CN117126399A - Hyperbranched polymer and preparation method and application thereof - Google Patents
Hyperbranched polymer and preparation method and application thereof Download PDFInfo
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- CN117126399A CN117126399A CN202111585286.0A CN202111585286A CN117126399A CN 117126399 A CN117126399 A CN 117126399A CN 202111585286 A CN202111585286 A CN 202111585286A CN 117126399 A CN117126399 A CN 117126399A
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- 229920000587 hyperbranched polymer Polymers 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000002351 wastewater Substances 0.000 claims abstract description 42
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 25
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000003277 amino group Chemical group 0.000 claims abstract description 6
- 239000003921 oil Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- 239000010779 crude oil Substances 0.000 claims description 10
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000006837 decompression Effects 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- UXKQNCDDHDBAPD-UHFFFAOYSA-N 4-n,4-n-diphenylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 UXKQNCDDHDBAPD-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000010355 oscillation Effects 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 3
- 229920000962 poly(amidoamine) Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012795 verification Methods 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
- B01D17/047—Breaking emulsions with separation aids
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a hyperbranched polymer. The hyperbranched polymer takes N, N' -diphenyl-p-phenylenediamine as a center, methyl acrylate and ethylenediamine as branched chains, amine groups as end groups, and benzene rings are introduced at the center core, so that demulsification of oily wastewater can be realized under normal temperature conditions, the demulsifier has the characteristics of low consumption and high demulsification efficiency, and when the concentration of the demulsifier is 80mg/L, the oil removal rate of the oily wastewater under normal temperature conditions can reach 99.57 percent, and the demulsifier is applicable to oily wastewater with high salinity and has good application and popularization prospects. The invention also provides a preparation method and application of the hyperbranched polymer.
Description
Technical Field
The invention relates to the technical field of petroleum additives, in particular to a hyperbranched polymer and a preparation method and application thereof.
Background
With the increase of the difficulty of crude oil extraction, polymer flooding and water flooding technologies have become the main oil extraction means of various large oil fields. In this process, the presence of natural emulsifiers in crude oil can lead to the production of large amounts of oily wastewater. Because of the existence of natural interfacial active substances such as asphaltene and the like in the oil-water interface, a compact film is formed, so that the oily wastewater is highly stable, and petroleum transportation and subsequent refining processes are seriously affected. Therefore, the oil-water separation research of the oily wastewater has important significance. Chemical demulsification is achieved by adding a certain amount of chemical agent into emulsion. Demulsifiers can be categorized as cationic, anionic and nonionic. Compared with the ionic demulsifier, the nonionic demulsifier is not easily influenced by electrolyte because of having an amphiphilic structure. The chemical demulsifier is a key of chemical demulsification, and the traditional demulsifier has the problems of low demulsification efficiency, large demulsifier dosage, overlong demulsification time, unclear water phase and the like, is sensitive to environment and the like, and is easy to cause environmental pollution. Therefore, it is an urgent need to invent a rapid, efficient, environmentally friendly demulsifier.
The hyperbranched polymer is a highly branched nonionic demulsifier with geometric and topological structures, is a specially designed macromolecule, and has certain size, shape and reactivity. They are easily adsorbed to the oil-water interface to replace the original interfacial active substances, so that the emulsion breaking agent has great potential for emulsion breaking. Hyperbranched polymers exhibit better performance than linear polymeric surfactants due to increased branching, higher interfacial activity, better penetration, and more active end groups, with the end amino groups increasing with increasing algebra.
Studies have shown that the properties of amine-based dendrimers are significantly better than current commercial demulsifiers. Hyperbranched is a mature research direction, and patents and articles have reported many about similar structures of hyperbranched polymers. For example, chinese patent literature with publication number CN105601941a, publication date 2016, 5 and 25 discloses the use of a polyamidoamine hyperbranched polymer as a demulsifier, wherein the polyamidoamine hyperbranched polymer has ethylenediamine as the center and amine as the end group; the number average molecular weight distribution of the polyamidoamine hyperbranched polymer is 6000-12000. In the prior art represented by the above patent document, the oil removal rate was 87% when the oil-in-water emulsion in which diesel oil was an oil phase was demulsified at a concentration of 80mg/L and settled at 60℃for 30 minutes. The oil removal rate is still to be further increased.
However, the demulsifiers provided at present have good demulsification effect at higher temperature, and the demulsifiers have no effect on crude oil emulsion.
Disclosure of Invention
Aiming at overcoming the defects and shortcomings of the prior art, the invention provides a hyperbranched polymer which can demulsifie oily wastewater at normal temperature and has higher oil removal rate.
Meanwhile, the invention also provides a preparation method of the hyperbranched polymer.
Finally, the invention also provides an application of the hyperbranched polymer.
The invention is realized by adopting the following technical scheme:
the hyperbranched polymer is characterized in that the hyperbranched polymer takes N, N' -diphenyl-p-phenylenediamine as a center, methyl acrylate and ethylenediamine as branched chains and amine groups as end groups.
A method for preparing a hyperbranched polymer, comprising the steps of:
s1, dissolving N, N' -diphenyl-p-phenylenediamine in a solvent, adding methyl acrylate into the solvent, and reacting at normal temperature to obtain an intermediate I;
s2, adding methyl acrylate and ethylenediamine into the intermediate I, reacting at normal temperature, and removing a solvent and an unreacted monomer through reduced pressure distillation to obtain an intermediate II;
s3, under the condition of decompression, carrying out gradient heating reaction on the intermediate II from 60-120 ℃ for 8-10 h to obtain a target product.
Further, in the step S1, the molar ratio of N, N' -diphenyl-p-phenylenediamine to methyl acrylate is 1:2.
further, in the step S1, N' -diphenyl-p-phenylenediamine and methyl acrylate are stirred and reacted for 20 to 30 hours at normal temperature, and the stirring speed is 250 to 350r/min.
Further, the molar ratio of the ethylenediamine to the N, N' -diphenyl-p-phenylenediamine is 1:13 to 15.
Further, the molar ratio of the total addition amount of methyl acrylate to ethylenediamine is 1:0.8 to 1.2.
Further, in the step S2, the intermediate I, methyl acrylate and ethylenediamine are stirred and reacted for 20 to 30 hours at normal temperature, and the stirring speed is 250 to 350r/min.
Further, the step S3 specifically adopts the following method to raise the temperature in gradient: reacting at 60 ℃ for 1h, raising the temperature to 80 ℃ for 1h, raising the temperature to 100 ℃ for 2h, and raising the temperature to 120 ℃ for 2h.
The application of the hyperbranched polymer in demulsification is characterized in that the hyperbranched polymer is dispersed into oily wastewater for demulsification, the demulsification temperature is 25-50 ℃, and the demulsification time is 60-240 min.
Further, the addition amount of the hyperbranched polymer in the oily wastewater is 20-100 mg/l, and the oil phase in the oily wastewater is crude oil.
Compared with the prior art, the invention has the following beneficial effects:
1. the hyperbranched polymer provided by the invention takes N, N' -diphenyl-p-phenylenediamine as a center, methyl acrylate and ethylenediamine as branched chains and amine groups as end groups, and a rigid group benzene ring is introduced into the position of a center core, so that normal-temperature demulsification of crude oil emulsion can be realized, effective oil-water separation can be realized, and the hyperbranched polymer has the characteristics of small consumption and high demulsification efficiency, and the oil removal rate of 80mg/L of the demulsifier can reach 99.57% under normal-temperature conditions through the verification of experimental data of an embodiment part;
2. the synthetic method of the hyperbranched polymer is simple, the reaction condition is mild, and the reaction is safe;
3. compared with other existing hyperbranched polymers, the hyperbranched polymer provided by the invention can be used for demulsifying crude oil emulsion, and the existing hyperbranched polyamide-amine polymer can only be used for demulsifying diesel oil emulsion and cannot be used for demulsifying crude oil emulsion.
Drawings
The invention will be described in further detail with reference to the drawings and detailed description, wherein:
FIG. 1 is a synthetic schematic representation of hyperbranched polymers provided by the present invention;
FIG. 2 is a hyperbranched polymer obtained in example 10 of the invention 1 HNMR diagram;
FIG. 3 is an infrared spectrum of the hyperbranched polymer prepared in example 10 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The invention provides a hyperbranched polymer, which takes N, N' -diphenyl-p-phenylenediamine as a center, methyl acrylate and ethylenediamine as branched chains and amine groups as end groups, and has the following structure schematic (the hyperbranched structure is changeable and complex, and the structure shown in figure 1 is a theoretical molecular structure schematic)
Example 2
The invention provides a specific preparation method of a hyperbranched polymer, which comprises the following steps:
(1) Dissolving N, N' -diphenyl-p-phenylenediamine in a solvent, adding methyl acrylate into the solvent, and reacting at normal temperature to obtain an intermediate I;
(2) Adding methyl acrylate and ethylenediamine into the intermediate I, reacting at normal temperature, and removing the solvent and the monomer which is not completely reacted through reduced pressure distillation to obtain an intermediate II;
(3) And under the condition of decompression, the intermediate II is subjected to gradient heating reaction for 10 hours from 60-120 ℃ to obtain the target product.
Example 3
On the basis of example 2, as a preferred embodiment of the present invention, the molar ratio of N, N' -diphenyl-p-phenylenediamine to methyl acrylate in step (1) is 1:2. the solvent used in step (1) is methanol.
Example 4
On the basis of example 2, as a preferred embodiment of the present invention, N' -diphenyl-p-phenylenediamine and methyl acrylate in step (1) are reacted under stirring at a stirring speed of 350r/min for 30 hours at normal temperature. The molar ratio of ethylenediamine to N, N' -diphenyl-p-phenylenediamine is 1:13; the molar ratio of the total addition of methyl acrylate to ethylenediamine in step (1) and step (2) is 1:0.8;
example 5
Based on example 2, as a preferred embodiment of the present invention, the molar ratio of ethylenediamine to N, N' -diphenyl-p-phenylenediamine was 1:14. the molar ratio of the total addition of methyl acrylate to ethylenediamine is 1:1.
and (3) in the step (2), the intermediate I, methyl acrylate and ethylenediamine are stirred at normal temperature for reaction for 20 hours, and the stirring speed is 250r/min.
The step (3) adopts the following method to raise the temperature in a gradient way: reacting at 60 ℃ for 1h, raising the temperature to 80 ℃ for 1h, raising the temperature to 100 ℃ for 2h, and raising the temperature to 120 ℃ for 2h. The invention ensures the iterative reaction by gradient temperature rise, reduces the occurrence probability of side reaction in the reaction process and improves the purity of the target product.
According to the invention, the reaction is carried out by optimizing the addition amount of each reactant, the stirring speed in the reaction process and adopting a gradient heating mode, so that fewer byproducts are produced in the reaction process, the produced product result is more controllable, and the synthesis rate of the hyperbranched polymer is also improved.
Example 6
The embodiment provides application of the hyperbranched polymer in demulsification, wherein the hyperbranched polymer is dispersed into oily wastewater for demulsification, the demulsification temperature is 30 ℃, and the demulsification time is 120min.
Example 7
On the basis of example 6, as a preferred embodiment of the invention, the hyperbranched polymer was added to the oily wastewater in an amount of 50mg/l. The addition amount is less than 20mg/l, and the demulsification effect is poor; the addition amount is more than 100mg/l, the demulsification effect is basically unchanged, and the economic cost is increased.
Example 8
On the basis of example 6, as a preferred embodiment of the present invention, the oil phase in the oily wastewater was diesel oil.
Example 9
The embodiment provides application of the hyperbranched polymer in demulsification, wherein the hyperbranched polymer is dispersed into oily wastewater for demulsification, the demulsification temperature is 50 ℃, and the demulsification time is 240min.
The addition amount of the hyperbranched polymer in the oily wastewater is 100mg/l, and the oil phase in the oily wastewater is crude oil.
Example 10
The embodiment 10 of the invention provides a preparation method of a hyperbranched polymer, which comprises the following steps:
(1) 2.60g (0.01 mol) of N, N' -diphenyl-p-phenylenediamine is dissolved in 30ml of methanol, then 1.72g (0.02 mol) of methyl acrylate is added dropwise into the solution, and after the solution is uniformly mixed, the mixed solution is stirred at the normal temperature (25 ℃) and reacts for 24 hours at the speed of 300r/min, so as to obtain an intermediate I;
(2) 8.41g (0.14 mol) of ethylenediamine and 10.33g (0.12 mol) of methyl acrylate are added into the first intermediate prepared in the step (1), the reaction is continued at the normal temperature and the stirring speed of 300r/min for 24 hours, and then the solvent methanol and other unreacted monomers are removed by reduced pressure distillation to obtain a second intermediate;
(3) Under the condition of decompression, reacting the intermediate II at 60 ℃ for 1h, reacting at 80 ℃ for 1h, reacting at 100 ℃ for 2h, reacting at 120 ℃ for 2h, naturally cooling the obtained reaction product to normal temperature, and then drying in vacuum to obtain the black-purple target product.
The hyperbranched polymer prepared in this example was subjected to 1 HNMR analysis, the test results of which are shown in fig. 2, shows that each peak position coincides with the H position at a different position in the hyperbranched polymer structure, as can be seen from fig. 2. The hyperbranched polymer prepared in this example was subjected to infrared test analysis, the test results of which are shown in fig. 3, and the results in fig. 2 and 3 were combined to confirm that this example 10 successfully synthesized the hyperbranched polymer shown in the above-described structure.
The hyperbranched polymer prepared in example 10 was dispersed in an oily wastewater emulsion for demulsification, the oil removal rate was tested by emulsion demulsification experiments, and the oil removal rate was calculated by testing the light transmittance and the residual oil content of the aqueous phase before and after demulsification. The oily wastewater is prepared by the following method: 5g of Hainan crude oil and 495ml of distilled water are thoroughly mixed and then stirred at 11000 r.min -1 Stirring at high speed for 20min at the rotating speed to obtain oily wastewater containing 1% of oil.
Application example 1:
preparing a demulsifier aqueous solution with the concentration of 1600mg/L (1600 ppm) from the hyperbranched polymer, adding 1mL of the demulsifier aqueous solution into 19mL of oily wastewater, namely, the concentration of the hyperbranched polymer in the oily wastewater is 80mg/L (80 ppm), uniformly mixing the materials through rapid oscillation, and after standing for 60min at normal temperature, measuring the light transmittance of an aqueous phase to be 54.4%, wherein the demulsification efficiency is 98.46%; after standing for 120min at normal temperature, the light transmittance of the water phase is measured to be 68.4%, and the demulsification efficiency is measured to be 98.86%; and then, after standing for 240min at normal temperature, the light transmittance of the water phase is 85.7%, and the demulsification efficiency is 99.58%.
Application example 2:
preparing a demulsifier aqueous solution with the concentration of 1600mg/L (1600 ppm) from the hyperbranched polymer, adding 1mL of the demulsifier aqueous solution into 19mL of oily wastewater, namely, the concentration of the hyperbranched polymer in the oily wastewater is 80mg/L (80 ppm), uniformly mixing the materials through rapid oscillation, and then, after standing for 60min at 50 ℃, measuring the light transmittance of an aqueous phase to be 61.4%, wherein the demulsification efficiency is 98.65%; after standing for 120min, the light transmittance of the water phase is measured to be 74.5%, and the demulsification efficiency is measured to be 99.02%; after standing for 240min, the transmittance of the aqueous phase was measured to be 89.7%, and the demulsification efficiency was measured to be 99.74%.
Application example 3:
the hyperbranched polymer is prepared into a demulsifier aqueous solution with the concentration of 400mg/L (400 ppm), 1mL of the demulsifier aqueous solution is added into 19mL of oily wastewater, namely the concentration of the hyperbranched polymer in the oily wastewater is 20mg/L (20 ppm), the hyperbranched polymer and the oily wastewater are uniformly mixed through rapid oscillation, and after standing for 240min at normal temperature, the light transmittance of the water phase is measured to be 69.8%, and the demulsification efficiency is 98.88%.
Application example 4:
the hyperbranched polymer is prepared into a demulsifier aqueous solution with the concentration of 400mg/L (400 ppm), 1mL of the demulsifier aqueous solution is added into 19mL of oily wastewater, namely the concentration of the hyperbranched polymer in the oily wastewater is 20mg/L (20 ppm), the hyperbranched polymer and the oily wastewater are uniformly mixed through rapid oscillation, and after standing for 240min at 50 ℃, the light transmittance of the water phase is measured to be 75.4%, and the demulsification efficiency is 99.12%.
Application example 5:
preparing a demulsifier aqueous solution with the concentration of 1600mg/L (1600 ppm) from the hyperbranched polymer, adding 1mL of the demulsifier aqueous solution into 19mL of oily wastewater, namely, the concentration of the hyperbranched polymer in the oily wastewater is 80mg/L (80 ppm), adding 0.2g of NaCl solid into the oily wastewater, uniformly mixing the mixture through rapid oscillation, and after standing for 240min at normal temperature, determining that the light transmittance of an aqueous phase is 80.6%, and the demulsification efficiency is 99.56%.
Comparative example 1:
adding 1mL of EDA (ethylenediamine) demulsifier aqueous solution with the concentration of 400ppm and 1mL of hyperbranched polymer aqueous solution in the embodiment 10 of the invention with the concentration of 400ppm into 19mL of oily wastewater or diesel emulsion respectively, namely, the EDA demulsifier in the oily wastewater of two groups of experimental bottles and the concentration of the hyperbranched polymer are 20mg/L (20 ppm), respectively and uniformly mixing through rapid oscillation, and standing the two groups of experimental bottles at normal temperature for 30min to find that the EDA demulsifier has no effect on the oily wastewater but has an effect on the diesel emulsion; the hyperbranched polymer has an effect on oily wastewater, but has no effect on diesel emulsion.
As can be seen from application examples 1-4 and comparative example 1, the hyperbranched polymer demulsifier taking N, N' -diphenyl-p-phenylenediamine as the center provided by the invention has good demulsification efficiency on oily wastewater, and the demulsifier has good demulsification effect at normal temperature, and the oil removal rate of 80mg/L hyperbranched polymer on oily wastewater emulsion reaches 98.46% in 60 min. The results show that the hyperbranched polymer taking N, N' -diphenyl-p-phenylenediamine as the center is used for demulsifiers, oil-containing wastewater can be demulsified under normal temperature, the consumption of the hyperbranched polymer is small, and the demulsification efficiency is high. Application example 5 shows that the hyperbranched demulsifier has better salt tolerance.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (10)
1. The hyperbranched polymer is characterized in that the hyperbranched polymer takes N, N' -diphenyl-p-phenylenediamine as a center, methyl acrylate and ethylenediamine as branched chains and amine groups as end groups.
2. The method of preparing the hyperbranched polymer according to claim 1, comprising the steps of:
s1, dissolving N, N' -diphenyl-p-phenylenediamine in a solvent, adding methyl acrylate into the solvent, and reacting at normal temperature to obtain an intermediate I;
s2, adding methyl acrylate and ethylenediamine into the intermediate I, reacting at normal temperature, and removing a solvent and an unreacted monomer through reduced pressure distillation to obtain an intermediate II;
s3, under the condition of decompression, carrying out gradient heating reaction on the intermediate II from 60-120 ℃ for 8-10 h to obtain a target product.
3. The method for preparing hyperbranched polymer according to claim 2, wherein the molar ratio of N, N' -diphenyl-p-phenylenediamine to methyl acrylate in the step S1 is 1:2.
4. the method for preparing hyperbranched polymer according to claim 2, wherein in the step S1, N' -diphenyl-p-phenylenediamine and methyl acrylate are stirred and reacted for 20 to 30 hours at normal temperature, and the stirring speed is 250 to 350r/min.
5. The method of preparing hyperbranched polymer according to claim 2 wherein the molar ratio of ethylenediamine to N, N' -diphenylp-phenylenediamine is 1:13 to 15.
6. The method for preparing hyperbranched polymer according to claim 2, wherein the molar ratio of the total amount of methyl acrylate added to ethylenediamine is 1:0.8 to 1.2.
7. The method for preparing hyperbranched polymer according to claim 2, wherein the intermediate I, methyl acrylate and ethylenediamine in the step S2 are stirred at room temperature for reaction for 20-30 hours, and the stirring speed is 250-350 r/min.
8. The method for preparing hyperbranched polymer according to claim 2, wherein the step S3 specifically adopts the following method to raise the temperature in gradient: reacting at 60 ℃ for 1h, raising the temperature to 80 ℃ for 1h, raising the temperature to 100 ℃ for 2h, and raising the temperature to 120 ℃ for 2h.
9. The use of the hyperbranched polymer according to claim 1 in demulsification, wherein the hyperbranched polymer is dispersed in oily wastewater for demulsification at a temperature of 25 to 50 ℃ for a time of 60 to 240 minutes.
10. The use of the hyperbranched polymer according to claim 9 in demulsification, wherein the hyperbranched polymer is added to the oily wastewater in an amount of 20-100 mg/l, and the oil phase in the oily wastewater is crude oil.
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