To mixture a.
2. 35.54g acrylamide is dissolved into 37.1g n, in n- dimethyl acetylamide, is subsequently poured in mixture a, will 1.39g benzoyl peroxide is dissolved in 9.28g toluene, is placed in constant pressure funnel, control drop velocity be 5/ min；Being subsequently agitated for speed increases to 500rpm, and temperature rises to 70 DEG C, isothermal reaction 5h, and reaction adds 1.39g inhibition after terminating Agent hydroquinone, stirs 35min, obtains product b.
3. product b temperature is reduced to 50 DEG C about, adds 26.95g 18-amine. and 29.76g 20 amine stirring and dissolving, so Add 1.39g p-methyl benzenesulfonic acid afterwards, then raise temperature to 90 DEG C, stir speed (S.S.) is 300rpm, after constant temperature 1.2h, is warming up to 140 DEG C, Stir speed (S.S.) is 400rpm, and mixing time is 5min, is cooled to room temperature, and then vacuum distillation removes solvent, obtain product c.
4. product c mass concentration is in 5% sodium carbonate liquor and remaining acid, then washed with 10% sodium-chloride water solution To neutral, precipitation, sucking filtration, finally it is dried under vacuum to constant weight, obtains this additive l6.
Embodiment 7
For verifying effect of the present invention, by the additive l of the present invention1、l2、l3、l4、l5、l6It is applied 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: freezing point 55 DEG C, paraffin content be 35.7%, viscosity is (50 DEG C) 34.52 × 104mpa s, density are 936.2kg/m3, moisture content be 21.56%.Shengli Oil Field high-content wax viscous crude m's Basic parameter is as follows: freezing point 43 DEG C, paraffin content be 31.4%, viscosity is that (50 DEG C) 1092mpa s, density are 960.9kg/m3, moisture content be 18.36%.Tables 1 and 2 is respectively the additive l of present invention synthesis1、l2、l3、l4、l5、l6Right Pour point depression experimental result in Shengli Oil Field high-content wax viscous crude h and m.
The additive of table 1 present invention synthesis is for the pour point depression experimental result of Shengli Oil Field high-content wax viscous crude h
Table 2 synthetic additive of the present invention is for the pour point depression experimental result of Shengli Oil Field high-content wax viscous crude m
By Tables 1 and 2 as can be seen that under the conditions of additive addition is 100ppm, the present invention can make high-content wax viscous crude h The freezing point of (paraffin content 35.7%) is minimum to reduce by 9 DEG C, can make the minimum fall of freezing point of high-content wax viscous crude m (paraffin content 31.4%) Low 8 DEG C.The synthetic method of this additive is simple, and consumption is few, easy to use, all has preferable pour point depression effect to different content of wax viscous crude Really, wellbore lift requirement, remarkable in economical benefits are met.

Claims (8)

1. a kind of additive for improving high-content wax viscous crude low temperature flowability, this additive is by maleic anhydride, acrylamide Form according to the ratio copolymerization that mol ratio is 1: 0.05～5: 0.5～6 with 2- vinyl imidazole, molecular weight 6000～50000g/ Mol, its general structure is:
In formula, in formula, r is 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.
2. the additive for improving high-content wax viscous crude low temperature flowability according to claim 1 is it is characterised in that institute The additive stated is formed according to the ratio copolymerization that mol ratio is 1: 0.5: 2 by maleic anhydride, acrylamide and 2- vinyl imidazole.
3. the preparation method of the additive for improving high-content wax viscous crude low temperature flowability according to claim 1 and 2, It is characterized in that, described preparation method specifically includes following steps:
(1) solvent and 2- vinyl imidazol are added in four-hole boiling flask, are passed through n2Protection, and stir 10 with 100～200rpm speed ～20min, is heated to 30～40 DEG C, secondly, adds maleic anhydride, stirs 2～10min with 50～100rpm speed, mixed Compound a；
(2) acrylamide of aforementioned proportion is dissolved into n, in n- dimethyl acetylamide, is subsequently poured in mixture a, will cause Agent is dissolved in toluene, and toluene consumption is 0.1～0.3 times of monomer gross mass, is placed in constant pressure funnel, controls dropping liquid Speed is 3～5/min；Being subsequently agitated for speed increases to 300～500rpm, and temperature rises to 50～90 DEG C, and isothermal reaction 2～ 6h, reaction adds hydroquinone of polymerization retarder after terminating, and stirs 30～40min, obtains product b；
(3) product b temperature is reduced to 40～50 DEG C about, adds mixing straight-chain fatty amine stirring and dissolving, mix straight chain fatty Amine addition is to be 1: 0.5～1 with the mol ratio of maleic anhydride, is subsequently adding catalyst p-methyl benzenesulfonic acid, catalyst 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 1～1.5h Afterwards, it is warming up to 110～150 DEG C, stir speed (S.S.) is 100～500rpm, mixing time is 2～7min, is cooled to room temperature, then subtracts Pressure is distilled off solvent, obtains product c；
(4) product c is first used mass concentration be in 5% sodium carbonate liquor and remaining acid, then washed with 10% sodium-chloride water solution To neutral, precipitation, sucking filtration, finally it is dried under vacuum to constant weight, obtains this additive.
4. the preparation method of the additive for improving high-content wax viscous crude low temperature flowability according to claim 3, its It is characterised by, described solvent is toluene or dimethylbenzene, consumption is 0.8～1.2 times of monomer gross mass.
5. the preparation method of the additive for improving high-content wax viscous crude low temperature flowability according to claim 3 or 4, It is characterized in that, described n, n- dimethyl acetylamide consumption is 0.1～0.5 times of monomer gross mass.
6. the preparation method of the additive for improving high-content wax viscous crude low temperature flowability according to claim 3, its Be characterised by, described initiator is benzoyl peroxide or azodiisobutyronitrile, consumption be monomer gross mass 0.5～ 3.5%.
7. the preparation method of the additive for improving high-content wax viscous crude low temperature flowability according to claim 3 or 4, It is characterized in that, described hydroquinone of polymerization retarder, consumption is the 0.5～3% of monomer gross mass.
8. the preparation method of the additive for improving high-content wax viscous crude low temperature flowability according to claim 7, its It is characterised by, described mixing straight-chain fatty amine is two kinds in lauryl amine, tetradecy lamine, cetylamine, 18-amine. and 20 amine, its Consumption is 1: 1 for mol ratio.
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CN110093609A (en) * 2019-05-07 2019-08-06 北京赛福贝特能源技术服务有限公司 Improve the method for unsaturated high-grade fatty acid imidazoline inhibitor frost resistance
CN111065658A (en) * 2017-07-06 2020-04-24 株式会社村田制作所 Polymers comprising imidazole derivatives and their use in electrochemical cells
CN116333711A (en) * 2023-05-30 2023-06-27 新疆科力新技术发展股份有限公司 Novel pour point depressant and preparation method thereof

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CN111065658A (en) * 2017-07-06 2020-04-24 株式会社村田制作所 Polymers comprising imidazole derivatives and their use in electrochemical cells
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CN110093609A (en) * 2019-05-07 2019-08-06 北京赛福贝特能源技术服务有限公司 Improve the method for unsaturated high-grade fatty acid imidazoline inhibitor frost resistance
CN110093609B (en) * 2019-05-07 2021-05-04 北京赛福贝特能源技术服务有限公司 Method for improving frost resistance of unsaturated higher fatty acid imidazoline corrosion inhibitor
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CN116333711B (en) * 2023-05-30 2023-08-11 新疆科力新技术发展股份有限公司 Pour point depressant and preparation method thereof

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