CN117343319A - Cationic polyamide-amine flocculant containing degradable imine bond and preparation method and application thereof - Google Patents
Cationic polyamide-amine flocculant containing degradable imine bond and preparation method and application thereof Download PDFInfo
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- 125000002091 cationic group Chemical group 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229920000768 polyamine Polymers 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- -1 alkyl dimethyl ethoxy ammonium bromide Chemical compound 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- XFHTVCMRNSBQCF-UHFFFAOYSA-N 4-(2-bromoethoxy)benzaldehyde Chemical compound BrCCOC1=CC=C(C=O)C=C1 XFHTVCMRNSBQCF-UHFFFAOYSA-N 0.000 claims description 8
- 238000005915 ammonolysis reaction Methods 0.000 claims description 8
- 238000007259 addition reaction Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims description 3
- QMHNQZGXPNCMCO-UHFFFAOYSA-N n,n-dimethylhexan-1-amine Chemical compound CCCCCCN(C)C QMHNQZGXPNCMCO-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000005189 flocculation Methods 0.000 abstract description 9
- 230000016615 flocculation Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 239000010802 sludge Substances 0.000 abstract description 3
- 238000010979 pH adjustment Methods 0.000 abstract 1
- 239000008394 flocculating agent Substances 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000011282 treatment Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CHACAISOHLFJMC-UHFFFAOYSA-N [Br-].C[NH+](OCC)C Chemical compound [Br-].C[NH+](OCC)C CHACAISOHLFJMC-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229920006317 cationic polymer Polymers 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- BUAXCDYBNXEWEB-UHFFFAOYSA-N 2-(chloromethyl)oxirane;n-methylmethanamine Chemical compound CNC.ClCC1CO1 BUAXCDYBNXEWEB-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- QISASCVEEIYAIO-UHFFFAOYSA-M [Br-].C(CCCCCCCCCCC)[N+](C)(C)OCC Chemical compound [Br-].C(CCCCCCCCCCC)[N+](C)(C)OCC QISASCVEEIYAIO-UHFFFAOYSA-M 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- YWWNNLPSZSEZNZ-UHFFFAOYSA-N n,n-dimethyldecan-1-amine Chemical group CCCCCCCCCCN(C)C YWWNNLPSZSEZNZ-UHFFFAOYSA-N 0.000 description 1
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical group CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 description 1
- LHYSDIRSUNHTMJ-UHFFFAOYSA-N o-ethylhydroxylamine;hydrobromide Chemical compound Br.CCON LHYSDIRSUNHTMJ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
- C08G69/50—Polymers modified by chemical after-treatment with aldehydes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a cationic polyamide-amine flocculant containing degradable imine bonds, a preparation method and application thereof. The cationic polyamide-amine flocculant containing degradable imine bonds has good flocculation oil removal effect on oilfield produced water, and the flocs can avoid forming oil sludge through pH adjustment.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a treatment technology of oilfield produced water, and specifically relates to a cationized polyamide-amine flocculant containing degradable imine bonds, and a preparation method and application thereof.
Background
The oil field produces a large amount of produced water during the production process, which contains a large amount of oil droplets, and the oil content needs to be reduced before reinjection or drainage can be performed. Flocculation is one of the most common treatments of oilfield produced water, and it adds a flocculant to the produced water to effect oil-water separation. The most commonly used organic flocculating agents in the current oil field are cationic polymers, mainly comprising dimethylamine-epichlorohydrin polycondensate, dimethyldiallylammonium chloride homopolymer, copolymer of acrylamide and cationic monomers (including methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride and the like), and cationized polyamide-amine and the like. The cationic polymer flocculant has the advantages of small addition amount, high oil removal speed, high oil removal rate and the like when treating oilfield produced water, but generally has certain viscosity in the treatment process, is easy to adhere to the wall of a processor, is not easy to desorb, and can form oil sludge when accumulating in daily life, so that the normal produced water treatment is affected. Therefore, the preparation of the cationic polymer flocculant which has good flocculation oil removal effect and is easy to treat after the flocs adhere to the wall surface has important practical significance. In view of this, the present invention proposes the synthesis of a cationized polyamide-amine flocculant containing degradable imine bonds, which flocs are easily desorbed from the wall surface by adjusting the pH value compared to conventional cationic polymer flocculants.
Disclosure of Invention
In view of the above, the present invention provides a cationized polyamide-amine flocculant containing a degradable imine bond and a method for producing the same, which are provided in the following embodiments.
A method for preparing a cationized polyamide-amine flocculant containing a degradable imine bond, comprising the steps of:
s1, preparing 4- (alkyl dimethyl ethoxy ammonium bromide) benzaldehyde by utilizing 4- (2-bromoethoxy) benzaldehyde to react with N, N-dimethyl alkylamine;
as a specific embodiment of the present invention, 4- (alkyldimethylethoxy ammonium bromide) benzaldehyde can be prepared as follows: dissolving 4- (2-bromoethoxy) benzaldehyde in a solvent to form a 4- (2-bromoethoxy) benzaldehyde solution, adding N, N-dimethyl alkylamine into the 4- (2-bromoethoxy) benzaldehyde solution under the condition of nitrogen protection and stirring, heating to 70-90 ℃, and reacting for 24-48 hours; removing the solvent by rotary evaporation, and recrystallizing by acetone to obtain a purified crude product; the solvent may be methanol or ethanol.
S2, preparing polyamide-amine by utilizing iterative reaction of ethylenediamine or polyamine and methyl acrylate;
dissolving ethylenediamine or polyamine in methanol or ethanol, dropwise adding methyl acrylate into the ethylenediamine or polyamine solution at 40 ℃ for an addition reaction, wherein the reaction time can be selected according to the needs, such as 24-48h; then adding ethylenediamine or polyamine into the reaction solution to carry out ammonolysis reaction, wherein the reaction time is selected according to the needs, such as 12-24 hours, finally adding a mixed solvent of ethanol and water, carrying out step-wise heating reaction at 60 ℃,80 ℃,100 ℃ and 120 ℃, and the reaction time of each temperature stage is selected according to the needs, such as 1-2 hours at 60 ℃, 1-2 hours at 80 ℃, 2-4 hours at 100 ℃ and 2-4 hours at 120 ℃; after the reaction, a polyamide-amine is obtained.
S3, mixing the 4- (alkyl dimethyl ethoxy ammonium bromide) benzaldehyde prepared in the step S1 with the polyamide-amine prepared in the step S2, and reacting for 24 hours at room temperature to obtain the cationic polyamide-amine flocculant containing degradable imine bonds.
The specific reaction mechanism is shown in figure 1.
In a specific embodiment of the present invention, the N, N-dimethyl alkylamine in step S1 is any one of N, N-dimethyl hexylamine, N-dimethyl N-octylamine, N-dimethyl N-decylamine, and N, N-dimethyl dodecylamine.
In a specific embodiment of the present invention, the polyamine in the step S2 is any one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
As a specific embodiment of the invention, the molar ratio of the amino active hydrogen to the acrylic ester in the step S2 addition reaction is 1:1, and the molar ratio of the ester group to the polyamine in the ammonolysis reaction is 1:1.
as a specific embodiment of the present invention, the molar ratio of 4- (alkyl dimethyl ethoxy ammonium bromide) benzaldehyde to primary amine in polyamide-amine in the step S3 is 1:1.
It is an object of the present invention to provide a cationized polyamide-amine flocculant containing degradable imine bonds prepared using the above scheme.
It is another object of the present invention to provide a use of the above-described cationic polyamide-amine flocculant containing a degradable imine bond, adding the cationic polyamide-amine flocculant containing a degradable imine bond to oilfield produced water having a first pH, stirring thoroughly to flocculate the water, and then adding a pH adjustor to reduce the pH of the oilfield produced water to a second pH, wherein the flocculated product (sludge) loses viscosity at the second pH.
As a specific embodiment of the invention, the first pH value is more than 5, and the second pH value is less than 5.
The invention has the advantages that:
the cationic polyamide-amine flocculant containing degradable imine bonds, which is prepared by the invention, can control the generation of flocs and lose the viscosity of the generated flocs by adjusting the pH value, and compared with the conventional cationic polymer flocculant, the flocs are easier to desorb from the wall surface.
Drawings
FIG. 1 is an infrared spectrum of a cationized polyamide-amine flocculant of degradable imine bonds prepared in example 1.
Detailed Description
The invention is further illustrated by, but not limited to, the following specific examples. The raw materials used in the examples are all conventional raw materials and are commercially available; the methods are prior art unless specified otherwise.
Example 1
Synthesis of S0, 4- (2-bromoethoxy) benzaldehyde
45.3g of potassium carbonate is weighed into a 1000mL three-necked flask, 300mL of acetonitrile and 71mL of 1, 2-dibromoethane are sequentially added under stirring, and the mixture is heated to 85 ℃ under the protection of nitrogen; 20g of 4-p-hydroxybenzaldehyde dissolved in 200mL of acetonitrile is dripped into a three-necked flask by using a constant pressure separating funnel, and the reaction is stopped after the dripping is finished for 24 hours; standing for 12h, filtering to obtain filtrate, and steaming to remove viscous liquid after acetonitrile; adding the viscous liquid into normal hexane, precipitating and filtering to obtain 4- (2-bromoethoxy) benzaldehyde;
synthesis of S1, 4- (n-hexane-based dimethyl ethoxy ammonium bromide) benzaldehyde
4.6g of 4- (2-bromoethoxy) benzaldehyde is weighed into a 500mL three-necked flask, 250mL of ethanol is added, and the mixture is heated to 50 ℃ under the protection of nitrogen; adding 5.2g of N, N-dimethyl-n-hexylamine under stirring, heating to 80 ℃ for reacting for 48 hours, and stopping the reaction; removing ethanol by rotary evaporation to obtain a crude product, and recrystallizing the crude product by acetone to obtain 4- (n-hexane-based dimethyl ethoxy ammonium bromide) benzaldehyde.
S2, synthesis of ethylenediamine-nucleated polyamide-amine
6.01g (0.1 mol) of ethylenediamine is weighed and dissolved in 10g of methanol, 34.44g (0.4 mol) of methyl acrylate is added dropwise at 40 ℃ and stirred for reaction for 24 hours; 24.04g (0.4 mol) of ethylenediamine is continuously added dropwise for reaction for 12 hours, then a mixed solvent (ethanol: water=1:1) is added so that the concentration of the reactant is 50%, the mixture is reacted for 1 hour at 60 ℃, for 1 hour at 80 ℃, for 2 hours at 100 ℃ and for 2 hours at 120 ℃ to obtain the ethylenediamine-nucleated polyamide-amine.
S3, synthesis of cationic polyamide-amine flocculant containing degradable imine bond
20g of the polyamide-amine solution obtained in the step S2 and 11.42g of 4- (n-hexane-based dimethyl ethoxy ammonium bromide) benzaldehyde are weighed into a three-necked flask, water is added until the concentration of the reactant is 25%, and the mixture is stirred and reacted for 24 hours at room temperature to obtain the cationized polyamide-amine flocculant 1 containing degradable imine bonds.
Example 2
The basic embodiment of this example is the same as that of example 1, except that in step S1 of this example, N-dimethylalkylamine is N, N-dimethyln-octylamine and in step S3, the addition amount of 4- (N-octyldimethylethoxy ammonium bromide) benzaldehyde is 13.9g, and finally a cationized polyamide-amine flocculant 2 having a degradable imine bond is obtained.
Example 3
The basic embodiment of this example is the same as that of example 1 except that N, N-dimethylalkylamine is N, N-dimethyln-decylamine in step S1 of this example and the addition amount of 4- (N-decane-dimethylethoxy ammonium bromide) benzaldehyde in step S3 is 16.4g, and finally a cationized polyamide-amine flocculant 3 having a degradable imine bond is obtained.
Example 4
The basic embodiment of this example is the same as that of example 1, except that N, N-dimethylalkylamine is N, N-dimethyldodecylamine in the step S1 of this example, and the addition amount of 4- (N-dodecyldimethylethoxyammonium bromide) benzaldehyde in the step S3 is 18.9g, to finally obtain a cationized polyamide-amine flocculant 4 having a degradable imine bond.
Example 5
The basic embodiment of this example is the same as that of example 1 except that in step S2 of this example, the polyamine is diethylenetriamine, the amount of initially dissolved in methanol is 10.3g (0.1 mol), the amount of acrylic acid ester added in the case of addition reaction is 0.5mol, the amount of diethylenetriamine added in the case of ammonolysis reaction is 0.5mol, and the amount of 4- (n-hexane-based dimethylethoxy ammonium bromide) benzaldehyde added in step S3 is 11.7g, and finally a cationized polyamide-amine flocculant 5 containing a degradable imine bond is obtained.
Example 6
The basic embodiment of this example is the same as that of example 1 except that in step S2 of this example, the polyamine is triethylenetetramine, the amount of the initially dissolved in methanol is 14.6g (0.1 mol), the amount of the acrylic acid ester added in the addition reaction is 0.6mol, the amount of triethylenetetramine added in the ammonolysis reaction is 0.6mol, and the amount of 4- (n-hexane-based dimethyl ethoxy ammonium bromide) benzaldehyde added in step S3 is 11.5g, thereby obtaining the cationic polyamide-amine flocculant 6 having a degradable imine bond.
Example 7
The basic embodiment of this example is the same as that of example 1 except that in step S2 of this example, the polyamine is tetraethylenepentamine, the mass of the initial solution in methanol is 18.9g (0.1 mol), the addition amount of the acrylic acid ester in the addition reaction is 0.7mol, the addition amount of the tetraethylenepentamine in the ammonolysis reaction is 0.7mol, and the addition amount of 4- (n-hexane-based dimethyl ethoxy ammonium bromide) benzaldehyde in step S3 is 11.7g, and finally the cationic polyamide-amine flocculant 7 containing a degradable imine bond is obtained.
Comparative example 1
The implementation of this example only proceeds with step S2 in example 1, and does not proceed with steps S0, S1 and S3.
Comparative example 2
The implementation of this example only proceeds with step S2 in example 5, and does not proceed with steps S0, S1 and S3.
Comparative example 3
The implementation of this example only proceeds with step S2 in example 6, and does not proceed with steps S0, S1 and S3.
Comparative example 4
The implementation of this example only proceeds with step S2 in example 7, and does not proceed with steps S0, S1 and S3.
To further illustrate the technical effects of the present invention, the present invention also provides relevant characterization and testing of the above examples and comparative examples in practical applications.
1. Infrared spectrum
Referring to fig. 1, fig. 1 is an infrared spectrum of a cationized polyamide-amine flocculant of degradable imine bond prepared in example 1.
In the figure, a peak of methylene is located at about 2943cm-1, a peak corresponding to C=O is located at 1680cm-1, a peak corresponding to imine is located at 1602cm-1, stretching vibration of C-N is located at 1158cm-1, stretching vibration of C-O-C is located at 1116cm-1, and a characteristic peak corresponding to benzene ring is located at 946 cm-1.
2. Effect of 4- (Alkyldimethyl ethoxy ammonium bromide) benzaldehyde species on flocculant Performance and floc viscosity
The oil removal rate and floc viscosity of the flocculant are evaluated by adopting an indoor self-made detachable inclined plate oil remover according to the experimental method described in section 2.1.3 of the preparation of a ternary surface active flocculant and research on flocculation mechanism of the Shuoshi (Xu Zipei, university of southwest petroleum, 2016) by taking the produced water of a certain oil field of Bohai sea as a treatment object (oil content 2200mg/L, pH > 5). As can be seen from Table 1, the oil removal rates of the flocculants of examples 1-4 of the present invention were all higher than that of comparative example 1, because the flocculants of examples 1-4 introduced quaternary ammonium cations and hydrophobic alkyl chains based on the flocculants of comparative example 1. The quaternary ammonium salt positive ions can further destroy the double electric layers on the surfaces of oil drops in the produced water, the stability of the oil drops is reduced, and a plurality of hydrophobic alkyl chains can adsorb and bridge between different oil drops to promote flocculation and oil removal. The floccules generated by the flocculating agents have viscosity and can adhere to the surface of the sloping plate, so that the sloping plate is increased in weight, and the higher the oil removal rate is, the larger the sloping plate is increased in weight. However, it was found that, for the 4 flocculants of examples 1 to 4, most of them lost viscosity and separated from the surface of the swash plate after soaking the swash plate in acidic water having ph=4 (60 ℃ for 20 min), resulting in a significant reduction in swash plate weight gain, whereas the flocculant of comparative example 1 did not. This is because the flocculants of examples 1 to 4 contain imine bonds, which are broken under acidic conditions, resulting in the flocculants of examples 1 to 4 losing quaternary ammonium salts and hydrophobic alkyl chains, and further resulting in a decrease in the viscosity of the flocs and easy removal from the swash plate surface.
TABLE 1 oil removal Rate and flocculation Properties of different flocculants for treating oilfield produced water
3. Effect of Polyamide-amine species on flocculant Properties and floc viscosity
The oil removal rate and floc viscosity of the flocculant are evaluated by adopting an indoor self-made detachable inclined plate oil remover according to the experimental method described in section 2.1.3 of the preparation of a ternary surface active flocculant and research on flocculation mechanism of the Shuoshi (Xu Zipei, university of southwest petroleum, 2016) by taking the produced water of a certain oil field of Bohai sea as a treatment object (oil content 2200mg/L, pH > 5). As can be seen from Table 2, the oil removal rates of the example flocculants were higher than those of the comparative example flocculants, and the results are the same as Table 1. As the degree of polyamide-amine branching increases, the oil removal rate of the example flocculants increases due to the increased degree of branching and the ability of the flocculants to flocculate to bridge. After soaking the swash plate in acidic water with ph=4 (60 ℃,20 min) after flocculation experiments, it was found that the floccules for the example floccules lost viscosity and were separated from the swash plate surface, resulting in a substantial reduction in swash plate weight gain, while the comparative floccules did not, which results are also consistent with table 1.
TABLE 2 oil removal and flocculation Properties for treatment of oilfield produced water with different flocculants
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the technical scope of the present invention disclosed in the embodiments of the present invention should be covered by the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (9)
1. A method for preparing a cationized polyamide-amine flocculant containing a degradable imine bond, comprising the steps of:
s1, preparing 4- (alkyl dimethyl ethoxy ammonium bromide) benzaldehyde by utilizing 4- (2-bromoethoxy) benzaldehyde to react with N, N-dimethyl alkylamine;
s2, preparing polyamide-amine by utilizing iterative reaction of polyamine or ethylenediamine and methyl acrylate;
s3, mixing the 4- (alkyl dimethyl ethoxy ammonium bromide) benzaldehyde prepared in the step S1 with the polyamide-amine prepared in the step S2, and reacting for 24 hours at room temperature to obtain the cationic polyamide-amine flocculant containing degradable imine bonds.
2. The method for preparing a cationized polyamide-amine flocculant containing a degradable imine bond according to claim 1, characterized in that: the N, N-dimethyl alkylamine in the step S1 is N, N-dimethyl hexylamine, N-dimethyl N-octylamine, N-dimethyl N-decylamine or N, N-dimethyl dodecylamine.
3. The method for preparing a cationized polyamide-amine flocculant containing a degradable imine bond according to claim 1, characterized in that: the polyamine in the step S2 is diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
4. The method for preparing a cationized polyamide-amine flocculant containing a degradable imine bond according to claim 1, characterized in that: step S2 includes the steps of:
s21, dissolving ethylenediamine or polyamine in methanol or ethanol, and dropwise adding methyl acrylate into the polyamine solution at 40 ℃ for addition reaction;
s22, adding ethylenediamine or polyamine into the addition product of the S21 to carry out ammonolysis reaction;
s23, adding a mixed solvent of ethanol and water into the ammonolysis product of S22, and sequentially carrying out constant-temperature reaction at 60 ℃,80 ℃,100 ℃ and 120 ℃ to obtain the polyamide-amine after the reaction is finished.
5. The method for preparing a cationized polyamide-amine flocculant containing a degradable imine bond according to claim 5, characterized in that: in the step S2, the molar ratio of the amino active hydrogen to the acrylic ester is 1:1, and the molar ratio of the ester group to the polyamine is 1 during the ammonolysis reaction: 1.
6. the method for preparing a cationized polyamide-amine flocculant containing a degradable imine bond according to claim 5, characterized in that: the molar ratio of 4- (alkyl dimethyl ethoxy ammonium bromide) benzaldehyde to primary amine in polyamide-amine in step S3 was 1:1.
7. A cationized polyamide-amine flocculant comprising a degradable imine bond prepared by the method of any one of claims 1-6.
8. Use of a cationized polyamide-amine flocculant containing a degradable imine bond according to claim 7, wherein: adding a polyamide-amine flocculant into oilfield produced water with a first pH value, and fully stirring to flocculate the oilfield produced water; and adding a pH regulator to reduce the pH value of the oilfield produced water to a second pH value so as to lose the viscosity of the flocculated product.
9. Use of a cationized polyamide-amine flocculant containing a degradable imine bond according to claim 8, wherein: the first PH value is greater than 5, and the second PH value is less than 5.
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