CN104163885A - Cationic polymer, preparation method and applications thereof - Google Patents
Cationic polymer, preparation method and applications thereof Download PDFInfo
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- CN104163885A CN104163885A CN201310183542.2A CN201310183542A CN104163885A CN 104163885 A CN104163885 A CN 104163885A CN 201310183542 A CN201310183542 A CN 201310183542A CN 104163885 A CN104163885 A CN 104163885A
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Abstract
The invention discloses a cationic polymer, a preparation method and applications thereof. The cationic polymer comprises a structural unit A and a structural unit B, the structural unit A is represented by the formula (1), and the structural unit B is represented by the formula (2). The structural unit A accounts for 1.2 to 13.4 wt% of the total weight of the structural units in the cationic polymer, and the structural unit B accounts for 86.6 to 98.8 wt% of the total weight of the structural units in the cationic polymer. The invention also provides a preparation method of the cationic polymer and an application of the cationic polymer as a reverse demulsifier. The provided cationic polymer has an excellent demulsifying and deoiling performance, and has a prominent effect on processing crude oil sewage especially sewage containing polymers.
Description
Technical field
The present invention relates to a kind of cationic polymers, the preparation method of this cationic polymers, the cationic polymers being prepared by the method, and described cationic polymers is as the application of reverse-phase emulsifier.
Background technology
Polymer flooding, as an effective production technique that improves recovery ratio, increases crude production rate, plays an important role in guarantee China oilfield stable production, and still, along with the expansion of polymer flooding application scale, the intractability of sewage also increases thereupon.
Compared with the condition of water quality of filled drive oil extraction-generated waste water, in polymer flooding oil-extraction wastewater (abbreviation polymer-bearing waste-water), not only oleaginousness is high, and contains a large amount of polymkeric substance.The existence of polymkeric substance has increased the viscosity of water, makes water take oily ability and strengthens, and has also increased the difficulty of oily water separation simultaneously.And utilize the conventional sewage treatment process polymer-contained sewage of water drive to be difficult to reach the water quality requirement on the former stratum of re-injection, so need the clear water of a large amount of low mineralizations to be used for configuring polymer flooding solution.Thereby make former water filling-sink drainage balance destroyed.Therefore, the processing of polymer-bearing waste-water has become one of important topic of oil-contaminated water of oil field processing.
Oleaginousness after current domestic sewage disposal rises to 1000-3000mg/L by original 200-300mg/L, even up to 5000mg/L.After such produced-water reinjection is underground, can cause serious injury stratum, reduce rate of permeation, also can affect the raising of oil recovery factor etc. simultaneously.Therefore, Oil extraction industrial expansion is badly in need of developing the new and effective reverse-phase emulsifier that can be applicable to the processing of oil-in-water (O/W) type milk sap.The reverse-phase emulsifier generally using is at present taking partial hydrolysis cationic polyacrylamide as main, and the shortcoming of partial hydrolysis cationic polyacrylamide is that at high temperature hydrolysis rate is fast, generates a large amount of carboxyls, divalent cation (Ca in carboxyl and water
2+, Mg
2+) irreversible fixation make polymkeric substance generation phase-splitting and precipitation, cause breakdown of emulsion de-oiling effect significantly to decline.Therefore, the performance of common partial hydrolysis cationic polyacrylamide is difficult to meet the service requirements of oil field raising oil recovery.
Therefore, how to prepare a kind of cationic polymers with good deoiling effect and be still one of important topic of this area as reverse-phase emulsifier.
Summary of the invention
The cationic polymers that object of the present invention provides a kind of cationic polymers and preparation method thereof and prepared by the method for the above-mentioned defect of prior art, and this cationic polymers is as the application of reverse-phase emulsifier.This cationic polymers possesses good breakdown of emulsion de-oiling performance, to the particularly obvious processing effect of crude oil polymer-bearing waste-water of former oily water.
The present inventor finds, introduces hydrophobic grouping in cationic polymers, can make the hydrophobic organic compound generation association in this hydrophobic grouping and polymer-bearing waste-water, and the demulsification that makes to flocculate increases.
To achieve these goals, the invention provides a kind of cationic polymers, this cationic polymers contains structural unit A and structural unit B, wherein, described structural unit A is the structural unit shown in formula (1), and described structural unit B is the structural unit shown in formula (2); And taking the gross weight of structural unit in described cationic polymers as benchmark, the content of described structural unit A is 1.2-13.4 % by weight, and the content of described structural unit B is 86.6-98.8 % by weight;
formula (1),
formula (2),
Wherein, R
1for the alkyl of C1-C4; R
3, R
4and R
5be the alkyl of C1-C2 independently of one another; R
2and R
7be the alkyl of hydrogen or C1-C4 independently of one another; R
6for the alkylidene group of C1-C3; X
-for Cl
-, Br
-or I
-.
The present invention also provides a kind of preparation method of cationic polymers, and this preparation method is included under emulsion polymerization condition, under initiator and tensio-active agent existence, makes a kind of monomer mixture in water, carry out polyreaction,
Wherein, described monomer mixture contains monomer D and monomer E, and described monomer D is the monomer shown in formula (3), and described monomer E is the monomer shown in formula (4); Taking the gross weight of monomer in described monomer mixture as benchmark, the content of described monomer D is 1.2-13.4 % by weight, and the content of described monomer E is 86.6-98.8 % by weight;
formula (3),
formula (4),
Wherein, R
1for the alkyl of C1-C4; R
3, R
4and R
5be the alkyl of C1-C2 independently of one another; R
2and R
7be the alkyl of hydrogen or C1-C4 independently of one another; R
6for the alkylidene group of C1-C3; X
-for Cl
-, Br
-or I
-.
The present invention also provides the cationic polymers being prepared by aforesaid method.
In addition, the present invention also provides the application of above-mentioned cationic polymers as reverse-phase emulsifier.
Cation type polymer provided by the invention possesses good breakdown of emulsion de-oiling performance, and to former oily water, particularly the effect of the breakdown of emulsion de-oiling of polymer-bearing waste-water is remarkable.Meanwhile, cationic polymers provided by the invention, preparation method is easy, and raw materials is easy to get.
Brief description of the drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the proton nmr spectra analysis chart of cationic polymers P1 in embodiment 1.
Fig. 2 is the infrared spectrogram of cationic polymers P1 in embodiment 1.
Fig. 3 is the proton nmr spectra analysis chart of cationic polymers P2 in embodiment 2.
Fig. 4 is the infrared spectrogram of cationic polymers P2 in embodiment 2.
Fig. 5 is the proton nmr spectra analysis chart of cationic polymers P3 in embodiment 3.
Fig. 6 is the infrared spectrogram of cationic polymers P3 in embodiment 3.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of cationic polymers, wherein, this cationic polymers contains structural unit A and structural unit B, and wherein, described structural unit A is the structural unit shown in formula (1), and described structural unit B is the structural unit shown in formula (2); And taking the gross weight of structural unit in described cationic polymers as benchmark, the content of described structural unit A is 1.2-13.4 % by weight, and the content of described structural unit B is 86.6-98.8 % by weight; The content of considering described structural unit A is during lower than 1.2 % by weight or higher than 13.4 % by weight, this cationic polymers is to the particularly treatment effect meeting variation of crude oil polymer-bearing waste-water of oily(waste)water, under preferable case, taking the gross weight of structural unit in described cationic polymers as benchmark, the content of described structural unit A is 3.2-9.8 % by weight, and the content of described structural unit B is 90.2-96.8 % by weight; Further, under preferable case, in described cationic polymers, the gross weight of structural unit is benchmark, and the content of described structural unit A is 5.1-7.8 % by weight, and the content of described structural unit B is 92.2-94.9 % by weight.
formula (1),
formula (2),
Wherein, R
1can be the alkyl of C1-C4, be preferably normal-butyl; R
3, R
4and R
5be the alkyl of C1-C2 independently of one another, be preferably methyl; R
2and R
7be the alkyl of hydrogen or C1-C4 independently of one another, under preferable case, R
2for hydrogen, R
7for methyl; R
6can be the alkylidene group of C1-C3, be preferably ethylidene, as-CH
2cH
2-; X-is Cl
-, Br
-or I
-, be preferably Cl
-.
In the present invention, described alkyl can be straight chain, can be also side chain.The example of the alkyl of described C1-C4 can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl.
In the present invention, the example of the alkylidene group of described C1-C3 can include but not limited to: methylene radical, ethylidene, sub-n-propyl, isopropylidene.Described alkylidene group refers to that alkane loses two residues after hydrogen atom, and described two hydrogen atoms can be two hydrogen atoms on same carbon atom, two hydrogen atoms on also can different carbon atoms, it can be straight chain, also can be side chain, for example, described ethylidene can be-CH
2cH
2-or-CH (CH
3)-.
According to the present invention, described cationic polymers is appearance colorless or flaxen solid.
In the present invention, the breakdown of emulsion de-oiling effect of described cationic polymers is improved significantly, this may be because described cationic polymers in introduce hydrophobic grouping, this hydrophobic grouping can by with polymer-bearing waste-water in hydrophobic organic compound generation association, the demulsification that makes to flocculate significantly increases.
In the present invention, the intrinsic viscosity of described cationic polymers and cationic degree can change in wider scope.In order to reach better breakdown of emulsion de-oiling effect, under preferable case, the intrinsic viscosity of described cationic polymers is 167-402cm
3/ g, more preferably 300-350cm
3/ g; The cationic degree of described cationic polymers is 0.0151-0.0351mmol/g, more preferably 0.0180-0.0210mmol/g.
In the present invention, it should be noted that, the cationic degree of described cationic polymers refers to the cationic content in the cationic polymers recording by polyvinyl alcohol well known in the art (PVSK) standardized solution volumetry.Testing method is as follows: the cationic polymers after purifying is dissolved in to distilled water, it is conventional amount used that concentration is joined by institute, use salt acid for adjusting pH value, add toluidine blue solution as indicator, with the titration of PVSK standardized solution, when sample solution becomes red-purple from blueness, and in the several seconds, be terminal when colour-fast.Calculate cationic degree by the amount that consumes PVSK standardized solution.
In the present invention, described intrinsic viscosity is the method according to GB12005.1-89, adopts Ubbelohde viscometer to record.
The present inventor finds under study for action, and the cationic polymers being made up of specific structural unit A and structural unit B can be obtained fabulous breakdown of emulsion de-oiling effect.For example, preferably, R
1for normal-butyl, R
2for hydrogen, R
3, R
4and R
5be methyl independently of one another, R
7for methyl, X
-for Cl
-, described structural unit A is the structural unit shown in formula (5), described structural unit B is the structural unit shown in formula (6),
formula (5),
formula (6),
Wherein, R
6can be the alkylidene group of C1-C3, be preferably ethylidene, as-CH
2cH
2-.
The present invention also provides a kind of preparation method of cationoid polymerisation, and this preparation method is included under emulsion polymerization condition, under initiator and tensio-active agent existence, makes a kind of monomer mixture in water, carry out polyreaction,
Wherein, described monomer mixture contains monomer D and monomer E, and described monomer D is the monomer shown in formula (3), and described monomer E is the monomer shown in formula (4); Taking the gross weight of monomer in described monomer mixture as benchmark, the content of described monomer D is 1.2-13.4 % by weight, and the content of described monomer E is 86.6-98.8 % by weight; The content of considering described structure monomer D is during lower than 1.2 % by weight or higher than 13.4 % by weight, this cationic polymers is to the particularly treatment effect meeting variation of crude oil polymer-bearing waste-water of oily(waste)water, under preferable case, taking the gross weight of monomer in described monomer mixture as benchmark, the content of described monomer D is 3.2-9.8 % by weight, and the content of described monomer E is 90.2-96.8 % by weight; Further, under preferable case, the content of described monomer D is 5.1-7.8 % by weight, and the content of described monomer E is 92.2-94.9 % by weight,
formula (3),
formula (4),
Wherein, R
1can be the alkyl of C1-C4, be preferably normal-butyl; R
3, R
4and R
5be the alkyl of C1-C2 independently of one another, be preferably methyl; R
2and R
7be the alkyl of hydrogen or C1-C4 independently of one another, under preferable case, R
2for hydrogen, R
7for methyl; R
6can be the alkylidene group of C1-C3, be preferably ethylidene, as-CH
2cH
2-; X
-for Cl
-, Br
-or I
-, be preferably Cl
-.
According to the present invention, the described cationic polymers of being prepared by this preparation method is appearance colorless or flaxen solid.
According to the present invention, the intrinsic viscosity of described cationic polymers and cationic degree can change in wider scope.In order to reach better breakdown of emulsion de-oiling effect, under preferable case, the intrinsic viscosity of described cationic polymers is 167-402cm
3/ g, more preferably 300-350cm
3/ g; The cationic degree of described cationic polymers is 0.0151-0.0351mmol/g, more preferably 0.0180-0.0210mmol/g.The measuring method of described intrinsic viscosity and cationic degree is consistent with narration above, does not repeat them here.
According to the present invention, the ratio of the gross weight of the weight to described monomer mixture and water and monomer mixture is not particularly limited, and can in wider scope, change.Under preferable case, the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture is 0.1-0.4:1, is preferably 0.2-0.3:1.
According to the present invention, the consumption of described tensio-active agent is not particularly limited, can in wider scope, change.Consider that described tensio-active agent can play in emulsion polymerization and reduce the surface tension of monomer and make monomer form the effect of micella, under preferable case, taking the gross weight of described monomer mixture as benchmark, the consumption of described tensio-active agent is 1-5 % by weight; Further under preferable case, taking the gross weight of described monomer mixture as benchmark, the consumption of described tensio-active agent is 2-4 % by weight.
According to the present invention, described tensio-active agent can be the tensio-active agent of various routines in this area, under preferable case, described tensio-active agent is for being selected from one or more in cetyl trimethylammonium bromide, Sodium dodecylbenzene sulfonate, alkylphenol polyoxyethylene (OP-10) and sorbitol anhydride oleate (Span-80).
According to the present invention, be not particularly limited the reinforced opportunity to described tensio-active agent, but consider that described tensio-active agent plays the effect that reduces the surface tension of monomer and make monomer formation micella, under preferable case, before adding initiator, described tensio-active agent is added to reaction system together with described monomer mixture.
According to the present invention, the mode of initiated polymerization can be the mode of this area routine, preferably, adopts initiator to cause.The present invention is not particularly limited the consumption of described initiator, can in wider scope, change, under preferable case, taking the gross weight of described monomer mixture as benchmark, the consumption of described initiator is 0.1-1 % by weight, further under preferable case, taking the gross weight of described monomer mixture as benchmark, the consumption of described initiator is 0.2-0.8 % by weight.
According to the present invention, described initiator can be the various initiators of this area routine, and for example described initiator is one or more in inorganic peroxide series initiators, redox series initiators and water-soluble azo series initiators.Preferably, described initiator is ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide-Sulfothiorine, hydrogen peroxide-iron protochloride, hydrogen peroxide-xitix, Potassium Persulphate-Sulfothiorine, 2,2 '-azo-bis-iso-dimethyl, 2,2 '-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride and 2, one or more in 2 '-azo two (2-amidine propane) dihydrochloride.
According to the present invention, described emulsion polymerization condition can be the emulsion polymerization condition of this area routine, for example, under rare gas element exists, carry out, and described emulsion polymerization condition comprises: temperature of reaction can, for 30-60 DEG C, be preferably 30-50 DEG C; Reaction times can be 0.5-7 hour, is preferably 3-6 hour.
The temperature of reaction of described emulsion polymerization refers to that polymerization reaction system is warmed up to a constant temp, adds initiator, and remains on the temperature while carrying out polyreaction under this steady temperature.
It should be noted that, in the time that described emulsion polymerization adopts inorganic peroxide series initiators and water-soluble azo series initiators simultaneously, described emulsion polymerization carries out two stages successively, and the reaction conditions of first stage comprises: temperature of reaction is 30-50 DEG C, and the reaction times is 0.5-4 hour; The reaction conditions of subordinate phase comprises: temperature of reaction is 50-60 DEG C, and the reaction times is 1-2 hour.
Described rare gas element comprises at least one in neutral element gas in the nitrogen of this area routine or the periodic table of elements, is preferably nitrogen.Described protection of inert gas is method known in those skilled in the art; for example pass in the middle of carrying out rare gas element protects except being included in polyreaction; also be included in and add initiator in reaction system, to pass into rare gas element before, to remove the dissolved oxygen in the aqueous solution.
In addition, the present inventor finds under study for action, and in the time that selected specific monomer D reacts with monomer E, the polymkeric substance of gained can be obtained good breakdown of emulsion de-oiling effect, for example, preferably, R
1for normal-butyl, R
2for hydrogen, R
3, R
4and R
5be methyl independently of one another, R
7for methyl, X
-for Cl
-time, described monomer D is the monomer shown in (7), described monomer E is the monomer shown in formula (8),
formula (7),
formula (8),
Wherein, R
6for the alkylidene group of C1-C3, be preferably ethylidene, as-CH
2cH
2-.
According to the present invention, described cationic polymers can carry out purification step by methods such as purifying precipitation, centrifugation, filtration, decant, hot water cohesions and obtain, and all can know these those skilled in the art, will repeat no more at this.
The present invention also provides the cationic polymers being made by above-mentioned preparation method.
In addition the cationic polymers that, cationic polymers provided by the invention and the method according to this invention prepare can be used as reverse-phase emulsifier and applies in the processing of former oily water and crude oil polymer-bearing waste-water.The method of application can be with reference to technological method well known to those skilled in the art.
According to the present invention, described cationic polymers, when for the treatment of former oily water or polymer-bearing waste-water, can directly use with solid form, also can use with the form of the aqueous solution of described cationic polymers.Under preferable case, the aqueous solution that contains cationic polymers of the present invention can be contacted with former oily water or polymer-bearing waste-water.The concentration of the aqueous solution of described cationic polymers is 0.5-1.5 % by weight.
According to the present invention, under preferable case, with respect to the former oily water of 1L, the consumption of the cations in aqueous solution polymkeric substance of described cationic polymers is 1-20mg, is preferably 3-10mg; The polymer-bearing waste-water that is 100mg with respect to 1L polymer content, the consumption of the cations in aqueous solution polymkeric substance of described cationic polymers is 50-200mg, is preferably 60-150mg.
According to the present invention, the polymkeric substance in crude oil polymer-bearing waste-water is not particularly limited, can be for example one or more in KYPAM-2 type polymkeric substance, KYPAM-6A type polymkeric substance and positive power II type polymkeric substance.
According to the present invention, the aqueous solution of described cationic polymers is not particularly limited with the condition that former oily water or polymer-bearing waste-water contact, the conventional contact conditions that can be well known to those skilled in the art, for example the temperature of contact can be 40-60 DEG C, is preferably 50-55 DEG C; The time of contact can be 0.5-4 hour, is preferably 1-3 hour.
In addition, cationic polymers provided by the invention can be processed crude oil (containing the poly-) sewage of various oleaginousness, and for example, the oleaginousness of described crude oil (containing poly-) sewage can be 1000-2000mg/L.Crude oil (containing the poly-) sewage of described oleaginousness can be taken from various sources, for example, and oilfield sewage, daily-use chemical industry sewage etc.
Cationic polymers provided by the invention can be used as reverse-phase emulsifier and uses, and also can be used as one of moiety of reverse-phase emulsifier and is used in conjunction with existing other emulsion splitters, to improve the broad-spectrum performance of reverse-phase emulsifier.Described existing other emulsion splitters can be for example by one or more in cats product, dithiocar-bamate, diallyldimethylammonium chloride homopolymer and the cationic polyacrylamide of epoxy chloropropane and polyamines reaction preparation.
Below will describe the present invention by embodiment.When understanding, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
In following examples, the intrinsic viscosity of cationic polymers, according to the method for GB12005.1-89, adopts Ubbelohde viscometer to record; Cationic degree records by polyvinyl alcohol (PVSK) standardized solution volumetry; The composition of molecular structure and structural unit adopt IR spectrum and
1h-NMR measures.
MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride in following embodiment is purchased from Zibo Nuo Ruding Trade Co., Ltd., and in addition, unless specified otherwise, the reagent of using in embodiment, comparative example and test case is commercially available product.
Embodiment 1
The present embodiment is used for illustrating cationic polymers provided by the invention and preparation method thereof.
(1) take 2.56 grams of butyl acrylates, 1.62 grams of cetyl trimethylammonium bromides, 78.7 grams of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and 244 grams of deionized waters and join in reactor, be stirred well to completely and dissolve.
(2) also pass into continuously nitrogen with air in nitrogen replacement reactor, be heated to 35 DEG C, add Sulfothiorine, the Potassium Persulphate (weight ratio of the two is 1:2) of 0.163 gram to start reaction.At 35 DEG C, keep reaction 6h.
(3) cooling, by dehydrated alcohol precipitation, dry, obtain white solid P1.
The intrinsic viscosity of cationic polymers P1 is 342.50, and cationic degree is 0.0181mmol/g, and monomer conversion is more than 99.9%.
P1 is carried out
1h-NMR measures, and measurement result as shown in Figure 1, determines that the cationic polymeric molecule obtaining has the structure shown in formula (9), and 1.049ppm place is C-CH
3proton peak, 1.167ppm place is the methylene radical-CH being connected with methyl in hydrophobic grouping butyl acrylate
2-proton peak, 3.226ppm place is N-CH in cation group
3proton peak, 3.805ppm place is the methylene radical-CH being connected with N
2-proton peak, 4.623-4.640ppm place is-CH
2the proton peak of O-; Wherein, formula (9) and m and n only express the type of structural unit, and do not represent the mode of connection of structural unit.The concrete numerical value of m and n determined by charging capacity, and m is 1:0.05 with the ratio of n, and this ratio is the mol ratio of the represented structural unit of m and n.
P1 is carried out to IR spectrometry, measurement result as shown in Figure 2,955.4cm
-1place is quaternary ammonium salt N
+(CH
3)
3charateristic avsorption band; 1158.5cm
-1and 1299cm
-1for the δ absorption peak of C-O; 1488.4 is (CH
2)
2δ absorption peak; 1646.7cm
-1for the γ absorption peak of C=O; 1731.5cm
-1for the charateristic avsorption band of ester group.In addition, at 3200-3500cm
-1between have a series of sharp peaks, be and N
+the CH connecting
3cH in molecule
2γ absorption peak.In addition, at 1660-1680cm
-1(C=C) crest disappears, and shows that two keys fracture occur and carried out polymerization.
More than test shows to have synthesized subject polymer.
formula (9).
Comparative example 1
Prepare polymkeric substance according to the method described in embodiment 1, different, in step (1), add again 27.08g Hydroxyethyl acrylate, form terpolymer DP1.The intrinsic viscosity that records multipolymer DP1 is 167, and cationic degree is 1.73mmol/g.
Comparative example 2
Prepare polymkeric substance according to the method described in embodiment 1, different, do not add butyl acrylate, form homopolymer DP2, the intrinsic viscosity that records homopolymer DP2 is 320.22, cationic degree is 0.0182mmol/g.
Embodiment 2
The present embodiment is used for illustrating cationic polymers provided by the invention and preparation method thereof.
(1) take 5.29 grams of butyl acrylates, 2.52 grams of cetyl trimethylammonium bromides, 78.7 grams of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and 335.96 grams of deionized waters and join in reactor, be stirred well to completely and dissolve.
(2) also pass into continuously nitrogen with air in nitrogen replacement reactor, be heated to 40 DEG C, add 0.420 gram 2,2 '-azo two (2-amidine propane) dihydrochloride starts reaction.At 40 DEG C, keep reaction 4h.
(3) cooling, by dehydrated alcohol precipitation, dry, obtain white solid P2.
The intrinsic viscosity of cationic polymers P2 is 344.34, and cationic degree is 0.0205mmol/g, and monomer conversion is more than 99.9%.
P2 is carried out
1h-NMR measures, and measurement result as shown in Figure 3, determines that the cationic polymeric molecule obtaining has the structure shown in formula (9), and 1.090ppm place is C-CH
3proton peak, 1.184-1.231ppm place is the methylene radical-CH being connected with methyl in hydrophobic grouping butyl acrylate
2-proton peak, 3.264ppm place is N-CH in cation group
3proton peak, 3.841-3.876ppm place is the methylene radical-CH being connected with N
2-proton peak, 4.565ppm place is-CH
2the proton peak of O-; Wherein, formula (9) and m and n only express the type of structural unit, and do not represent the mode of connection of structural unit.The concrete numerical value of m and n determined by charging capacity, and m is 1:0.109 with the ratio of n, and this ratio is the mol ratio of the represented structural unit of m and n.
P2 is carried out to IR spectrometry, measurement result as shown in Figure 4,955.9cm
-1for quaternary ammonium salt N
+(CH
3)
3charateristic avsorption band; 1151.6cm
-1and 1299cm
-1for the δ absorption peak of C-O; 1479.9 is (CH
2)
2δ absorption peak; 1639.3cm
-1for the γ absorption peak of C=O; 1727.8cm
-1for the charateristic avsorption band of ester group.In addition, at 3200-3500cm
-1between have a series of sharp peaks, be and N
+the CH connecting
3cH in molecule
2γ absorption peak.In addition, at 1660-1680cm
-1(C=C) crest disappears, and shows that two keys fracture occur and carried out polymerization.
More than test shows to have synthesized subject polymer.
Embodiment 3
The present embodiment is used for illustrating cationic polymers provided by the invention and preparation method thereof.
(1) take 8.58 grams of butyl acrylates, 3.5 grams of cetyl trimethylammonium bromides, 78.7 grams of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and 203.6 grams of deionized waters and join in reactor, be stirred well to completely and dissolve.
(2) also pass into continuously nitrogen with air in nitrogen replacement reactor, be heated to 30 DEG C, add Sulfothiorine, the Potassium Persulphate and 2 of 0.7268 gram, 2 '-azo two (2-amidine propane) dihydrochloride (three's weight ratio is 1:2:1) starts reaction.After reaction 4h, temperature of reaction is increased to 50 DEG C, continues reaction 2h.
(3) cooling, by dehydrated alcohol precipitation, dry, obtain faint yellow solid P3.
The intrinsic viscosity of cationic polymers P3 is 314.85, and cationic degree is 0.0204mmol/g, and monomer conversion is more than 99.9%.
P3 is carried out
1h-NMR measures, and measurement result as shown in Figure 5, determines that the cationic polymeric molecule obtaining has the structure shown in formula (9), and 1.086ppm place is C-CH
3proton peak, 1.185-1.232ppm place is the methylene radical-CH being connected with methyl in hydrophobic grouping butyl acrylate
2-proton peak, 3.325ppm place is N-CH in cation group
3proton peak, 3.877ppm place is the methylene radical-CH being connected with N
2-proton peak, 4.535ppm place is-CH
2the proton peak of O-; Wherein, formula (9) and m and n only express the type of structural unit, and do not represent the mode of connection of structural unit.The concrete numerical value of m and n determined by charging capacity, and m is 1:0.177 with the ratio of n, and this ratio is the mol ratio of the represented structural unit of m and n.
P3 is carried out to IR spectrometry, measurement result as shown in Figure 6,953.6cm
-1place is quaternary ammonium salt N
+(CH
3)
3charateristic avsorption band; 1157.3cm
-1and 1268.4cm
-1for the δ absorption peak of C-O; 1488.6 is (CH
2)
2δ absorption peak; 1646.8cm
-1for the γ absorption peak of C=O; 1732.3cm
-1for the charateristic avsorption band of ester group.In addition, at 3200-3500cm
-1between have a series of sharp peaks, be and N
+the CH connecting
3cH in molecule
2γ absorption peak.In addition, at 1660-1680cm
-1(C=C) crest disappears, and shows that two keys fracture occur and carried out polymerization.
More than test shows to have synthesized subject polymer.
Test case 1
Using soluble in water respectively as reverse-phase emulsifier the SF-Y001 type cationic polyacrylamide HPAM of cationic polymers P2, DP1 and the production of four directions, Wen County material for water treatment company limited, be made into respectively the aqueous solution that concentration is 1.5 % by weight.
By above-mentioned reverse-phase emulsifier, (oleaginousness is 2000mg/L with the lonely three former oily waters in station respectively, not containing polymkeric substance) at 50 DEG C, react 0.5 hour, observe the water-oil interface after contact according to SY/T5797-93 method, then carry out oily water separation and measure oil removal rate, according to the oleaginousness in SY/T0530-93 method test gained water, and the outward appearance of observing water, result is as shown in table 1.
Table 1
Can find out from the data of table 1, under identical condition, compare with HPAM with DP1, cationic polymers P2 provided by the invention is to not containing the crude oil sewage degrease better effects if of polymkeric substance, and reverse-phase emulsifier P2 adds the concentration of sewage well below DP1 and HPAM.
Test case 2
Cationic polymers P1-P3, DP1, DP2 is soluble in water respectively using HPAM as reverse-phase emulsifier, be made into respectively the aqueous solution that concentration is 1 % by weight.
By the aqueous solution of above-mentioned reverse-phase emulsifier, (oleaginousness is 2000mg/L with the former oily water of Gudao oilfield at the lonely bigeminy station of containing polymkeric substance, lonely three stations, lonely tetrad station and the former oily water of Henan Oil Field respectively, be 100mg/L, the positive power II type polymkeric substance that polymkeric substance provides for oil field containing poly-amount).At 55 DEG C, react 1 hour, observe the water-oil interface after contact according to SY/T5797-93 method, then carry out oily water separation and measure oil removal rate, according to the oleaginousness in SY/T0530-93 method test gained water, and the outward appearance of observing water, result is as shown in table 2.Because DP1 is not obvious for the former oily water demulsification that contains polymkeric substance, therefore do not list in table.
Table 2
Can find out from the data of table 2, under identical condition, compare with HPAM with DP2, cationic polymers P1-P3 provided by the invention is to the crude oil sewage degrease better effects if that contains polymkeric substance.In addition, cationic polymers provided by the invention has good deoiling effect to different types of former oily water.
Test case 3
Using cationic polymers P1-P3 as reverse-phase emulsifier, be made into respectively the aqueous solution that concentration is 0.5 % by weight.
By the aqueous solution of above-mentioned reverse-phase emulsifier, (oleaginousness is 2000mg/L with the orphan's three former oily waters in station that contain polymkeric substance respectively, be 100mg/L containing poly-amount, the KYPAM-6A polymkeric substance that polymkeric substance provides for oil field), at 40 DEG C, react 1 hour, observe the water-oil interface after contact and measure oil removal rate according to SY/T5797-93 method, then carrying out oily water separation, according to the oleaginousness in SY/T0530-93 method test gained water, and the outward appearance of observing water, result is shown in table 3.
Table 3
Data by table 3 can find out, cationic polymers P1-P3 provided by the invention can obtain good deoiling effect under the condition of different concentration.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (15)
1. a cationic polymers, is characterized in that, this cationic polymers contains structural unit A and structural unit B, and wherein, described structural unit A is the structural unit shown in formula (1), and described structural unit B is the structural unit shown in formula (2); And taking the gross weight of structural unit in described cationic polymers as benchmark, the content of described structural unit A is 1.2-13.4 % by weight, and the content of described structural unit B is 86.6-98.8 % by weight;
formula (1),
formula (2),
Wherein, R
1for the alkyl of C1-C4; R
3, R
4and R
5be the alkyl of C1-C2 independently of one another; R
2and R
7be the alkyl of hydrogen or C1-C4 independently of one another; R
6for the alkylidene group of C1-C3; X
-for Cl
-, Br
-or I
-.
2. cationic polymers according to claim 1, wherein, the intrinsic viscosity of described cationic polymers is 167-402cm
3/ g, the cationic degree of described cationic polymers is 0.0151-0.0351mmol/g.
3. cationic polymers according to claim 1, wherein, R
1for normal-butyl, R
2for hydrogen, R
3, R
4and R
5be methyl independently of one another, R
6for ethylidene, R
7for methyl, X
-for Cl
-.
4. cationic polymers according to claim 1, wherein, taking the gross weight of structural unit in described cationic polymers as benchmark, the content of described structural unit A is 3.2-9.8 % by weight, the content of described structural unit B is 90.2-96.8 % by weight.
5. a preparation method for cationic polymers, this preparation method is included under emulsion polymerization condition, under initiator and tensio-active agent existence, makes a kind of monomer mixture in water, carry out polyreaction,
Wherein, described monomer mixture contains monomer D and monomer E, and described monomer D is the monomer shown in formula (3), and described monomer E is the monomer shown in formula (4); Taking the gross weight of monomer in described monomer mixture as benchmark, the content of described monomer D is 1.2-13.4 % by weight, and the content of described monomer E is 86.6-98.8 % by weight;
formula (3),
formula (4),
Wherein, R
1for the alkyl of C1-C4; R
3, R
4and R
5be the alkyl of C1-C2 independently of one another; R
2and R
7be the alkyl of hydrogen or C1-C4 independently of one another; R
6for the alkylidene group of C1-C3; X
-for Cl
-, Br
-or I
-.
6. preparation method according to claim 5, wherein, it is 167-402cm that described emulsion polymerization condition makes the intrinsic viscosity of gained cationic polymers after emulsion polymerization
3/ g, the cationic degree of described cationic polymers is 0.0151-0.0351mmol/g.
7. preparation method according to claim 5, wherein, R
1for normal-butyl, R
2for hydrogen, R
3, R
4and R
5be methyl independently of one another, R
6for ethylidene, R
7for methyl, X
-for Cl
-.
8. preparation method according to claim 5, wherein, the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture is 0.1-0.4:1, is preferably 0.2-0.3:1.
9. preparation method according to claim 5, wherein, taking the gross weight of described monomer mixture as benchmark, the consumption of described tensio-active agent is 1-5 % by weight, preferably, taking the gross weight of described monomer mixture as benchmark, the consumption of described tensio-active agent is 2-4 % by weight.
10. preparation method according to claim 9, wherein, described tensio-active agent is to be selected from one or more in cetyl trimethylammonium bromide, Sodium dodecylbenzene sulfonate, alkylphenol polyoxyethylene and sorbitol anhydride oleate.
11. preparation methods according to claim 5, wherein, taking the gross weight of described monomer mixture as benchmark, the consumption of described initiator is 0.1-1 % by weight, preferably, taking the gross weight of described monomer mixture as benchmark, the consumption of described initiator is 0.2-0.8 % by weight.
12. preparation methods according to claim 11, wherein, described initiator is inorganic peroxide series initiators, one or more in redox series initiators and water-soluble azo series initiators, preferably, described initiator is ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide-Sulfothiorine, hydrogen peroxide-iron protochloride, hydrogen peroxide-xitix, Potassium Persulphate-Sulfothiorine, 2, 2 '-azo-bis-iso-dimethyl, 2, 2 '-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride and 2, one or more in 2 '-azo two (2-amidine propane) dihydrochloride.
13. according to the preparation method described in any one in claim 5-12, and wherein, described emulsion polymerization carries out under rare gas element exists, and the condition of described emulsion polymerization comprises: temperature of reaction is 30-60 DEG C, and the reaction times is 0.5-7 hour.
The cationic polymers that preparation method in 14. claim 5-13 described in any one makes.
Cationic polymers in 15. claim 1-4 and 14 described in any one is as the application of reverse-phase emulsifier.
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| CN112584910B (en) * | 2018-08-29 | 2023-03-14 | 埃科莱布美国股份有限公司 | Multi-charged ionic compounds derived from polyamines, compositions thereof and their use as reverse demulsifiers for 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 |
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| 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 |
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| 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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