CN104163885B - A kind of cationic polymer and its preparation method and application - Google Patents
A kind of cationic polymer and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of cationic polymer and its preparation method and application.Wherein, it is formula that the cationic polymer contains construction unit A and construction unit B, the construction unit A（1）Shown construction unit, the construction unit B is formula（2）Shown construction unit；And on the basis of the gross weight of construction unit in the cationic polymer, the content of the construction unit A is 86.6 98.8 weight % for the content of 1.2 13.4 weight %, the construction unit B.Present invention also offers a kind of cationic polymer preparation method and the cationic polymer as reverse-phase emulsifier application.The cationic polymer that the present invention is provided possesses excellent demulsification oil separated rate, to the obvious processing effect of crude oil sewage particularly polymer-bearing waste-water.
Description
Technical field
The present invention relates to a kind of cationic polymer, the preparation method of the cationic polymer is prepared by the method
Cationic polymer, and the cationic polymer is used as the application of reverse-phase emulsifier.
Background technology
Effective production technique that polymer flooding improves recovery ratio, increases crude output as one, is ensureing China oil field
Played an important role in stable yields, but with the expansion of polymer flooding application scale, the intractability of sewage also increases therewith
Plus.
Compared with the condition of water quality of filled drive oil extraction-generated waste water, polymer flooding oil-extraction wastewater（Abbreviation polymer-bearing waste-water）In not only contain
Oil mass is high, and contains substantial amounts of polymer.The presence of polymer increased the viscosity of water phase, and water is mutually taken oily ability strengthens,
The difficulty of water-oil separating is also increased simultaneously.And be difficult to reach back using water drive conventional sewage handling process polymer-contained sewage
The water quality requirement of note original place layer, so needing the clear water of a large amount of low mineralizations for configuring polymer flooding solution.So that original annotation
Water-sewerage balance is destroyed.Therefore, the treatment of polymer-bearing waste-water turned into oil-contaminated water of oil field treatment important topic it
One.
The oil content after country's sewage disposal rises to 1000-3000mg/L by original 200-300mg/L at present, or even
Up to 5000mg/L.Stratum can be caused serious injury behind such produced-water reinjection underground, permeability be reduced, while also can shadow
Ring raising of oil recovery factor etc..Therefore, the development urgent need development of oil extraction industry can be suitably used for oil-in-water（O/W）Type emulsus
The new and effective reverse-phase emulsifier of liquid treatment.The reverse-phase emulsifier for commonly using at present is with partial hydrolysis PAMC
Based on, and the shortcoming of partial hydrolysis PAMC is that hydrolysis rate is fast at high temperature, generates substantial amounts of carboxyl, carboxyl
With bivalent cation in water（Ca2+, Mg2+）Irreversible binding cause that polymer occurs split-phase and to precipitate, cause demulsification de-oiling to be imitated
Fruit is remarkably decreased.Therefore, the performance of common partial hydrolysis PAMC is difficult to meet oil field raising oil recovery
The use requirement of rate.
Therefore, how to prepare a kind of cationic polymer with excellent deoiling effect as reverse-phase emulsifier is still this
One of the important topic in field.
The content of the invention
The purpose of the present invention for the drawbacks described above of prior art provide a kind of cationic polymer and preparation method thereof and
The cationic polymer prepared by the method, and the cationic polymer is used as the application of reverse-phase emulsifier.The sun from
Sub- polymer possesses excellent demulsification oil separated rate, to the obvious processing effect of crude oil sewage particularly crude oil polymer-bearing waste-water.
It was found by the inventors of the present invention that introduce hydrophobic grouping in cationic polymer, then can make the hydrophobic grouping with
There is association in the hydrophobic organic compound in polymer-bearing waste-water, increase flocculation demulsification.
To achieve these goals, the present invention provides a kind of cationic polymer, and the cationic polymer contains structure list
First A and construction unit B, wherein, the construction unit A is formula（1）Shown construction unit, the construction unit B is formula（2）Institute
The construction unit for showing；And on the basis of the gross weight of construction unit in the cationic polymer, the content of the construction unit A
It is 1.2-13.4 weight %, the content of the construction unit B is 86.6-98.8 weight %；
Formula（1）,Formula（2）,
Wherein, R1It is the alkyl of C1-C4；R3、R4And R5It is each independently the alkyl of C1-C2；R2And R7Independently of one another
It is hydrogen or the alkyl of C1-C4；R6It is the alkylidene of C1-C3；X-It is Cl-、Br-Or I-。
Present invention also offers a kind of preparation method of cationic polymer, the preparation method is included in emulsion polymerization
Under the conditions of, in the presence of initiator and surfactant, make a kind of monomer mixture that polymerisation is carried out in water,
Wherein, it is formula that the monomer mixture contains monomer D and monomer E, the monomer D（3）Shown monomer, the list
Body E is formula（4）Shown monomer；On the basis of the gross weight of monomer in the monomer mixture, the content of the monomer D is
The content of 1.2-13.4 weight %, the monomer E is 86.6-98.8 weight %；
Formula（3）,Formula（4）,
Wherein, R1It is the alkyl of C1-C4；R3、R4And R5It is each independently the alkyl of C1-C2；R2And R7Independently of one another
It is hydrogen or the alkyl of C1-C4；R6It is the alkylidene of C1-C3；X-It is Cl-、Br-Or I-。
Present invention also offers the cationic polymer prepared by the above method.
Additionally, present invention also offers above-mentioned cationic polymer as reverse-phase emulsifier application.
The cation type polymer that the present invention is provided possesses excellent demulsification oil separated rate, crude oil sewage is particularly containing poly-
The effect is significant of the demulsification de-oiling of sewage.Meanwhile, the cationic polymer that the present invention is provided, preparation method is simple, preparing raw material
It is easy to get.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with following tool
Body implementation method is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the proton nmr spectra analysis chart of the cationic polymer P 1 of embodiment 1.
Fig. 2 is the infrared spectrogram of the cationic polymer P 1 of embodiment 1.
Fig. 3 is the proton nmr spectra analysis chart of the cationic polymer P 2 of embodiment 2.
Fig. 4 is the infrared spectrogram of the cationic polymer P 2 of embodiment 2.
Fig. 5 is the proton nmr spectra analysis chart of the cationic polymer P 3 of embodiment 3.
Fig. 6 is the infrared spectrogram of the cationic polymer P 3 of embodiment 3.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of cationic polymer, wherein, the cationic polymer contains construction unit A and construction unit
B, wherein, the construction unit A is formula（1）Shown construction unit, the construction unit B is formula（2）Shown construction unit；
And on the basis of the gross weight of construction unit in the cationic polymer, the content of the construction unit A is 1.2-13.4 weights
The content of amount %, the construction unit B is 86.6-98.8 weight %；Content in view of the construction unit A is less than 1.2 weight %
Or during higher than 13.4 weight %, the cationic polymer can become to the treatment effect of oil-polluted water particularly crude oil polymer-bearing waste-water
Difference, under preferable case, on the basis of the gross weight of construction unit in the cationic polymer, the content of the construction unit A
It is 3.2-9.8 weight %, the content of the construction unit B is 90.2-96.8 weight %；Further preferably in the case of, it is described sun from
In sub- polymer on the basis of the gross weight of construction unit, the content of the construction unit A is 5.1-7.8 weight %, the structure list
The content of first B is 92.2-94.9 weight %.
Formula（1）,Formula（2）,
Wherein, R1Can be the alkyl of C1-C4, preferably normal-butyl；R3、R4And R5It is each independently the alkane of C1-C2
Base, preferably methyl；R2And R7It is each independently the alkyl of hydrogen or C1-C4, under preferable case, R2It is hydrogen, R7It is methyl；R6
Can be the alkylidene of C1-C3, preferably ethylidene, such as-CH2CH2-；X- is Cl-、Br-Or I-, preferably Cl-。
In the present invention, the alkyl can be straight chain, or side chain.The example of the alkyl of the C1-C4 can
To include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group.
In the present invention, the example of the alkylidene of the C1-C3 can be included but is not limited to：Methylene, ethylidene, sub- positive third
Base, isopropylidene.The alkylidene refers to the residue after alkane loses two hydrogen atoms, and described two hydrogen atoms can be same
Two hydrogen atoms on individual carbon atom, it is also possible to two hydrogen atoms on different carbon atoms, can be straight chain, or branch
Chain, for example, the ethylidene can be-CH2CH2- or-CH (CH3)-。
According to the present invention, the cationic polymer is appearance colorless or flaxen solid.
In the present invention, the demulsification de-oiling effect of the cationic polymer is improved significantly, and this is probably because described
Hydrophobic grouping is introduced in cationic polymer, the hydrophobic grouping can be formed by with the hydrophobic organic compound in polymer-bearing waste-water
Cooperation is used, and dramatically increases flocculation demulsification.
In the present invention, the intrinsic viscosity and cationic degree of the cationic polymer can change in scope wider.
In order to reach preferably demulsification de-oiling effect, under preferable case, the intrinsic viscosity of the cationic polymer is 167-402cm3/
G, more preferably 300-350cm3/g；The cationic degree of the cationic polymer is 0.0151-0.0351mmol/g, more preferably
It is 0.0180-0.0210mmol/g.
In the present invention, it is necessary to explanation, the cationic degree of the cationic polymer refers to by known in this field
Polyvinyl alcohol（PVSK）The content of the cation in the cationic polymer that standard liquid titration is measured.Method of testing is such as
Under：Cationic polymer after purification is dissolved in distilled water, matches somebody with somebody concentration for conventional amount used, use salt acid for adjusting pH value, add first
Aniline blue solution is titrated as indicator with PVSK standard liquids, when sample solution is changed into aubergine, and several seconds not from blueness
Terminal is during colour fading.Cationic degree is calculated by the gauge for consuming PVSK standard liquids.
In the present invention, the intrinsic viscosity is the method according to GB12005.1-89, is measured using Ubbelohde viscometer.
The present inventor has found that the cation being made up of specific construction unit A and construction unit B gathers under study for action
Compound can obtain fabulous demulsification de-oiling effect.For instance, it is preferred that R1It is normal-butyl, R2It is hydrogen, R3、R4And R5Independently of one another
It is methyl, R7It is methyl, X-It is Cl-, i.e., described construction unit A is formula（5）Shown construction unit, the construction unit B is formula
（6）Shown construction unit,
Formula（5）,Formula（6）,
Wherein, R6Can be the alkylidene of C1-C3, preferably ethylidene, such as-CH2CH2-。
The present invention also provides a kind of preparation method of cationic polymerization, and the preparation method is included in emulsion polymerization condition
Under, in the presence of initiator and surfactant, make a kind of monomer mixture that polymerisation is carried out in water,
Wherein, it is formula that the monomer mixture contains monomer D and monomer E, the monomer D（3）Shown monomer, the list
Body E is formula（4）Shown monomer；On the basis of the gross weight of monomer in the monomer mixture, the content of the monomer D is
The content of 1.2-13.4 weight %, the monomer E is 86.6-98.8 weight %；Content in view of the structures alone D is less than
1.2 weight % or during higher than 13.4 weight %, treatment of the cationic polymer to oil-polluted water particularly crude oil polymer-bearing waste-water
Effect can be deteriorated, and under preferable case, on the basis of the gross weight of monomer in the monomer mixture, the content of the monomer D is
The content of 3.2-9.8 weight %, the monomer E is 90.2-96.8 weight %；In the case of further preferably, the content of the monomer D
It is 5.1-7.8 weight %, the content of the monomer E is 92.2-94.9 weight %,
Formula（3）,Formula（4）,
Wherein, R1Can be the alkyl of C1-C4, preferably normal-butyl；R3、R4And R5It is each independently the alkane of C1-C2
Base, preferably methyl；R2And R7It is each independently the alkyl of hydrogen or C1-C4, under preferable case, R2It is hydrogen, R7It is methyl；R6Can
Think the alkylidene of C1-C3, preferably ethylidene, such as-CH2CH2-；X-It is Cl-、Br-Or I-, preferably Cl-。
According to the present invention, the cationic polymer prepared by the preparation method is appearance colorless or flaxen solid
Body.
According to the present invention, the intrinsic viscosity and cationic degree of the cationic polymer can become in scope wider
It is dynamic.In order to reach preferably demulsification de-oiling effect, under preferable case, the intrinsic viscosity of the cationic polymer is 167-
402cm3/ g, more preferably 300-350cm3/g；The cationic degree of the cationic polymer is 0.0151-0.0351mmol/g,
More preferably 0.0180-0.0210mmol/g.The assay method of the intrinsic viscosity and cationic degree be described above it is consistent,
This is repeated no more.
According to the present invention, to the weight of the monomer mixture and the ratio of water and the gross weight of monomer mixture without spy
Do not limit, can be changed in scope wider.Under preferable case, the weight of the monomer mixture mixes with water and monomer
The ratio of the gross weight of thing is 0.1-0.4：1, preferably 0.2-0.3：1.
According to the present invention, the consumption to the surfactant is not particularly limited, and can become in scope wider
It is dynamic.Can be played in emulsion polymerization in view of the surfactant reduces the surface tension of monomer and forms monomer
The effect of micella, under preferable case, on the basis of the gross weight of the monomer mixture, the consumption of the surfactant is 1-
5 weight %；In the case of further preferably, on the basis of the gross weight of the monomer mixture, the consumption of the surfactant is
2-4 weight %.
According to the present invention, the surfactant can be various conventional surfactants, preferable case in this area
Under, the surfactant is selected from cetyl trimethylammonium bromide, neopelex, APES
（OP-10）And sorbitol anhydride oleate（Span-80）In one or more.
According to the present invention, the charging opportunity to the surfactant is not particularly limited, but in view of the surface
Activating agent plays a part of to reduce the surface tension of monomer and monomer is formed micella, under preferable case, before adding initiator,
The surfactant is added into reaction system together with the monomer mixture.
According to the present invention, the mode of initiated polymerization can be the conventional mode in this area, it is preferable that use initiator
Triggered.The present invention is not particularly limited to the consumption of the initiator, can be changed in scope wider, preferably feelings
Under condition, on the basis of the gross weight of the monomer mixture, the consumption of the initiator is 0.1-1 weight %, further preferred feelings
Under condition, on the basis of the gross weight of the monomer mixture, the consumption of the initiator is 0.2-0.8 weight %.
Such as according to the present invention, the initiator can be the conventional various initiators in this area, and described initiator is nothing
One or more in machine peroxide series initiators, redox series initiators and water-soluble azo series initiators.Preferably,
The initiator be ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide-sodium thiosulfate, hydrogen peroxide-frerrous chloride,
Hydrogen peroxide-ascorbic acid, potassium peroxydisulfate-sodium thiosulfate, 2,2 '-azo-bis-iso-dimethyl, 2,2 '-azo [2- (2-
Imidazoline -2- bases) propane] one or more in dihydrochloride and 2,2 '-azo two (2- amidine propanes) dihydrochloride.
According to the present invention, the emulsion polymerization condition can be the conventional emulsion polymerization condition in this area, example
As carried out in the presence of an inert gas, the emulsion polymerization condition includes：Reaction temperature can be 30-60 DEG C, preferably
30-50℃；Reaction time can be 0.5-7 hours, preferably 3-6 hours.
The reaction temperature of the emulsion polymerization refers to that polymerization reaction system is warmed up to a stationary temperature, and addition is drawn
Hair agent, and temperature when carrying out polymerisation is maintained under the steady temperature.
It should be noted that when simultaneously the emulsion polymerization uses inorganic peroxide series initiators and water solubility idol
During nitrogen series initiators, the emulsion polymerization carries out two stages successively, and the reaction condition of first stage includes：Reaction temperature
It it is 30-50 DEG C, the reaction time is 0.5-4 hours；The reaction condition of second stage includes：Reaction temperature is 50-60 DEG C, during reaction
Between be 1-2 hours.
In nitrogen or the periodic table of elements of the inert gas including this area routine in group 0 element gas at least
One kind, preferably nitrogen.Inert gas shielding method known to those skilled in the art, such as it is poly- except being included in
Close reaction carry out in the middle of be passed through beyond inert gas protected, be additionally included in the forward direction reaction system for adding initiator and be passed through
Inert gas, to remove the dissolved oxygen in the aqueous solution.
Additionally, the present inventor has found under study for action, and when selected specific monomer D and monomer E are reacted, institute
The polymer for obtaining can obtain preferably demulsification de-oiling effect, for instance, it is preferred that R1It is normal-butyl, R2It is hydrogen, R3、R4And R5Each
It independently is methyl, R7It is methyl, X-It is Cl-When, i.e., described monomer D is（7）Shown monomer, the monomer E is formula（8）Institute
The monomer for showing,
Formula（7）,Formula（8）,
Wherein, R6It is the alkylidene of C1-C3, preferably ethylidene, such as-CH2CH2-。
According to the present invention, the cationic polymer can be coagulated by purifying precipitation, centrifugation, filtering, decantation, hot water
The method such as poly- carries out purification step and obtains, and this those skilled in the art can be known, will not be described in great detail herein.
Present invention also offers the cationic polymer as obtained in above-mentioned preparation method.
Additionally, the cationic polymer that the cationic polymer and the method according to the invention of present invention offer are prepared
Can be applied in the treatment of crude oil sewage and crude oil polymer-bearing waste-water as reverse-phase emulsifier.The method of application is referred to ability
Technical method known to field technique personnel.
According to the present invention, the cationic polymer when for processing crude oil sewage or polymer-bearing waste-water, can directly with
Solid form is used, it is also possible to used in the form of the aqueous solution of the cationic polymer.Under preferable case, will can contain
The aqueous solution of cationic polymer of the invention is contacted with crude oil sewage or polymer-bearing waste-water.The aqueous solution of the cationic polymer
Concentration be 0.5-1.5 weight %.
, according to the invention it is preferred in the case of, the crude oil sewage relative to 1L, the aqueous solution middle-jiao yang, function of the spleen and stomach of the cationic polymer
The consumption of ionomer is 1-20mg, preferably 3-10mg；It is the polymer-bearing waste-water of 100mg, institute relative to 1L polymer contents
The consumption for stating the cations in aqueous solution polymer of cationic polymer is 50-200mg, preferably 60-150mg.
According to the present invention, the polymer in crude oil polymer-bearing waste-water is not particularly limited, for example, can be KYPAM-2 types
One or more in polymer, KYPAM-6A types polymer and the type polymer of positive force II.
According to the present invention, do not have to the condition that the aqueous solution of the cationic polymer is contacted with crude oil sewage or polymer-bearing waste-water
Have and especially limit, the Conventional contact condition that can be well known to those skilled in the art, the temperature of such as contact can be 40-
60 DEG C, preferably 50-55 DEG C；The time of contact can be 0.5-4 hours, preferably 1-3 hours.
Additionally, the cationic polymer that the present invention is provided can process the crude oil of various oil content（Containing poly-）Sewage, for example,
The crude oil（Containing poly-）The oil content of sewage can be 1000-2000mg/L.The crude oil of the oil content（Containing poly-）Sewage can be with
Various sources are taken from, for example, oilfield sewage, daily-use chemical industry sewage etc..
The cationic polymer that the present invention is provided can be used as reverse-phase emulsifier, it is also possible to used as reverse-phase emulsifier
One of constituent is used cooperatively with existing other demulsifiers, to improve the broad-spectrum performance of reverse-phase emulsifier.It is described existing
Other demulsifiers, for example, can be to react the cationic surfactant, the two thio ammonia that prepare by epoxychloropropane and polyamines
One or more in base formates, diallyldimethylammonium chloride homopolymers and PAMC.
Below will the present invention will be described in detail by embodiment.When understanding, specific implementation described herein
Mode is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The intrinsic viscosity of following examples cationic polymer according to the method for GB12005.1-89, using Ubbelohde viscosity
Measure；Cationic degree passes through polyvinyl alcohol（PVSK）Standard liquid titration is measured；The composition of molecular structure and construction unit
Using IR spectrum and1H-NMR is determined.
MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride in following embodiments is purchased from Zibo Nuo Ruding Trade Co., Ltd.s,
In addition, unless specifically indicated, the reagent used in embodiment, comparative example and test case is commercially available product.
Embodiment 1
The present embodiment is used to illustrate cationic polymer of present invention offer and preparation method thereof.
（1）Weigh 2.56 grams of butyl acrylates, 1.62 grams of cetyl trimethylammonium bromides, 78.7 grams of methacryloxypropyls
Ethyl-trimethyl salmiac and 244 grams of deionized waters are added in reactor, are stirred well to and are completely dissolved.
（2）Nitrogen is passed through with air in nitrogen displacement reactor and continuously, is heated to 35 DEG C, add 0.163 gram
Sodium thiosulfate, potassium peroxydisulfate（The weight ratio of the two is 1：2）Start reaction.Reaction 6h is kept at 35 DEG C.
（3）Cooling, is precipitated with absolute ethyl alcohol, is dried, and obtains white solid P1.
The intrinsic viscosity of cationic polymer P1 is 342.50, and cationic degree is 0.0181mmol/g, and monomer conversion is
More than 99.9%.
P1 is carried out1H-NMR is determined, and measurement result is as shown in figure 1, determine that the cationic polymeric molecule for obtaining has formula
（9）Shown structure, is C-CH at 1.049ppm3Proton peak, at 1.167ppm in hydrophobic grouping butyl acrylate with first
Connected methylene-the CH of base2- proton peak, be N-CH in cation group at 3.226ppm3Proton peak, be at 3.805ppm
Methylene-the CH being connected with N2- proton peak, at 4.623-4.640ppm be-CH2The proton peak of O-；Wherein, formula（9）And m
The type of construction unit is only represented with n, and does not indicate that the connected mode of construction unit.The concrete numerical value of m and n is true by inventory
Fixed, the ratio of m and n is 1：0.05, the ratio is the mol ratio of the construction unit represented by m and n.
IR spectroscopic assays, measurement result are carried out to P1 as shown in Fig. 2 955.4cm-1It is quaternary ammonium salt N to locate+(CH3)3Feature
Absworption peak；1158.5cm-1And 1299cm-1It is the δ absworption peaks of C-O；1488.4 is (CH2)2δ absworption peaks；1646.7cm-1It is C=
The γ absworption peaks of O；1731.5cm-1It is the characteristic absorption peak of ester group.Additionally, in 3200-3500cm-1Between have a series of sharp peaks, be
With N+The CH of connection3CH in molecule2γ absworption peaks.In addition, in 1660-1680cm-1（C=C）Crest disappears, and shows that double bond occurs
Fracture is polymerized.
Test above shows to have synthesized subject polymer.
Formula（9）.
Comparative example 1
Method according to embodiment 1 prepares polymer, unlike, in step（1）In add 27.08g propylene
Sour hydroxyl ethyl ester, forms terpolymer DP1.It is 167 to measure the intrinsic viscosity of copolymer DP1, and cationic degree is 1.73mmol/g.
Comparative example 2
Method according to embodiment 1 prepares polymer, unlike, butyl acrylate is added without, form homopolymers
DP2, it is 320.22 to measure the intrinsic viscosity of homopolymers DP2, and cationic degree is 0.0182mmol/g.
Embodiment 2
The present embodiment is used to illustrate cationic polymer of present invention offer and preparation method thereof.
（1）Weigh 5.29 grams of butyl acrylates, 2.52 grams of cetyl trimethylammonium bromides, 78.7 grams of methacryloxypropyls
Ethyl-trimethyl salmiac and 335.96 grams of deionized waters are added in reactor, are stirred well to and are completely dissolved.
（2）Nitrogen is passed through with air in nitrogen displacement reactor and continuously, is heated to 40 DEG C, add 0.420 gram 2,
2 '-azo two (2- amidine propanes) dihydrochloride starts reaction.Reaction 4h is kept at 40 DEG C.
（3）Cooling, is precipitated with absolute ethyl alcohol, is dried, and obtains white solid P2.
The intrinsic viscosity of cationic polymer P2 is 344.34, and cationic degree is 0.0205mmol/g, and monomer conversion is
More than 99.9%.
P2 is carried out1H-NMR is determined, and measurement result is as shown in figure 3, determine that the cationic polymeric molecule for obtaining has formula
（9）Shown structure, is C-CH at 1.090ppm3Proton peak, be hydrophobic grouping butyl acrylate at 1.184-1.231ppm
In the methylene-CH that is connected with methyl2- proton peak, be N-CH in cation group at 3.264ppm3Proton peak, 3.841-
It is methylene-the CH being connected with N at 3.876ppm2- proton peak, at 4.565ppm be-CH2The proton peak of O-；Wherein, formula（9）
And m and n only represent the type of construction unit, and the connected mode of construction unit is not indicated that.The concrete numerical value of m and n is by throwing
Doses determines that the ratio of m and n is 1：0.109, the ratio is the mol ratio of the construction unit represented by m and n.
IR spectroscopic assays, measurement result are carried out to P2 as shown in figure 4,955.9cm-1It is quaternary ammonium salt N+(CH3)3Characteristic absorption
Peak；1151.6cm-1And 1299cm-1It is the δ absworption peaks of C-O；1479.9 is (CH2)2δ absworption peaks；1639.3cm-1It is C=O's
γ absworption peaks；1727.8cm-1It is the characteristic absorption peak of ester group.Additionally, in 3200-3500cm-1Between have a series of sharp peaks, be and N+
The CH of connection3CH in molecule2γ absworption peaks.In addition, in 1660-1680cm-1（C=C）Crest disappears, and shows that double bond occurs disconnected
Split and be polymerized.
Test above shows to have synthesized subject polymer.
Embodiment 3
The present embodiment is used to illustrate cationic polymer of present invention offer and preparation method thereof.
（1）Weigh 8.58 grams of butyl acrylates, 3.5 grams of cetyl trimethylammonium bromides, 78.7 grams of methacryloxypropyls
Ethyl-trimethyl salmiac and 203.6 grams of deionized waters are added in reactor, are stirred well to and are completely dissolved.
（2）Nitrogen is passed through with air in nitrogen displacement reactor and continuously, is heated to 30 DEG C, add 0.7268 gram
Sodium thiosulfate, potassium peroxydisulfate and 2,2 '-azo two (2- amidine propanes) dihydrochloride（The weight ratio of three is 1：2：1）Start
Reaction.After reaction 4h, reaction temperature is increased to 50 DEG C, continues to react 2h.
（3）Cooling, is precipitated with absolute ethyl alcohol, is dried, and obtains faint yellow solid P3.
The intrinsic viscosity of cationic polymer P3 is 314.85, and cationic degree is 0.0204mmol/g, and monomer conversion is
More than 99.9%.
P3 is carried out1H-NMR is determined, and measurement result is as shown in figure 5, determine that the cationic polymeric molecule for obtaining has formula
（9）Shown structure, is C-CH at 1.086ppm3Proton peak, be hydrophobic grouping butyl acrylate at 1.185-1.232ppm
In the methylene-CH that is connected with methyl2- proton peak, be N-CH in cation group at 3.325ppm3Proton peak,
It is methylene-the CH being connected with N at 3.877ppm2- proton peak, at 4.535ppm be-CH2The proton peak of O-；Wherein, formula（9）
And m and n only represent the type of construction unit, and the connected mode of construction unit is not indicated that.The concrete numerical value of m and n is by throwing
Doses determines that the ratio of m and n is 1：0.177, the ratio is the mol ratio of the construction unit represented by m and n.
IR spectroscopic assays, measurement result are carried out to P3 as shown in fig. 6,953.6cm-1It is quaternary ammonium salt N to locate+(CH3)3Feature is inhaled
Receive peak；1157.3cm-1And 1268.4cm-1It is the δ absworption peaks of C-O；1488.6 is (CH2)2δ absworption peaks；1646.8cm-1It is C=
The γ absworption peaks of O；1732.3cm-1It is the characteristic absorption peak of ester group.Additionally, in 3200-3500cm-1Between have a series of sharp peaks, be
With N+The CH of connection3CH in molecule2γ absworption peaks.In addition, in 1660-1680cm-1（C=C）Crest disappears, and shows that double bond occurs
Fracture is polymerized.
Test above shows to have synthesized subject polymer.
Test case 1
By cationic polymer P2, DP1 and the SF-Y001 types sun of Wen County four directions material for water treatment Co., Ltd production from
Sub- polyacrylamide HPAM distinguishes soluble in water as reverse-phase emulsifier, and the aqueous solution that concentration is 1.5 weight % is made into respectively.
By above-mentioned reverse-phase emulsifier respectively with lonely three stations crude oil sewage（Oil content is 2000mg/L, without polymer）
Reacted 0.5 hour at 50 DEG C, according to the oil-water interfaces after the observation contact of SY/T5797-93 methods, then carry out water-oil separating simultaneously
Oil removal rate is determined, according to the oil content that SY/T0530-93 methods are tested in gained water phase, and the outward appearance of water phase is observed, as a result existed
As shown in table 1.
Table 1
Be can be seen that at identical conditions from the data of table 1, compared with DP1 and HPAM, the cation that the present invention is provided
2 pairs of crude oil sewage deoiling effects without polymer of polymer P are more preferable, and reverse-phase emulsifier P2 adds the concentration of sewage much
Less than DP1 and HPAM.
Test case 2
Cationic polymer P1-P3, DP1, DP2 are distinguished soluble in water using HPAM as reverse-phase emulsifier, is made into respectively
Concentration is the aqueous solution of 1 weight %.
By the aqueous solution of above-mentioned reverse-phase emulsifier respectively with the lonely bigeminy station containing polymer, lonely three station, lonely tetrad station
Gudao oilfield crude oil sewage and Henan Oil Field crude oil sewage（Oil content is 2000mg/L, is 100mg/L containing poly- amount, gathers
The type polymer of positive force II that compound is provided for oil field）.Reacted 1 hour at 55 DEG C, observed according to SY/T5797-93 methods and contacted
Oil-water interfaces afterwards, then carry out water-oil separating and determine oil removal rate, are tested in gained water phase according to SY/T0530-93 methods
Oil content, and the outward appearance of water phase is observed, as a result as shown in table 2.Because DP1 is for the crude oil sewage demulsification containing polymer
Not substantially, therefore do not listed in table.
Table 2
Be can be seen that at identical conditions from the data of table 2, compared with DP2 and HPAM, the cation that the present invention is provided
Polymer P 1-P3 is more preferable to the crude oil sewage deoiling effect containing polymer.Additionally, the cationic polymer pair that the present invention is provided
Different types of crude oil sewage has preferable deoiling effect.
Test case 3
Using cationic polymer P1-P3 as reverse-phase emulsifier, the aqueous solution that concentration is 0.5 weight % is made into respectively.
By the aqueous solution of above-mentioned reverse-phase emulsifier respectively with the lonely three stations crude oil sewage containing polymer（Oil content is
2000mg/L, is 100mg/L, the KYPAM-6A polymer that polymer is provided for oil field containing poly- amount）, reacted 1 hour at 40 DEG C,
The oil-water interfaces after contact are observed according to SY/T5797-93 methods and determine oil removal rate, water-oil separating is then carried out, according to SY/
Oil content in T0530-93 methods test gained water phase, and the outward appearance of water phase is observed, as a result shown in table 3.
Table 3
By the data of table 3 can be seen that the present invention offer cationic polymer P1-P3 under conditions of different concentration
Preferable deoiling effect can be obtained.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (13)
1. a kind of application of cationic polymer as reverse-phase emulsifier in polymer-bearing waste-water treatment, the system of the cationic polymer
Preparation Method is included under the conditions of emulsion polymerization, in the presence of initiator and surfactant, a kind of monomer mixture is existed
Polymerisation is carried out in water,
Wherein, it is the monomer shown in formula (3), the monomer E that the monomer mixture contains monomer D and monomer E, the monomer D
Monomer shown in formula (4)；On the basis of the gross weight of monomer in the monomer mixture, the content of the monomer D is 3.2-
The content of 9.8 weight %, the monomer E is 90.2-96.8 weight %；
Wherein, R1It is the alkyl of C1-C4；R3、R4And R5It is each independently the alkyl of C1-C2；R2And R7It is each independently hydrogen
Or the alkyl of C1-C4；R6It is the alkylidene of C1-C3；X-It is Cl-、Br-Or I-,
The initiator is in inorganic peroxide series initiators, redox series initiators and water-soluble azo series initiators
One or more,
The surfactant is selected from cetyl trimethylammonium bromide, neopelex, alkylphenol-polyethenoxy
One or more in ether and sorbitol anhydride oleate,
The emulsion polymerization condition causes that the intrinsic viscosity of gained cationic polymer after emulsion polymerization is 167-
402cm3/ g, the cationic degree of the cationic polymer is 0.0151-0.0351mmol/g.
2. application according to claim 1, wherein, R1It is normal-butyl, R2It is hydrogen, R3、R4And R5It is each independently methyl,
R6It is ethylidene, R7It is methyl, X-It is Cl-。
3. application according to claim 1, wherein, weight and water and the gross weight of monomer mixture of the monomer mixture
The ratio of amount is 0.1-0.4：1.
4. application according to claim 3, wherein, weight and water and the gross weight of monomer mixture of the monomer mixture
The ratio of amount is 0.2-0.3：1.
5. application according to claim 1, wherein, on the basis of the gross weight of the monomer mixture, the surface is lived
Property agent consumption be 1-5 weight %.
6. application according to claim 5, wherein, on the basis of the gross weight of the monomer mixture, the surface is lived
Property agent consumption be 2-4 weight %.
7. application according to claim 1, wherein, on the basis of the gross weight of the monomer mixture, the initiator
Consumption be 0.1-1 weight %.
8. application according to claim 7, wherein, on the basis of the gross weight of the monomer mixture, the initiator
Consumption be 0.2-0.8 weight %.
9. application according to claim 1, wherein, the initiator is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, mistake
Hydrogen oxide-sodium thiosulfate, hydrogen peroxide-frerrous chloride, hydrogen peroxide-ascorbic acid, potassium peroxydisulfate-sodium thiosulfate, 2,
In 2 '-azo [2- (2- imidazoline -2- bases) propane] dihydrochloride and 2,2 '-azo two (2- amidine propanes) dihydrochloride one
Plant or various.
10. the application according to any one in claim 1-9, wherein, the emulsion polymerization is deposited in inert gas
Carried out under, the condition of the emulsion polymerization includes：Reaction temperature is 30-60 DEG C, and the reaction time is 0.5-7 hours.
11. applications according to claim 1, wherein, the cationic polymer is with the aqueous solution of cationic polymer
Form is used, and is the polymer-bearing waste-water of 100mg, the cations in aqueous solution of the cationic polymer relative to 1L polymer contents
The consumption of polymer is 50-200mg.
12. applications according to claim 1, wherein, what the aqueous solution of the cationic polymer was contacted with polymer-bearing waste-water
Temperature is 40-60 DEG C, and the time of contact is 0.5-4 hours.
13. applications according to claim 1, wherein, polymer in the polymer-bearing waste-water is KYPAM-2 types polymer,
One or more in KYPAM-6A types polymer and the type polymer of positive force II.
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| AU2019327459C1 (en) * | 2018-08-29 | 2023-06-01 | Ecolab Usa Inc. | Multiple charged ionic compounds derived from polyamines and compositions thereof and use thereof as reverse emulsion breakers in oil and gas operations |
| CN113831479A (en) * | 2020-06-08 | 2021-12-24 | 中国石油化工股份有限公司 | Lignin-based amphoteric polymer containing super-long chain structure and preparation method and application thereof |
| CN114426632B (en) * | 2020-10-10 | 2023-04-11 | 中国石油化工股份有限公司 | Amphoteric polyelectrolyte, preparation method thereof, polymeric flocculant and oily sewage treatment method |
| CN113698531B (en) * | 2021-03-10 | 2022-11-15 | 西南石油大学 | Reverse demulsifier for treating oilfield produced liquid and preparation method thereof |
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| US5643460A (en) * | 1994-01-14 | 1997-07-01 | Nalco/Exxon Energy Chemicals, L. P. | Method for separating oil from water in petroleum production |
| CN101319026A (en) * | 2008-06-18 | 2008-12-10 | 江苏飞翔化工股份有限公司 | Method for preparing cationic polymer for auxiliary colophony dispersion in colophony sizing agent |
| CN102850480B (en) * | 2011-06-30 | 2014-08-27 | 中国石油化工股份有限公司 | Polymer and its preparation method and application, and processing method for oily sewage |
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| Mucoadhesive interactions of amphiphilic cationic copolymers based on [2-(methacryloyloxy)ethyl]trimethylammonium chloride;Nataliya A等;《International Journal of Pharmaceutics》;20070223;第339卷(第1期);第25-32页 * |
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