CN113831480B - Bio-based amphoteric polymer and preparation method and application thereof - Google Patents
Bio-based amphoteric polymer and preparation method and application thereof Download PDFInfo
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- CN113831480B CN113831480B CN202010582283.0A CN202010582283A CN113831480B CN 113831480 B CN113831480 B CN 113831480B CN 202010582283 A CN202010582283 A CN 202010582283A CN 113831480 B CN113831480 B CN 113831480B
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- ammonium chloride
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- itaconic acid
- trimethyl ammonium
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- 229920000642 polymer Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 36
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 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 claims abstract description 31
- 239000010865 sewage Substances 0.000 claims abstract description 23
- 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 claims abstract description 23
- 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 claims abstract description 22
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 20
- 239000010779 crude oil Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 29
- 239000003999 initiator Substances 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 230000000977 initiatory effect Effects 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- 239000012990 dithiocarbamate Substances 0.000 claims description 2
- 150000004659 dithiocarbamates Chemical class 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003208 petroleum Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- -1 sulfonic groups Chemical group 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- 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
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
Abstract
The invention relates to a bio-based amphoteric polymer and a preparation method and application thereof. The bio-based amphoteric polymer is polymerized by lignosulfonate, itaconic acid and at least one substance selected from methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride and dimethyl diallyl ammonium chloride. The polymer flocculant containing the amphoteric polymer has the advantages of environmental protection and good demulsification and deoiling effects on crude oil sewage. Meanwhile, the amphoteric polymers with different proportions can be selected according to different crude oil sewage to prepare corresponding polymeric flocculant, so that the broad-spectrum performance of the flocculant is improved. In addition, both lignosulfonate and itaconic acid are important bio-based chemical raw materials. The wide application of the bio-based raw material can effectively solve the problems caused by the exhaustion of petroleum resources and environmental pollution, and has very important significance.
Description
Technical Field
The invention belongs to the field of sewage treatment, and particularly relates to a bio-based amphoteric polymer and a preparation method and application thereof.
Background
The flocculant plays an important role in solid-liquid separation in the treatment process of industrial wastewater and domestic sewage, and has excellent performance, and the ideal treatment effect can be obtained by controlling proper dosage and a mixing method and adding a subsequent reasonable precipitation filtration process. Therefore, the development of a novel and efficient flocculant is a target of attention of water treatment workers at home and abroad. The most widely used organic polymeric flocculant is polyacrylamide at present, but the monomer of the organic polymeric flocculant has three-induced toxicity and causes secondary pollution to water, so that the search for efficient and environment-friendly flocculant becomes a hot spot of current research.
The water-soluble amphoteric polymer is a water-soluble polymer which contains positive and negative charge groups on a polymer chain unit, and has unique performance compared with a water-soluble anion or cation polymer containing only one charge. For example, the amphoteric polymer used as the flocculant has the application characteristics of being applicable to a pollution system with coexisting anions and cations, wide pH value application range, good salt resistance and the like, and is a research hot spot at home and abroad.
The lignosulfonate is one of main byproducts in the paper industry, and contains groups such as phenolic hydroxyl groups, alcoholic hydroxyl groups, sulfonic groups, carboxyl groups and the like in the structure, so that the lignosulfonate has good water solubility, adsorptivity, amphipathy and the like, and is widely applied to the fields of water treatment agents, ion exchangers, water reducers and the like. Lignosulfonate is a natural polymer material, but has low average relative molecular mass and few active adsorption points, so that the application of lignosulfonate in flocculant is limited, and some chemical modification is needed to improve the application performance of lignosulfonate.
Itaconic acid is a completely biodegradable biomass chemical material with great development potential, can be prepared by fermenting corn or potato starch and the like, and is a biomass chemical material which is truly natural and belongs to nature. Itaconic acid is an unsaturated binary organic acid, has an active double bond and two carboxyl groups in the molecule, is a bio-based monomer with higher polymerization activity, and can perform a series of reactions such as esterification, polymerization, addition and the like.
Dimethyl diallyl ammonium chloride is a monomer with an unsaturated carbon-carbon double bond group and a quaternary ammonium salt group, and the polymer is the only synthesized cationic quaternary ammonium salt polyelectrolyte approved by the public health agency (U.S. P.H.S.) for drinking water purification treatment, and is widely applied to the fields of water treatment, petroleum drilling, papermaking and the like.
At present, a green and environment-friendly flocculant using a biological base as a raw material is needed to be provided.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the bio-based amphoteric polymer, and the flocculant containing the bio-based amphoteric polymer has the advantages of environmental protection and good demulsification and deoiling effects on crude oil sewage.
To this end, a first aspect of the present invention provides a bio-based amphoteric polymer polymerized from lignin sulfonate, itaconic acid and at least one selected from methacryloxyethyl trimethyl ammonium chloride (DMC), acryloxyethyl trimethyl ammonium chloride (DAC) and dimethyl diallyl ammonium chloride (DMDAAC).
In some embodiments of the invention, the lignosulfonate is 2.7 to 58.8 parts by weight; the weight part of the itaconic acid is 5.4 to 62.5 parts; the weight part of the methacryloyloxyethyl trimethyl ammonium chloride is more than or equal to 0, the weight part of the acryloyloxyethyl trimethyl ammonium chloride is more than or equal to 0, the weight part of the dimethyl diallyl ammonium chloride is more than or equal to 0, and the sum of the weight parts of the methacryloyloxyethyl trimethyl ammonium chloride, the acryloyloxyethyl trimethyl ammonium chloride and the dimethyl diallyl ammonium chloride is 20-89.3.
In a second aspect, the present invention provides a process for the preparation of a polymer according to the first aspect of the invention, comprising the steps of:
s1, mixing lignosulfonate, an initiator 1 and a solvent, and then adding at least one of methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride and dimethyl diallyl ammonium chloride and an initiator 2 to start reaction;
s2, mixing itaconic acid solution with the reaction system of the step S1, and reacting to obtain a product solution;
s3, cooling the product solution obtained in the step S2, and then precipitating and drying to obtain a brown solid of the polymer; or cooling the product solution obtained in the step S2 to obtain the aqueous solution of the polymer.
In some embodiments of the present invention, the lignosulfonate is 2.7 to 58.8 parts by weight; the weight part of the itaconic acid is 5.4 to 62.5 parts; the weight part of the methacryloxyethyl trimethyl ammonium chloride (DMC) is more than or equal to 0, the weight part of the acryloxyethyl trimethyl ammonium chloride (DAC) is more than or equal to 0, the weight part of the dimethyl diallyl ammonium chloride (DMDAAC) is more than or equal to 0, and the weight part of DMC+DAC+DMDAAC is 20-89.3.
The lignosulfonate is not particularly limited in the present invention, and for example, the lignosulfonate may be sodium lignosulfonate or the like.
In some embodiments of the invention, the initiator 1 and initiator 2 are each independently selected from CaCl 2 -H 2 O 2 Initiation system, fe 2+ -H 2 O 2 One or more of an initiating system and a peroxide initiating system.
In some preferred embodiments of the invention, the initiator 1 and initiator 2 are each independently selected from CaCl 2 -H 2 O 2 Initiation system, ferrous sulfate-H 2 O 2 One or more of an initiating system, potassium persulfate and ammonium persulfate.
In a further preferred embodiment of the invention, the initiator 1 is selected from CaCl 2 -H 2 O 2 Initiation system and/or ferrous sulfate-H 2 O 2 And an initiating system, wherein the initiator 2 is selected from potassium persulfate and/or ammonium persulfate.
In other embodiments of the invention, the initiator 1 is present in an amount of 0 to 30 parts by weight and is other than 0; and/or the initiator 2 is 0 to 1.5 parts by weight and not 0.
In some embodiments of the invention, in step S1, the solvent is deionized water; preferably, the solvent is used in step S1 in an amount such that the raw material content in the solution is 10wt% to 50wt%. In the invention, the raw materials consist of lignosulfonate, itaconic acid and at least one substance selected from methacryloxyethyl trimethyl ammonium chloride (DMC), acryloxyethyl trimethyl ammonium chloride (DAC) and dimethyl diallyl ammonium chloride (DMDAAC).
In some embodiments of the invention, in step S2, the pH of the itaconic acid solution is between 6 and 7.
In other embodiments of the present invention, in step S2, the itaconic acid solution is added dropwise to the reaction system of step S1 over 20 to 60 minutes.
In some embodiments of the invention, in step S2, the time of the reaction is at least 6 hours.
In other embodiments of the present invention, in step S3, precipitation is performed using absolute ethanol or acetone.
In some preferred embodiments of the invention, the method may comprise the steps of:
t1, adding lignosulfonate, an initiator 1 and a solvent into a reactor;
t2, replacing air in the reactor by inert gas, continuously introducing the inert gas, heating the reactor, and then adding at least one of methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride and dimethyl diallyl ammonium chloride and an initiator 2 to start reaction;
t3, dissolving itaconic acid with a solvent, and then adjusting the pH value of the solution to obtain an itaconic acid solution; then adding the itaconic acid solution into a reaction system of the step T2, and continuing to react to obtain a product solution;
t4, cooling the product solution obtained in the step T3, and then precipitating and drying to obtain a brown solid of the polymer; or cooling the product solution obtained in the step T3 to obtain the aqueous solution of the polymer.
In some embodiments of the invention, in step T2, the temperature within the reactor is heated to 40-80 ℃. That is, in the step T2, at least one of methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride and dimethyl diallyl ammonium chloride and the initiator 2 are added into the reactor to start the reaction at 40 to 80 ℃.
The inert gas used in step T2 is not particularly limited, and may be, for example, nitrogen or the like.
In some embodiments of the present invention, the solvent employed in step T3 is deionized water.
In some embodiments of the invention, the method specifically comprises the steps of:
(1) Adding sodium lignin sulfonate, an initiator 1 and solvent deionized water into a reactor, and fully stirring until the sodium lignin sulfonate, the initiator 1 and the solvent deionized water are completely dissolved;
(2) Replacing air in the reactor by nitrogen, continuously introducing nitrogen, heating to raise the temperature, and adding at least one of methacryloxyethyl trimethyl ammonium chloride (DMC), acryloxyethyl trimethyl ammonium chloride (DAC) and dimethyl diallyl ammonium chloride (DMDAAC) and an initiator 2 to start reaction at the temperature of 40-80 ℃;
(3) Dissolving itaconic acid with deionized water, and regulating the pH value to 6-7 to obtain itaconic acid solution; dropwise adding itaconic acid solution with the pH value regulated into the reaction system in the step (2), and continuing to react for at least 6 hours after the completion of dropwise adding for 20-60 minutes to obtain a product solution;
(4) Cooling the product solution obtained in the step (3), precipitating with absolute ethyl alcohol or acetone, and drying to obtain a brown solid of the polymer; or cooling the product solution obtained in the step (3), and then directly discharging the product solution to obtain the aqueous solution of the polymer.
In a third aspect the present invention provides the use of a polymer according to the first aspect of the present invention or a polymer prepared by the method of the second aspect of the present invention in the treatment of crude oil sewage.
In a fourth aspect, the present invention provides a process for treating crude oil sewage comprising contacting said crude oil sewage with a polymeric flocculant comprising a polymer as described in the first aspect of the present invention or a polymer prepared by the process of the second aspect of the present invention, thereby obtaining treated crude oil sewage.
In some embodiments of the invention, the temperature of the contacting is 40 to 60 ℃, preferably 50 to 55 ℃.
In other embodiments of the invention, the time of contact is from 0.5 to 4 hours, preferably from 1 to 3 hours.
In the present invention, the polymeric flocculant may be an aqueous solution containing the amphoteric polymer, a solution product obtained by the above-mentioned amphoteric polymer production method, or an aqueous solution of a solid product obtained by the above-mentioned amphoteric polymer production method.
In the present invention, the amphoteric polymer is used in the form of a solution thereof when used for treating crude oil sewage.
In some embodiments of the invention, the concentration of the polymer in the polymeric flocculant is 0.5 to 30wt%.
In the present invention, the amount of the polymeric flocculant may be the same as or different from the prior art. Preferably, the polymer is used in an amount of 10 to 200mg, more preferably 50 to 150mg, per 1L of crude oil wastewater.
The polymer of the invention can be directly used as the polymeric flocculant, and can also be used as one of the components of the polymeric flocculant to be matched with other existing flocculants so as to improve the broad-spectrum performance of the flocculant.
In some embodiments of the invention, the additional flocculant is selected from one or more of cationic surfactants prepared by reacting epichlorohydrin with polyamines, dithiocarbamates, diallyldimethylammonium chloride homopolymers, and cationic polyacrylamides.
In the present invention, the crude oil sewage to be treated may be crude oil (polymer-containing) sewage of various oil contents. The crude oil sewage may be of various sources, for example, oilfield sewage, daily chemical sewage, etc.
The beneficial effects of the invention are as follows: the amphoteric polymer is prepared from lignosulfonate, itaconic acid and the components selected from methacryloxyethyl trimethyl ammonium chloride (DMC) and acryloxyethylAt least one of trimethylammonium chloride (DAC) and dimethyldiallylammonium chloride (DMDAAC) is prepared by aqueous solution free radical graft copolymerization method using CaCl 2 -H 2 O 2 Initiation system, fe 2+ -H 2 O 2 The polymer flocculant containing the prepared amphoteric polymer has good demulsification and deoiling effects on crude oil sewage. The amphoteric polymer-containing polymeric flocculant can be prepared from the amphoteric polymers with different proportions according to different raw oil sewage, so that the corresponding polymeric flocculant can be prepared, and the broad-spectrum performance of the flocculant is improved. In addition, both lignosulfonate and itaconic acid are important bio-based chemical raw materials. The wide application of the bio-based raw material can effectively solve the problems caused by the exhaustion of petroleum resources and environmental pollution, and has very important significance.
Detailed Description
In order that the invention may be more readily understood, the invention will be further described in detail with reference to the following examples, which are given by way of illustration only and are not limiting in scope of application. The starting materials or components used in the present invention may be prepared by commercial or conventional methods unless specifically indicated.
Example 1
The operation steps are as follows:
step 1, adding 0.5 g of sodium lignin sulfonate, 0.25 g of ferrous sulfate, 0.8 g of hydrogen peroxide and 18 g of solvent deionized water into a reactor, and fully stirring until the solution is completely dissolved.
Step 2, replacing air in the reactor with nitrogen, continuously introducing nitrogen, heating to raise the temperature, and adding 2 g of an aqueous solution of methacryloyloxyethyl trimethyl ammonium chloride (DMC) with a concentration of 80wt%, 1 g of an aqueous solution of acryloyloxyethyl trimethyl ammonium chloride (DAC) with a concentration of 60wt%, 1 g of an aqueous solution of dimethyldiallylammonium chloride (DMDAAC) with a concentration of 60wt% and 0.015 g of potassium persulfate to start the reaction.
And 3, dissolving 1 gram of itaconic acid monomer by using 10 grams of deionized water, and regulating the pH value to be 6-7 to obtain an aqueous solution of itaconic acid. And (3) dropwise adding the itaconic acid aqueous solution with the pH value regulated into the reaction system, and finishing the dropwise adding after 60 minutes. The reaction was continued for 6.5 hours.
And 4, cooling, precipitating with absolute ethyl alcohol, and drying to obtain the brown solid of the amphoteric polymer.
In this embodiment, the amphoteric polymer is synthesized from the following raw materials in parts by weight: 11.6 parts of sodium lignin sulfonate, 23.2 parts of itaconic acid, 37.2 parts of DMC, 14.0 parts of DAC and 14.0 parts of DMDAAC; wherein the weight parts of DMC+DAC+DMDAAC are 65.2 parts.
Example 2
The operation steps are as follows:
step 1, adding 1.2 g of sodium lignin sulfonate, 0.5 g of ferrous sulfate, 1 g of hydrogen peroxide and 30 g of solvent deionized water into a reactor, and fully stirring until the solution is completely dissolved.
Step 2, replacing air in the reactor with nitrogen, continuously introducing nitrogen, heating to raise the temperature, and adding 4 g of aqueous solution of methacryloyloxyethyl trimethyl ammonium chloride (DMC) with the concentration of 80wt%, 1 g of aqueous solution of acryloyloxyethyl trimethyl ammonium chloride (DAC) with the concentration of 60wt% and 0.03 g of ammonium persulfate to start the reaction at the temperature of 60 ℃.
And 3, dissolving 0.8 g of itaconic acid monomer with 6 g of deionized water, and adjusting the pH value to 6-7 to obtain an aqueous solution of itaconic acid. And (3) dropwise adding the itaconic acid aqueous solution with the pH value regulated into the reaction system, and finishing the dropwise adding after 40 minutes. The reaction was continued for 6 hours.
And 4, cooling, precipitating with acetone, and drying to obtain the brown solid of the amphoteric polymer.
In this embodiment, the amphoteric polymer is synthesized from the following raw materials in parts by weight: 20.7 parts of sodium lignin sulfonate, 13.8 parts of itaconic acid, 55.2 parts of DMC and 10.3 parts of DAC; wherein the weight portion of DMC+DAC+DMDAAC is 65.5 portions.
Example 3
The operation steps are as follows:
step 1, adding 2 g of sodium lignin sulfonate, 1 g of ferrous sulfate, 2.5 g of hydrogen peroxide and 12 g of solvent deionized water into a reactor, and fully stirring until the solution is completely dissolved.
Step 2, replacing air in the reactor with nitrogen, continuously introducing nitrogen, heating to raise the temperature, and adding 3 g of 80wt% concentration methacrylic oxyethyl trimethyl ammonium chloride (DMC) aqueous solution, 1.8 g of 60wt% concentration dimethyl diallyl ammonium chloride (DMDAAC) aqueous solution and 0.07 g of potassium persulfate to start the reaction at 80 ℃.
And 3, dissolving 0.4 g of itaconic acid monomer with 5 g of deionized water, and adjusting the pH value to 6-7 to obtain an aqueous solution of itaconic acid. And (3) dropwise adding the itaconic acid aqueous solution with the pH value regulated into the reaction system, and finishing the dropwise adding after 20 minutes. The reaction was continued for 7.5 hours.
And 4, cooling, and directly discharging by using a solution product to obtain the amphoteric polymer aqueous solution.
In this embodiment, the amphoteric polymer is synthesized from the following raw materials in parts by weight: 34.0 parts of sodium lignin sulfonate, 6.8 parts of itaconic acid, 40.8 parts of DMC and 18.4 parts of DMDAAC; wherein, the weight part of DMC+DAC+DMDAAC is 59.2 parts.
Comparative example 1
The cationic polymer was prepared according to the method of ZL201310183542.2 example 1.
Application example 1
The polymers of example 2 and comparative example 1 and SF-Y001 type cationic polyacrylamide manufactured by Wen county tetragonal water treatment materials Co., ltd. With good effect on the market at present were used as reverse demulsifiers in the amounts shown in Table 1 below to prepare aqueous solutions having a concentration of 1.5 wt%.
The above 3 reverse demulsifier aqueous solutions were reacted with crude oil sewage (oil content: 2000 mg/l) of Liaohe oil field at 60℃for 1 hour, the oil-water interface after contact was observed according to the SY/T5797-93 method, then oil-water separation was performed, the oil content in the obtained aqueous phase was measured according to the SY/T5797-93 method, and the appearance of the aqueous phase was observed, and the results are shown in Table 1 below.
TABLE 1
From the test results, the bio-based amphoteric polymer prepared in the example 2 has a good demulsification and deoiling effect on Liaohe crude oil sewage, and is obviously superior to the cationic polyacrylamide and the cationic polymer prepared in the comparative example 1.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (18)
1. A bio-based amphoteric polymer, which is polymerized by lignosulfonate, itaconic acid and at least two substances selected from methacryloxyethyltrimethylammonium chloride, acryloxyethyltrimethylammonium chloride and dimethyldiallylammonium chloride; the lignin sulfonate comprises 2.7-58.8 parts by weight; the weight part of the itaconic acid is 5.4-62.5 parts; the weight part of the methacryloyloxyethyl trimethyl ammonium chloride is more than or equal to 0, the weight part of the acryloyloxyethyl trimethyl ammonium chloride is more than or equal to 0, the weight part of the dimethyl diallyl ammonium chloride is more than or equal to 0, and the sum of the weight parts of the methacryloyloxyethyl trimethyl ammonium chloride, the acryloyloxyethyl trimethyl ammonium chloride and the dimethyl diallyl ammonium chloride is 20-89.3.
2. A process for preparing the polymer of claim 1, comprising the steps of:
s1, mixing lignosulfonate, an initiator 1 and a solvent, and then adding at least one of methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride and dimethyl diallyl ammonium chloride and an initiator 2 to start reaction;
s2, mixing itaconic acid solution with the reaction system of the step S1, and reacting to obtain a product solution;
s3, cooling the product solution obtained in the step S2, and then precipitating and drying to obtain a brown solid of the polymer; or cooling the product solution obtained in the step S2 to obtain the aqueous solution of the polymer.
3. The method of claim 2, wherein initiator 1 and initiator 2 are each independently selected from CaCl 2 -H 2 O 2 Initiation system, fe 2+ - H 2 O 2 One or more of an initiating system and a peroxide initiating system.
4. A method according to claim 3, wherein initiator 1 and initiator 2 are each independently selected from CaCl 2 -H 2 O 2 Initiation system, ferrous sulfate-H 2 O 2 One or more of an initiating system, potassium persulfate and ammonium persulfate.
5. The method according to claim 4, wherein the initiator 1 is selected from CaCl 2 -H 2 O 2 Initiation system and/or ferrous sulfate-H 2 O 2 And an initiating system, wherein the initiator 2 is selected from potassium persulfate and/or ammonium persulfate.
6. The method according to claim 5, wherein the initiator 1 is 0 to 30 parts by weight and not 0; and/or the weight part of the initiator 2 is 0-1.5 parts and is not 0.
7. The method according to any one of claims 2 to 6, wherein in step S1, the solvent is deionized water; and/or the solvent in the step S1 is used in an amount such that the content of the raw materials in the solution is 10-50 wt%.
8. The method according to any one of claims 2 to 6, wherein in step S2, the pH of the itaconic acid solution is 6 to 7.
9. The method according to claim 8, wherein the itaconic acid solution is added dropwise to the reaction system of step S1 within 20 to 60 minutes.
10. The method of claim 9, wherein the time of the reaction is at least 6 hours;
and/or in step S3, absolute ethyl alcohol or acetone is adopted for precipitation.
11. Use of a polymer according to claim 1 or a polymer prepared by a process according to any one of claims 2 to 10 in the treatment of crude oil sewage.
12. A method for treating crude oil sewage, comprising contacting the crude oil sewage with a polymeric flocculant comprising the polymer of claim 1 or the polymer produced by the method of any one of claims 2 to 10, thereby obtaining treated crude oil sewage.
13. The method of claim 12, wherein the contacting is at a temperature of 40-60 ℃; the contact time is 0.5-4 hours.
14. The method of claim 13, wherein the contacting is at a temperature of 50-55 ℃; the contact time is 1-3 hours.
15. The method according to any one of claims 12 to 14, wherein the concentration of the polymer in the polymeric flocculant is 0.5 to 30wt%.
16. The method according to claim 15, wherein the polymer is used in an amount of 10 to 200mg per 1L of crude oil wastewater.
17. The method of claim 16, wherein the polymer is used in an amount of 50 to 150mg in the polymeric flocculant.
18. The method according to any one of claims 12-14, wherein the polymeric flocculant further comprises an additional flocculant; the other flocculant is selected from one or more of cationic surfactants prepared by reacting epichlorohydrin with polyamine, dithiocarbamates, diallyldimethyl ammonium chloride homopolymers and cationic polyacrylamides.
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