CN106632839B - A kind of organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering and preparation method thereof - Google Patents
A kind of organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering and preparation method thereof Download PDFInfo
- Publication number
- CN106632839B CN106632839B CN201611205704.8A CN201611205704A CN106632839B CN 106632839 B CN106632839 B CN 106632839B CN 201611205704 A CN201611205704 A CN 201611205704A CN 106632839 B CN106632839 B CN 106632839B
- Authority
- CN
- China
- Prior art keywords
- heavy crude
- organic
- silicon
- thinner
- amphipathic polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to organic-silicon-modified amphipathic polymer type heavy crude thinners of a kind of easy breaking emulsion and dewatering and preparation method thereof, and the thinner preparation step is as follows: acrylamide, double bond containing organosilicon quaternary ammonium salt and solvent being mixed evenly, mixed liquor is obtained；It is passed through nitrogen, 60~80 DEG C is heated to, initiator is added under stiring, in 60~80 DEG C, 5~12 hours is reacted, obtains reaction solution；It will be poured into acetone or alcohol after reaction solution cooling, through suction filtration, immersion, washing, drying to get heavy crude thinner.Preparation method of the invention is easy to operate, cost is relatively low, and the thinner being prepared has preferable temperature-resistant anti-salt and viscosity reducing effect under low concentration, and is easy to breaking emulsion and dewatering, reduces later period water process difficulty.The thinner does not need to use with other additive compounds, and excellent combination property is again environmentally protective.
Description
Technical field
The present invention relates to a kind of organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering and its preparation sides
Method belongs to thickened oil recovery thinner technical field.
Background technique
With the continuous intensification of oil exploitation degree, ratio shared by viscous crude resource is increasing, but viscous crude Yin Qimi
Degree is high, viscosity is big, keeps its exploitation, transport, storage difficult.Current reducing thick oil viscosity technology has reducing viscosity by emulsifying, physics viscosity reduction and micro-
Biological viscosity reduction method etc., wherein thick-oil emulsified adhesive-reducing production technique is that application range is most wide and most economical effective method.Viscous crude
Thinner generallys use the mode of surfactant compound, and surfactant used is generally nonionic surfactant, yin
Ionic surface active agent, amphoteric surfactant, wherein have compared with high-temperature resistant ability be anionic surfactant and it is non-from
Son-anion amphoteric surfactant.The core of thick-oil emulsified adhesive-reducing is the screening of thinner, does not require nothing more than the viscosity reduction to viscous crude
Effect is good, and emulsifying rate is fast, scattered with viscous crude effect, does not form big oil droplet, also requires emulsification system too stable, have
Conducive to the breaking emulsion and dewatering of Produced Liquid.Good heavy crude thinner has the spy for flowing dispersion and static layering after requiring reducing thick oil viscosity
Point.
In recent years, China scientific research personnel has developed a variety of property for the thickened oil recovery requirement under the conditions of different mineral reserve
The excellent emulsifying pour depressor of energy, wherein the polymer emulsified thinner of copolymerization/condensation polymer type can be with mating surface activating agent and certain bases
The characteristics of group, have many advantages, such as that dosage is few, viscosity reduction is high-efficient and temperature-resistant anti-salt to medium-high viscosity viscous crude.Organosilicon (polymer) table
Research and application of the face activating agent on oil drilling and crude oil demulsification have pertinent literature and patent report, and as viscous crude
The pertinent literature that uses of exploitation thinner, patent then report less.
It is compound thick that 103450868 A of Chinese patent literature CN discloses a kind of Heat-resistant salt-tolerant water-soluble amphipathic polymer
Oily thinner.By acrylamide, hydrophobic alkyl acrylamide, acrylamido alkyl ammomium chloride quaternary ammonium salt and nonionic polyoxyalkylene third
Olefin(e) acid ester quaternary random copolymerization at amphipathic polymer be combined as component A and Small molecular surfactant B component, add
The ability of its viscosity reduction viscous crude is better than OP-10 and poly- table binary complex system etc. when concentration 0.3%.
102516972 A of Chinese patent literature CN discloses a kind of water base viscous crude drop of combed modified polyorganosiloxane anion
Stick.The thinner uses main chain as dimethyl silicone polymer, and side chain is chain alkyl, propylidene polyoxyethylene polyoxypropylene
The comb-type structure of ether organic acid esters salt, main side chain are connected with Si-C chemical bond, and surface-active and interfacial activity are strong, dense adding
Temperature-resistant anti-salt and hydrolytic Resistance are good when spending 0.5%, have good viscosity reduction ability to viscous crude.The inventive method is with poly- methyl hydrogen
Siloxanes, hexamethyldisiloxane, octamethylcy-clotetrasiloxane etc. are primary raw material, through overbalance copolymerization, chloroplatinic acid-catalysis silicon
Hydrogen addition, anionic three-step reaction are completed, and processing step is many and diverse, at high cost.
Currently, polymerization species heavy crude thinner in actual use mostly need to be with other additive compounds, organopolysiloxane
The problems such as class heavy crude thinner price is higher, and it is more stable that the two exists simultaneously emulsification system, is unfavorable for Produced Liquid breaking emulsion and dewatering.
Summary of the invention
In view of the deficiencies of the prior art, the present invention, which provides one kind not only, has temperature-resistant anti-salt and viscosity reducing effect but also is easy to be demulsified de-
The organic-silicon-modified amphipathic polymer type heavy crude thinner of water.The thinner does not need to use with other additive compounds, comprehensive
It can be excellent and environmentally protective.
The present invention also provides a kind of preparation sides of the organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering
Method.
Technical scheme is as follows:
A kind of organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering, the heavy crude thinner is by third
The amphipathic polymer that acrylamide and double bond containing organosilicone quaternary ammonium reactant salt generate, has structure shown in formula (I):
Wherein: R ' is H or CH3；X:y=100:0.5~5.0；
R are as follows:
Wherein: A is O or NH；A=2~4；B=2~4；R1For CH3Or C2H5；R2For CH3Or C2H5；R3、R4、R5Independently
Selected from OSi (CH3)3、OCH3、OC2H5Or C1-C3 alkyl, R3、R4、R5It is identical or different；X is Cl, Br or I.
It is preferred according to the present invention, in the R group, A NH, a=3, b=3, R1、R2It is CH3, R3、R4、R5It is
OSi(CH3)3, X Cl；
Alternatively, A is O, a=2, b=3, R1、R2It is CH3, R3、R4、R5It is OC2H5, X Cl.
Preferred according to the present invention, the double bond containing organosilicon quaternary ammonium salt has structure shown in formula (II):
Wherein: A, a, b, R ', R1、R2、R3、R4、R5, the meaning of X it is identical as meaning in formula (I)；
Preferably, R ' is CH3, A NH, a=3, b=3, R1、R2It is CH3, R3、R4、R5It is OSi (CH3)3, X Cl；
Alternatively, R ' is CH3, A O, a=2, b=3, R1、R2It is CH3, R3、R4、R5It is OC2H5, X Cl.
Preferred according to the present invention, the heavy crude thinner is white powder, weight average molecular weight are as follows: (1~5) × 106。
A kind of preparation method of the organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering, including step is such as
Under:
Acrylamide, double bond containing organosilicon quaternary ammonium salt and solvent are mixed evenly, mixed liquor is obtained；Nitrogen is passed through,
60~80 DEG C are heated to, initiator is added under stiring, in 60~80 DEG C, 5~12 hours is reacted, obtains reaction solution；It will reaction
Liquid cooling is but poured into acetone or alcohol afterwards, through suction filtration, immersion, washing, drying to get heavy crude thinner.
It is preferred according to the present invention, the mass ratio of the acrylamide and double bond containing organosilicon quaternary ammonium salt be 100:5~
25；Preferably, the mass ratio of the acrylamide and double bond containing organosilicon quaternary ammonium salt is 100:10~15.
It is preferred according to the present invention, the solvent be acetone, tetrahydrofuran, benzene, toluene, hexamethylene, glycol dimethyl ether,
The combination of one or more of 1,4- dioxane, N,N-dimethylformamide or DMAC N,N' dimethyl acetamide；
Preferably, the solvent is tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, n,N-Dimethylformamide or N, N- dimethyl second
The combination of one or more of amide.
Preferred according to the present invention, the solid content of the mixed liquor is 10~20wt%；Preferably, the mixed liquor is consolidated
Content is 15wt%.
Preferred according to the present invention, the initiator is azo-initiator, organic peroxy class initiator, inorganic peroxy class
The combination of one or more of initiator or redox type initiators；The quality of the initiator be acrylamide and
The 0.05~2% of double bond containing organosilicon quaternary ammonium salt gross mass；
Preferably, the initiator is azodiisobutyronitrile；The quality of the initiator is acrylamide and double bond containing
The 0.5~1.0% of organosilicon quaternary ammonium salt gross mass.
Preferred according to the present invention, the reaction temperature is 65~75 DEG C.
It is preferred according to the present invention, it is filtered obtained product acetone or alcohol and impregnates and wash 5~10 times, 60 DEG C are true
Sky is 24~72 hours dry.
Preferred according to the present invention, the preparation method of the double bond containing organosilicon quaternary ammonium salt comprises the following steps that
Alkyl acryl amido tertiary amine or alkyl acrylic ester group tertiary amine, haloalkyl silane and solvent are mixed equal
It is even；In 60~90 DEG C, reacts 36~72 hours, be cooled to room temperature；Through vacuum rotary steam, washing to get double bond containing organosilicon season
Ammonium salt.
Preferably, the alkyl acryl amido tertiary amine or alkyl acrylic ester group tertiary amine have structure shown in formula (III):
Wherein: A, a, R ', R1、R2Meaning it is identical as meaning in formula (I).
Preferably, the haloalkyl silane has structure shown in formula (IV):
Wherein, b, R3、R4、R5, the meaning of X it is identical as meaning in formula (I).
Preferably, mole of the alkyl acryl amido tertiary amine or alkyl acrylic ester group tertiary amine and haloalkyl silane
Than for 1:1~3；It is further preferred that the alkyl acryl amido tertiary amine or alkyl acrylic ester group tertiary amine and halogenated alkyl
The molar ratio of silane is 1:1.5~2.0.
Preferably, the solvent is methanol, ethyl alcohol, isopropanol, dimethyl sulfoxide, tetrahydrofuran, N, N- dimethyl formyl
The combination of one or more of amine or acetone；The quality of the solvent is alkyl acryl amido tertiary amine or alkyl
1~2 times of perester radical tertiary amine and haloalkyl silane gross mass；It is further preferred that the solvent is acetone, ethyl alcohol or isopropyl
The combination of one or more of alcohol；The quality of the solvent is alkyl acryl amido tertiary amine or alkyl acrylic ester group
1.5 times of tertiary amine and haloalkyl silane gross mass.
Preferably, the reaction temperature is 75~85 DEG C, and the reaction time is 48~72 hours.
Preferably, the mode of washing is with ether or petroleum ether 3~5 times.
The advantage of technical solution of the present invention is:
Organic silicon surfactant has the characteristics that strong, the of the invention drop of low surface tension, high temperature resistant, dispersion moistening performance
Organic functional silicon base is introduced into polymer architecture side chain using acrylamide as primary raw material and obtains organic-silicon-modified two by stick
Close polymer-type heavy crude thinner has the characteristics that simple process, cost is relatively low.
The thinner has the preferable ability for reducing oil water interfacial tension, and emulsifying capacity is strong, but it emulsifies rear stability
It is suitable for, is conducive to the breaking emulsion and dewatering of Produced Liquid, reduces later period water process difficulty.
Organic-silicon-modified amphipathic polymer type heavy crude thinner provided by the invention does not need and alkali, small molecule surface-active
Other additive compounds such as agent, being used alone under low concentration (≤0.1%) both has preferable heat-resistant salt-resistant performance and viscosity reduction
Effect.
Detailed description of the invention
Fig. 1 is the infrared spectrum of organosilicone quaternary ammonium salt monomer SQ1 in embodiment 1.
Fig. 2 is the infrared spectrum of organic-silicon-modified amphipathic polymer type heavy crude thinner PASQ1-1 prepared by embodiment 1.
Specific embodiment
The present invention is described further combined with specific embodiments below, but not limited to this.
Experimental method described in following embodiments is unless otherwise specified conventional method simultaneously；The reagent and material
Material, unless otherwise specified, commercially obtains.
Embodiment 1
(1) synthesis of organosilicone quaternary ammonium salt monomer SQ1
By (N, N- dimethylamino-propyl) Methacrylamide 4.26g, 3- chloropropyl three (three silyloxies) silane
18.62g and isopropanol 34.32g is added in three-necked flask, stirs evenly.At 82 DEG C of temperature, after reaction 60 hours, it is cooled to
Room temperature；Vacuum rotary steam removes most of solvent and the unreacted raw material in part.Remaining distillate is washed 3~5 times with ether,
Obtain organosilicone quaternary ammonium salt monomer SQ1 10.17g, yield 75%；
Synthetic reaction formula is as follows:
(2) synthesis of heavy crude thinner PASQ1-1
42.6g acrylamide (AM), 2.13g organosilicone quaternary ammonium salt monomer SQ1,298.2g N, N- dimethyl are weighed respectively
Formamide (DMF), which is added, has thermometer, N2In the four-hole boiling flask of airway, reflux condenser and agitating device, lower logical N is stirred2
It is warming up to 70 ± 5 DEG C after 30 minutes, weighs 0.224g azodiisobutyronitrile, is added in reaction flask in three batches, keeps reaction temperature
At 70 ± 5 DEG C, 12 hours are reacted, are poured into after reaction solution cooled to room temperature in 500ML acetone, is filtered by vacuum, obtain
White powdery solids are obtained organosilicon and are changed with being dried in vacuo 48 hours at acetone (300ML × 5) washing by soaking 5 times, 60 DEG C
Property amphipathic polymer type heavy crude thinner product PASQ1-1 38.5g, yield 86.0%.
Synthesized PASQ1-1 has structure as follows:
Fig. 1 is the infrared spectrum of organosilicone quaternary ammonium salt monomer SQ1 in the present embodiment.As shown in Figure 1,3240cm-1、
1654cm-1And 1206cm-1It is the characteristic absorption peak of amide groups, 1120~1051cm-1Two asymmetrical peak dissymmetric peaks are flexible for Si-O-Si
Vibration absorption peak, 840cm-1And 750cm-1It is Si- (CH3)3The stretching vibration absworption peak of middle Si-C, 1256cm-1For Si-CH3's
The deformation vibration the absworption peak of Si-C, 1630cm-1、976cm-1And 923cm-1It is the characteristic absorption peak of C=C key, 3415cm-1With
1465cm-1Corresponding two peaks are nitrogen cation, 3415cm-1It is capped.The presence of these characteristic peaks shows to contain in target product
Double bond, amide groups, siloxy and nitrogen cation.
Nuclear-magnetism (1H NMR) test data of organosilicone quaternary ammonium salt monomer SQ1 is as follows in the present embodiment:1H(NMR)
(CDCl3):0.05-0.12ppm(SiOSiCH3,27H),0.43-0.53ppm(CH2CH2CH2Si,2H),5.3-5.7ppm(CH2
=C, 2H), 3.2-3.3ppm (CH2CH2CH2N, 2H), 3.1-3.2ppm (CH2CH2NCH2CH2, 4H), 3.0-3.1ppm
(CH3NCH3, 6H), 2.6-2.7ppm (CH2CH2CH2N),2.0-2.1ppm(CH2CH2CH2Si, 2H), 1.7-1.8ppm
(CH2CH2CH2Si,2H),1.6-1.7ppm(NHCH2CH2CH2, 1H).
Fig. 2 is the infrared spectrum of organic-silicon-modified amphipathic polymer type heavy crude thinner PASQ1-1 manufactured in the present embodiment.
As shown in Figure 2,3340cm-1For the N-H stretching vibration peak of primary amine (AM) in PASQ1-1 structure, 3195cm-1For secondary amine (SQ)
N-H stretching vibration peak, 1666cm-1For the C=0 stretching vibration peak of amide (AM), 1453cm-1For the mixing in-plane bending of amide
Vibration peak, 1120~1051cm-1Two asymmetrical peak dissymmetric peaks are Si-O-Si stretching vibration absworption peak, 840cm-1And 750cm-1It is Si-
(CH3)3The stretching vibration absworption peak of middle Si-C, 1260cm-1For Si-CH3Si-C deformation vibration the absworption peak, 3415cm-1For
The characteristic peak of quaternary ammonium cations is capped, in 1000~900cm-1There is not the O=C stretching vibration peak of vinyl monomer in section,
Show that polymerization reaction carries out completely, without monomer residue.
The nuclear-magnetism (1H NMR) of organic-silicon-modified amphipathic polymer type heavy crude thinner PASQ1-1 manufactured in the present embodiment is surveyed
It is as follows to try data:
1H(NMR)(D2O):0.06-0.11ppm(SiOSiCH3,27H),0.53ppm(CH2CH2CH2Si,2H),3.26ppm
(CH2CH2CH2N, 2H), 3.13ppm (CH2CH2NCH2CH2, 4H), 3.01ppm (CH3NCH3, 6H), 2.78ppm
(CH2CH2CH2N),2.13ppm(CH2CHCO,1H),2.12ppm(CH2CH2CH2Si,2H),1.705ppm(CH2CH2CH2S i,
2H),1.69ppm(NHCH2CH2CH2, 1H), 1.585ppm (CH2CHC,4H),1.07ppm(CH2CCH3, 3H).Prepared by proof
Thinner have expected structure.
Embodiment 2~5
The synthetic method of heavy crude thinner PASQ1-2, PASQ1-3, PASQ1-4 and PASQ1-5 are as described in Example 1, institute
Unlike: SQ1 is different from the mass ratio of AM (as shown in table 1 below), other consistent.
Table 1: Examples 1 to 5 heavy crude thinner PASQ1 experimental result
| Thinner | SQ1/AM (%) | Yield (%) | Molecular weight (× 106) | |
| Embodiment 1 | PASQ1-1 | 5 | 86.0 | 1.8 |
| Embodiment 2 | PASQ1-2 | 10 | 86.9 | 2.8 |
| Embodiment 3 | PASQ1-3 | 15 | 88.0 | 3.6 |
| Embodiment 4 | PASQ1-4 | 20 | 85.0 | 4.0 |
| Embodiment 5 | PASQ1-5 | 25 | 84.1 | 4.5 |
Embodiment 6
(1) synthesis of organosilicone quaternary ammonium salt monomer SQ2
By dimethylaminoethyl methacrylate 3.93g, 3- chloropropyl (triethoxy) silane 12.04g and ethyl alcohol
23.96g is added in three-necked flask, stirs evenly.At 78 DEG C of temperature, after reaction 72 hours, it is cooled to room temperature, vacuum rotary steam removes
Remove the unreacted raw material of most of solvent and part.By remaining distillate with petroleum ether 3~5 times, organosilicon season is obtained
Ammonium salt monomer SQ2 6.96g, yield 70%；
Synthetic reaction formula is as follows:
(2) synthesis of heavy crude thinner PASQ2
42.6g acrylamide, 4.26g organosilicone quaternary ammonium salt monomer SQ2,312.4g tetrahydrofuran are weighed, is added with temperature
Degree meter, N2In the four-hole boiling flask of airway, reflux condenser and agitating device, lower logical N is stirred270 ± 5 are warming up to after 30 minutes
DEG C, 0.234g azodiisobutyronitrile is weighed, is added in reaction flask in three batches, keeps reaction temperature at 70 ± 5 DEG C, is reacted 10 small
When, it is poured into after reaction solution cooled to room temperature in 500ML acetone, is filtered by vacuum, obtains white powdery solids, use acetone
It is dried in vacuo 48 hours at (300ML × 5) washing by soaking 5 times, 60 DEG C, obtains organic-silicon-modified amphipathic polymer heavy crude thinner
PASQ2 product 41.05g, yield 87.6%, molecular weight 2.6 × 106。
Synthesized PASQ2 has structure as follows:
Test example 1
The viscosity-reducing performance of heavy crude thinner PASQ1-2, PASQ2 are evaluated
Organic-silicon-modified amphipathic polymer type heavy crude thinner is configured to the aqueous solution of series of concentrations gradient, at 50 DEG C
At (simulated formation temperature), thinner aqueous solution is added to according to grease volume ratio 7:3 after being stirred 2 hours in viscous crude and forms cream
Shape liquid, using Brookfield II+viscosimeter of DV- (rotator type SC4-31), experimental viscosity value test temperature is 50 DEG C, shearing
Rate is 7.34s-1, the viscosity of test emulsion of crude oil under reservoir conditions.Viscous crude sample is provided by certain oil field, wherein viscous crude 1 is
Common heavy oil (electric dehydration), viscosity is 1350mPas at 50 DEG C；Viscous crude 2 is common heavy oil (electric dehydration), and viscosity is at 50 DEG C
4200mPa·s；Viscous crude 3 is super-viscous oil, and viscosity is 83000mPas at 50 DEG C.
Table 2: viscosity reducing effect of the heavy crude thinner to different viscosities viscous crude
Note: viscosity reducing effect are as follows: viscosity break ratio/thinner use concentration.
As shown in Table 2, PASQ1 series thinner all has good viscosity reducing effect to viscous crude 1, viscous crude 2 and viscous crude 3,
PASQ2 thinner has preferable viscosity reducing effect to viscous crude 1 and viscous crude 2, to viscous crude 3 without viscosity reducing effect；To the viscosity reduction effect of viscous crude 1
Fruit PASQ2 is better than PASQ1, is better than PASQ2 to the viscosity reducing effect PASQ1 of viscous crude 2.
Test example 2
The evaluation of thinner PASQ1-2 salt resistant character
The mineralized water that graded series are prepared according to table 3 prepares heavy crude thinner PASQ1-2 solution with mineralized water, and concentration is
1.0g/L is mixed, viscosity reduction of the thinner under different salinities under temperature 50 C according to the oil-water ratio (oil sample is viscous crude 2) of 7:3
Rate is as shown in table 4.
Table 3: mineralized water formula
Table 4: the viscosity break ratio of thinner PASQ1-2 under different salinities
| Total salinity (mg/L) | Viscosity (mPas) | Viscosity break ratio (%) | |
| Blank | 0 | 135 | 90 |
| 1 | 9374 | 145 | 89.3 |
| 2 | 23435 | 169 | 87.5 |
| 3 | 34786 | 225 | 83.3 |
| 4 | 37496 | 248.4 | 81.6 |
As shown in Table 4, the viscosity break ratio of thinner is reduced with the increase of salinity, but total salinity reaches
When 37496mg/L, viscosity break ratio is still greater than 80%, illustrates that PASQ1 thinner has certain salt tolerance.
Test example 3
The evaluation of thinner PASQ1 heat resistance
Thinner PASQ1-1, PASQ1-2 and PASQ1-3 are configured to the aqueous solution that concentration is 1.0g/L, in 65 DEG C of constant temperature
Under the conditions of carry out solution age processing, sample at regular intervals, and with viscous crude (oil sample be viscous crude 2) with grease volume ratio 7:3
Mixing, stirs 2 hours formation emulsion, tests its viscosity.
Table 5: influence of the ageing time to viscosity break ratio
Viscosity break ratio
As shown in Table 5, after aging in 15 days, the viscosity break ratio of thinner illustrates that PASQ1 drops substantially there is no variation
Stick has certain ageing-resistant performance.
Test example 4
Forming emulsion intercalation method after viscous crude addition thinner can evaluate
Thinner PASQ1-2 and PASQ2 are configured to aqueous solution respectively, concentration 1.0g/L, (oil sample is thick according to grease
The oil ratio mixing that 2) volume ratio is 7:3,2 hours formation emulsion is stirred under conditions of temperature is 50 DEG C, pours into sample bottle
In, it is measured, is measured using the TURBISCAN LAB stability analysis tester developed by French FORMULACTION company
Parameter is: temperature is 50 DEG C, and sweep parameter is each minute run-down, sweep time: 0.5 hour.
Table 6: viscous crude adds the dehydration rate of formation lotion after thinner
| Sample | Dehydration rate |
| PASQ1-2 | 76.2% |
| PASQ2 | 84.2% |
As shown in Table 6, in 0.5 hour, the dehydration rate for adding the emulsion of PASQ2 thinner (concentration 1.0g/L) reaches
84.2%, the dehydration rate for adding the emulsion of PASQ1 thinner (concentration 1.0g/L) is slightly lower, is 76.2%.Add two kinds of drops
Emulsion after stick, fast dewatering in a relatively short period of time, having reached after reducing thick oil viscosity has flowing dispersion and stands point
The characteristics of layer.
Claims (12)
1. a kind of organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering, which is characterized in that the viscous crude drop
Stick is the amphipathic polymer generated by acrylamide and double bond containing organosilicone quaternary ammonium reactant salt, has structure shown in formula (I):
Wherein: R ' is H or CH3；X:y=100:0.5~5.0；
R are as follows:
Wherein: A is O or NH；A=2~4；B=2~4；R1For CH3Or C2H5；R2For CH3Or C2H5；R3、R4、R5Independently selected from
OSi(CH3)3、OCH3、OC2H5Or C1-C3 alkyl, R3、R4、R5It is identical or different；X is Cl, Br or I.
2. the organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering according to claim 1, feature
It is, in the R group, A NH, a=3, b=3, R1、R2It is CH3, R3、R4、R5It is OSi (CH3)3, X Cl；
Alternatively, A is O, a=2, b=3, R1、R2It is CH3, R3、R4、R5It is OC2H5, X Cl.
3. the organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering according to claim 1, feature
It is, the double bond containing organosilicon quaternary ammonium salt has structure shown in formula (II):
Wherein: A, a, b, R ', R1、R2、R3、R4、R5, the meaning of X it is identical as meaning in formula (I).
4. the organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering according to claim 3, feature
It is, the R ' in formula (II) is CH3, A NH, a=3, b=3, R1、R2It is CH3, R3、R4、R5It is OSi (CH3)3, X Cl.
5. the organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering according to claim 3, feature
It is, the R ' in formula (II) is CH3, A O, a=2, b=3, R1、R2It is CH3, R3、R4、R5It is OC2H5, X Cl.
6. the organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering according to claim 1, feature
It is, the heavy crude thinner is white powder, weight average molecular weight are as follows: (1~5) × 106。
7. the organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering as described in any one of claims 1 to 6
Preparation method, comprise the following steps that
Acrylamide, double bond containing organosilicon quaternary ammonium salt and solvent are mixed evenly, mixed liquor is obtained；It is passed through nitrogen, is heated
To 60~80 DEG C, initiator is added under stiring, in 60~80 DEG C, reacts 5~12 hours, obtains reaction solution；Liquid cooling will be reacted
But it pours into acetone or alcohol afterwards, through suction filtration, immersion, washing, drying to get heavy crude thinner.
8. the preparation side of the organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering according to claim 7
Method, which is characterized in that the mass ratio of the acrylamide and double bond containing organosilicon quaternary ammonium salt is 100:5~25.
9. the preparation side of the organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering according to claim 7
Method, which is characterized in that the solvent is acetone, tetrahydrofuran, benzene, toluene, hexamethylene, glycol dimethyl ether, Isosorbide-5-Nitrae-dioxy six
The combination of one or more of ring, N,N-dimethylformamide or DMAC N,N' dimethyl acetamide；
The initiator is that azo-initiator, organic peroxy class initiator, inorganic peroxy class initiator or redox class are drawn
Send out the combination of one or more of agent；The quality of the initiator is acrylamide and double bond containing organosilicon quaternary ammonium salt
The 0.05~2% of gross mass.
10. the preparation of the organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering according to claim 7
Method, which is characterized in that the solid content of the mixed liquor is 10~20wt%.
11. the preparation of the organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering according to claim 7
Method, which is characterized in that the reaction temperature is 65~75 DEG C.
12. the preparation of the organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering according to claim 7
Method, which is characterized in that the preparation method of the double bond containing organosilicon quaternary ammonium salt comprises the following steps that
Alkyl acryl amido tertiary amine or alkyl acrylic ester group tertiary amine, haloalkyl silane and solvent are mixed evenly；
In 60~90 DEG C, reacts 36~72 hours, be cooled to room temperature；Through vacuum rotary steam, washing to get double bond containing organosilicone quaternary ammonium
Salt；
The molar ratio of the alkyl acryl amido tertiary amine or alkyl acrylic ester group tertiary amine and haloalkyl silane is 1:1~3；
The solvent is in methanol, ethyl alcohol, isopropanol, dimethyl sulfoxide, tetrahydrofuran, N,N-dimethylformamide or acetone
A combination of one or more；The quality of the solvent be alkyl acryl amido tertiary amine or alkyl acrylic ester group tertiary amine and
1~2 times of haloalkyl silane gross mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611205704.8A CN106632839B (en) | 2016-12-23 | 2016-12-23 | A kind of organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611205704.8A CN106632839B (en) | 2016-12-23 | 2016-12-23 | A kind of organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106632839A CN106632839A (en) | 2017-05-10 |
| CN106632839B true CN106632839B (en) | 2018-12-14 |
Family
ID=58826811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611205704.8A Active CN106632839B (en) | 2016-12-23 | 2016-12-23 | A kind of organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106632839B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880213B (en) * | 2017-11-21 | 2019-12-24 | 山东大学 | Siloxane quaternary ammonium salt modified amphiphilic polymer super-extra-heavy oil viscosity reducer and preparation method and application thereof |
| CN108585611A (en) * | 2018-05-15 | 2018-09-28 | 佛山市华通混凝土有限公司 | A kind of strong concrete thinner and preparation method thereof |
| CN110686164B (en) * | 2019-02-27 | 2021-03-02 | 山东宝龙达实业集团有限公司 | Method for reducing viscosity of crude oil |
| CN110144205A (en) * | 2019-05-20 | 2019-08-20 | 陈光辉 | A kind of high efficiency heavy crude thinner and preparation method thereof |
| CN111662408B (en) * | 2020-07-14 | 2021-11-12 | 中海石油(中国)有限公司 | Oil displacement system suitable for high-temperature high-salt oil reservoir |
| CN112442350B (en) * | 2020-12-01 | 2022-05-24 | 山东德仕化工有限公司 | Thick oil cold recovery huff and puff viscosity reducer and preparation method and application thereof |
| CN112322133A (en) * | 2020-12-03 | 2021-02-05 | 上海瑞君电泳涂料有限公司 | Thick film impact-resistant corrosion-resistant cathode electrophoretic coating and preparation process thereof |
| CN113861957B (en) * | 2021-11-04 | 2022-09-30 | 中国石油大学(北京) | Double-base nano viscosity reducer and application thereof in heavy oil recovery and recovery method |
| CN114957572B (en) * | 2022-04-14 | 2023-04-28 | 山东大学 | Imine bond modified quaternary ammonium salt amphiphilic block polymer and preparation method and application thereof |
| CN115806648B (en) * | 2022-12-28 | 2024-02-13 | 科之杰新材料集团有限公司 | Polycarboxylate superplasticizer prepared from viscosity reducing macromonomer and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516972B (en) * | 2011-12-07 | 2014-01-01 | 南京美思德新材料有限公司 | Comb-shaped modified polysiloxane anion water-base thick oil viscosity reducer and synthesizing method thereof |
| CN103450868A (en) * | 2013-08-12 | 2013-12-18 | 新疆天普石油天然气工程技术有限公司 | Heat-resistant salt-tolerant water-soluble amphiphilic polymer composite thick oil viscosity reducer |
| CN104140803B (en) * | 2013-10-29 | 2017-02-08 | 中国石油化工股份有限公司 | Thick oil dispersion viscosity reducer and preparation method thereof |
| CN103772605B (en) * | 2014-01-23 | 2015-12-02 | 中国海洋石油总公司 | A kind of preparation method of cationic polymers |
| CN103772604B (en) * | 2014-01-23 | 2015-12-09 | 中国海洋石油总公司 | A kind of cationic polymers |
| CN103897117B (en) * | 2014-04-09 | 2016-03-30 | 中国海洋石油总公司 | A kind of amphiphilic quatemay ammonium inner salt and preparation method thereof and application |
| CN104327225B (en) * | 2014-10-15 | 2017-04-19 | 山东大学 | Nano SiO2 composite material thickened oil viscosity reducer and preparation method thereof |
-
2016
- 2016-12-23 CN CN201611205704.8A patent/CN106632839B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106632839A (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106632839B (en) | A kind of organic-silicon-modified amphipathic polymer type heavy crude thinner of easy breaking emulsion and dewatering and preparation method thereof | |
| CN111072974B (en) | Method for preparing polyether modified polysiloxane | |
| US5118775A (en) | Fluoroorganopolysiloxane and a process for preparing the same | |
| CN107880213A (en) | Super super-heavy crude viscosity-reducing agent of amphipathic polymer that a kind of siloxane quaternary ammonium is modified and preparation method and application | |
| CN105297427B (en) | A kind of compound for improving amino-modified silicone oil based carbon fiber finish heat resistance and its preparation and application | |
| CN101648123B (en) | Nonionic aqueous POSS-based polymer surfactant | |
| CN105367802A (en) | Polyether modified phenyl hydrogen-containing silicone oil and preparation method thereof | |
| CN109575294A (en) | A kind of V-arrangement dimethyl silicone polymer polyoxyethylene ether mono acrylic ester and preparation method thereof | |
| CN110862543B (en) | Preparation method of hyperbranched hydrogen-containing siloxane supercritical carbon dioxide thickener | |
| CN104448323A (en) | Starlike pectinate polyether-organosilicone copolymer and preparation method thereof | |
| Li et al. | Green glucamine-based trisiloxane surfactant: Surface activity, aggregate behavior, and superspreading on hydrophobic surfaces | |
| CN104001350B (en) | Method for improving performances of antifoaming agent for circuit board cleaning | |
| US20230391959A1 (en) | Preparation method for and application of modified siloxane-based supercritical carbon dioxide thickener | |
| Xu et al. | Synthesis and aqueous solution properties of a novel nonionic, amphiphilic comb-type polyacrylamide | |
| CN109942819A (en) | A kind of preparation method of straight chain ladder-like poly-phenyl silsesquioxane | |
| Feng et al. | Study of polysiloxanes containing epoxy groups: I. Synthesis and characterization of polysiloxanes containing 3-(2, 3-epoxypropoxy) propyl groups | |
| CN106750324A (en) | A kind of poly- quaternary ammonium polyethers dimethyl silicone polymer and preparation method thereof and hand feel finishing agent | |
| EP0797612A1 (en) | Method for preparing essentially cyclene-free polyorganosiloxanes and organofunctional siloxanes | |
| CN101780385B (en) | Preparation method of fluorosilicon oil with high-efficiency defoaming performance | |
| CN104829839B (en) | A kind of fluoro organosilicon polymer and preparation method thereof | |
| Wang et al. | Synthesis and Characterization of Polysiloxane Grafted Polyamide‐Amine Surfactants | |
| US5914420A (en) | Perfluorinated organo substituted cyylosiloxanes and copolymers prepared from these cyclosiloxahes | |
| US5116928A (en) | Process for preparing a fluoroorganopolysiloxane | |
| Hou et al. | Polysiloxanes with quaternary ammonium groups for SPPO aqueous emulsions | |
| Fortuniak et al. | Reactions of tertiary hydroxyalkylamines with 3-halogenopropyl substituted polysiloxanes: a route to water soluble and amphiphilic silicones |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |