CN113831480A - 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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- CN113831480A CN113831480A CN202010582283.0A CN202010582283A CN113831480A CN 113831480 A CN113831480 A CN 113831480A CN 202010582283 A CN202010582283 A CN 202010582283A CN 113831480 A CN113831480 A CN 113831480A
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- ammonium chloride
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- itaconic acid
- crude oil
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- 229920000642 polymer Polymers 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 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 32
- 239000010779 crude oil Substances 0.000 claims abstract description 21
- 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 21
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 20
- 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 19
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000008394 flocculating agent Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 29
- 239000003999 initiator Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 17
- 239000002351 wastewater Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 230000000977 initiatory effect Effects 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 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
- 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
- 150000002978 peroxides Chemical class 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
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- 239000012990 dithiocarbamate Substances 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 239000010865 sewage Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 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
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 229920005552 sodium lignosulfonate Polymers 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 235000003891 ferrous sulphate Nutrition 0.000 description 6
- 239000011790 ferrous sulphate Substances 0.000 description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920006317 cationic polymer Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 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
- 125000000129 anionic group Chemical group 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- -1 cationic quaternary ammonium salt Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 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
- 125000002887 hydroxy group Chemical group [H]O* 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000867 polyelectrolyte Polymers 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
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a bio-based amphoteric polymer and a preparation method and application thereof. The bio-based amphoteric polymer is prepared by polymerizing lignosulfonate, itaconic acid and at least one selected from methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride and dimethyl diallyl ammonium chloride. The polymeric flocculant containing the amphoteric polymer has the advantages of environmental protection and good demulsification and deoiling effects on crude oil sewage. Meanwhile, amphoteric polymers with different proportions can be selected according to different crude oil sewage to prepare corresponding polymeric flocculants, so that the broad-spectrum performance of the flocculants is improved. In addition, both lignosulfonates and itaconic acid are important bio-based chemical feedstocks. The wide application of the bio-based raw materials 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, has excellent performance, and can obtain ideal treatment effect by controlling proper dosage and mixing method and adding subsequent reasonable precipitation filtration process. Therefore, the development of novel and efficient flocculating agents is a target of attention of a wide range of water treatment workers at home and abroad. At present, the most widely used organic polymeric flocculant is polyacrylamide, but the monomer of the organic polymeric flocculant has toxicity caused by three causes and causes secondary pollution to water, so that the exploration of the efficient and environment-friendly flocculant becomes a hotspot of current research.
The water-soluble amphoteric polymer is a water-soluble polymer containing both positive and negative charge groups on the polymer chain unit, and has more unique properties than a water-soluble anionic or cationic polymer containing only one charge. For example, the amphoteric polymer used as the flocculant is a hot research at home and abroad due to the application characteristics of suitability for a pollution system with coexisting anions and cations, wide pH value application range, good salt resistance and the like.
Lignosulfonate is one of main byproducts in the papermaking industry, and the lignosulfonate has a structure containing phenolic hydroxyl, alcoholic hydroxyl, sulfonic acid, carboxyl and other groups, so that the lignosulfonate has good water solubility, adsorbability, amphipathy and other properties, and is widely applied to the fields of water treatment agents, ion exchangers, water reducing agents and the like. Lignosulfonate is a natural high molecular material, but has low average relative molecular mass and few active adsorption points, so that the application of the lignosulfonate in a flocculating agent is limited, and chemical modifications are needed to improve the application performance of the lignosulfonate.
Itaconic acid is a completely biodegradable biomass chemical raw 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 from nature in a real sense and is attributed to nature. Itaconic acid is 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 carry out a series of reactions such as esterification, polymerization, addition and the like.
Dimethyl diallyl ammonium chloride is a monomer with unsaturated carbon-carbon double bond groups and quaternary ammonium salt groups, and a polymer of the dimethyl diallyl ammonium chloride is the only synthetic cationic quaternary ammonium salt polyelectrolyte approved by the U.S. public health administration (U.S. P.H.S.) for drinking water purification treatment, and is widely applied to the fields of water treatment, petroleum drilling, paper making and the like.
At present, the need of providing a green and environment-friendly flocculant using bio-based raw materials is urgent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a 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, the present invention provides, in a first aspect, a bio-based amphoteric polymer polymerized from a lignosulfonate, itaconic acid, and at least one selected from the group consisting of methacryloyloxyethyltrimethyl ammonium chloride (DMC), acryloyloxyethyltrimethyl ammonium chloride (DAC), and dimethyldiallylammonium chloride (DMDAAC).
In some embodiments of the invention, the lignosulfonate is 2.7-58.8 parts by weight; the weight part of the itaconic acid is 5.4-62.5; the weight portion of the methacryloyloxyethyl trimethyl ammonium chloride is more than or equal to 0, the weight portion of the acryloyloxyethyl trimethyl ammonium chloride is more than or equal to 0, the weight portion of the dimethyl diallyl ammonium chloride is more than or equal to 0, and the sum of the weight portions 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 methacryloyloxyethyltrimethyl ammonium chloride, acryloyloxyethyltrimethyl ammonium chloride and dimethyldiallylammonium chloride and the initiator 2 to start to react;
s2, mixing the 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, precipitating and drying to obtain 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 2.7-58.8 parts by weight; the weight part of the itaconic acid is 5.4-62.5; the weight portion of the methacryloyloxyethyl trimethyl ammonium chloride (DMC) is not less than 0, the weight portion of the acryloyloxyethyl trimethyl ammonium chloride (DAC) is not less than 0, the weight portion of the dimethyldiallylammonium chloride (DMDAAC) is not less than 0, and the weight portions of the DMC + DAC + DMDAAC are 20-89.3.
The lignosulfonate in the present invention is not particularly limited, and may be, for example, sodium lignosulfonate.
In some embodiments of the invention, the initiator 1 and the initiator 2 are each independently selected from CaCl2-H2O2Initiation System, Fe2+-H2O2One or more of an initiating system and a peroxide initiating system.
In some preferred embodiments of the present invention, the initiator 1 and the initiator 2 are each independently selected from CaCl2-H2O2Initiating system, ferrous sulfate-H2O2One 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 CaCl2-H2O2Initiating system and/or ferrous sulfate-H2O2And (2) an initiating system, wherein the initiating agent 2 is selected from potassium persulfate and/or ammonium persulfate.
In other embodiments of the present invention, the initiator 1 is 0 to 30 parts by weight and is not 0; and/or the initiator 2 is 0-1.5 parts by weight and is 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 10 wt% to 50 wt%. In the present invention, the feedstock is comprised of lignosulfonate, itaconic acid, and at least one substance selected from the group consisting of methacryloyloxyethyltrimethyl ammonium chloride (DMC), acryloyloxyethyltrimethyl ammonium chloride (DAC), and dimethyldiallylammonium chloride (DMDAAC).
In some embodiments of the invention, in step S2, the pH of the itaconic acid solution is 6-7.
In other embodiments of the present invention, in step S2, the itaconic acid solution is added dropwise to the reaction system of step S1 within 20 to 60 minutes.
In some embodiments of the invention, in step S2, the reaction time 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 present invention, the method may comprise the steps of:
t1, adding lignosulfonate, initiator 1 and solvent to the reactor;
t2, replacing air in the reactor with inert gas and 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 adjusting the pH value of the solution to obtain an itaconic acid solution; then adding the itaconic acid solution into the reaction system in the step T2, and continuing to react to obtain a product solution;
t4, cooling the product solution obtained in the step T3, precipitating and drying to obtain 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 present invention, in the step T2, the temperature in the reactor is heated to 40-80 ℃. That is, in step T2, at least one of methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride and dimethyldiallylammonium chloride and the initiator 2 are added to the reactor at 40 to 80 ℃ to start the reaction.
The inert gas used in step T2 is not specifically limited in the present invention, and for example, the inert gas may be nitrogen or the like.
In some embodiments of the present invention, the solvent used in step T3 is deionized water.
In some embodiments of the invention, the method specifically comprises the steps of:
(1) adding sodium lignosulfonate, an initiator 1 and solvent deionized water into a reactor, and fully stirring until the sodium lignosulfonate, the initiator 1 and the solvent deionized water are completely dissolved;
(2) replacing air in the reactor with nitrogen, continuously introducing the 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 adjusting the pH value to 6-7 to obtain an itaconic acid solution; dripping itaconic acid solution with the adjusted pH value into the reaction system in the step (2), continuing to react for at least 6 hours after finishing dripping for 20-60 minutes to obtain product solution;
(4) cooling the product solution obtained in the step (3), precipitating with absolute ethyl alcohol or acetone, and drying to obtain brown solid of the polymer; or after the product solution obtained in the step (3) is cooled, directly discharging the product solution to obtain the aqueous solution of the polymer.
In a third aspect, the invention provides the use of a polymer according to the first aspect of the invention or a polymer prepared by the method of the second aspect in the treatment of crude oil wastewater.
In a fourth aspect, the present invention provides a method for treating crude oil wastewater, which comprises contacting the crude oil wastewater with a polymeric flocculant comprising the polymer according to the first aspect of the present invention or the polymer prepared by the method according to the second aspect, thereby obtaining treated crude oil wastewater.
In some embodiments of the invention, the temperature of the contacting is 40 to 60 ℃, preferably 50 to 55 ℃.
In other embodiments of the present invention, the contact time is 0.5 to 4 hours, preferably 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 method for producing an amphoteric polymer, or an aqueous solution of a solid product obtained by the method for producing an amphoteric polymer.
In the present invention, the amphoteric polymer is used in the form of its solution when used for treating crude oil wastewater.
In some embodiments of the present invention, the concentration of the polymer in the polymeric flocculant is 0.5 to 30 wt%.
In the present invention, the amount of the polymeric flocculant may be the same as or different from that of the prior art. Preferably, the amount of the polymer in the polymeric flocculant is 10-200 mg, more preferably 50-150 mg, relative to 1L of crude oil wastewater.
The polymer can be directly used as the polymeric flocculant or can be used as one of the components of the polymeric flocculant to be matched with other conventional flocculants so as to improve the broad-spectrum performance of the flocculant.
In some embodiments of the invention, the other flocculant is selected from one or more of a cationic surfactant prepared by the reaction of epichlorohydrin and a polyamine, a dithiocarbamate, a diallyldimethylammonium chloride homopolymer and a cationic polyacrylamide.
In the present invention, the crude oil-containing wastewater to be treated may be crude oil (polymer-containing) wastewater having various oil contents. The crude oil wastewater can be from various sources, such as oil field wastewater, domestic chemical wastewater, and the like.
The invention has the beneficial effects that: the amphoteric polymer is prepared from lignosulfonate, itaconic acid and at least one substance selected from methacryloxyethyltrimethyl ammonium chloride (DMC), acryloxyethyltrimethyl ammonium chloride (DAC) and dimethyldiallylammonium chloride (DMDAAC) by aqueous solution free radical graft copolymerization method using CaCl2-H2O2Initiation System, Fe2+-H2O2The initiating system, the peroxide initiating system or the composite initiating system, and the polymeric flocculant containing the prepared amphoteric polymer has good demulsification and deoiling effects on crude oil sewage. The amphoteric polymer flocculant containing the amphoteric polymer can be prepared into corresponding polymeric flocculant by selecting amphoteric polymers with different proportions according to different crude oil sewage, so that the broad-spectrum performance of the flocculant is improved. In addition, both lignosulfonates and itaconic acid are important bio-based chemical feedstocks. The wide application of the bio-based raw materials 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 present invention may be more readily understood, the following detailed description will proceed with reference being made to examples, which are intended to be illustrative only and are not intended to limit the scope of the invention. The starting materials or components used in the present invention may be commercially or conventionally prepared unless otherwise specified.
Example 1
The method comprises the following operation steps:
step 1, adding 0.5 g of sodium lignosulfonate, 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 sodium lignosulfonate, the ferrous sulfate, the hydrogen peroxide and the solvent deionized water are completely dissolved.
And 2, replacing the air in the reactor with nitrogen, continuously introducing the nitrogen, heating, raising the temperature, and adding 2 g of an aqueous solution of 80 wt% of methacryloyloxyethyl trimethyl ammonium chloride (DMC), 1 g of an aqueous solution of 60 wt% of acryloyloxyethyl trimethyl ammonium chloride (DAC), 1 g of an aqueous solution of 60 wt% of dimethyldiallylammonium chloride (DMDAAC) and 0.015 g of potassium persulfate to start the reaction at the temperature of 50 ℃.
And 3, dissolving 1 g of itaconic acid monomer by using 10 g of deionized water, and adjusting the pH value to 6-7 to obtain an itaconic acid aqueous solution. And (4) dropwise adding the itaconic acid aqueous solution with the adjusted pH value into the reaction system, and finishing dropwise adding within 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 example, the amphoteric polymer is synthesized from the following raw materials in parts by weight: 11.6 parts sodium lignosulfonate, 23.2 parts itaconic acid, 37.2 parts DMC, 14.0 parts DAC, and 14.0 parts DMDAAC; wherein, the weight portion of DMC + DAC + DMDAAC is 65.2 portions.
Example 2
The method comprises the following operation steps:
step 1, adding 1.2 g of sodium lignosulfonate, 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 sodium lignosulfonate, the ferrous sulfate, the hydrogen peroxide and the solvent deionized water are completely dissolved.
And 2, replacing the air in the reactor with nitrogen, continuously introducing the nitrogen, heating, raising the temperature, and adding 4 g of an aqueous solution of 80 wt% of methacryloyloxyethyl trimethyl ammonium chloride (DMC), 1 g of an aqueous solution of 60 wt% of acryloyloxyethyl trimethyl ammonium chloride (DAC) and 0.03 g of ammonium persulfate to start reaction at the temperature of 60 ℃.
And 3, dissolving 0.8 g of itaconic acid monomer by 6 g of deionized water, and adjusting the pH value to 6-7 to obtain an itaconic acid aqueous solution. And (4) dropwise adding the itaconic acid aqueous solution with the adjusted pH value into the reaction system, and finishing dropwise adding within 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 example, the amphoteric polymer is synthesized from the following raw materials in parts by weight: 20.7 parts of sodium lignosulfonate, 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 method comprises the following operation steps:
step 1, adding 2 g of sodium lignosulfonate, 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 sodium lignosulfonate, the ferrous sulfate, the hydrogen peroxide and the solvent deionized water are completely dissolved.
And 2, replacing the air in the reactor with nitrogen, continuously introducing the nitrogen, heating, raising the temperature, and adding 3 g of an 80 wt% aqueous solution of methacryloyloxyethyl trimethyl ammonium chloride (DMC), 1.8 g of a 60 wt% aqueous solution of dimethyldiallylammonium chloride (DMDAAC) and 0.07 g of potassium persulfate to start the reaction at the temperature of 80 ℃.
And 3, dissolving 0.4 g of itaconic acid monomer by using 5 g of deionized water, and adjusting the pH value to 6-7 to obtain an itaconic acid aqueous solution. And (4) dropwise adding the itaconic acid aqueous solution with the adjusted pH value into the reaction system, and finishing dropwise adding within 20 minutes. The reaction was continued for 7.5 hours.
And 4, cooling, and directly discharging the solution product to obtain the amphoteric polymer aqueous solution.
In this example, the amphoteric polymer is synthesized from the following raw materials in parts by weight: 34.0 parts sodium lignosulfonate, 6.8 parts itaconic acid, 40.8 parts DMC and 18.4 parts DMDAAC; wherein, the weight portion of DMC + DAC + DMDAAC is 59.2 portions.
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, which is currently commercially available from Wenxian county Water treatment materials Co., Ltd. and which is commercially effective, were used as reverse demulsifiers in the amounts shown in Table 1 below to prepare aqueous solutions having a concentration of 1.5% by weight, respectively.
The 3 kinds of reverse demulsifier aqueous solutions were reacted with crude oil wastewater (oil content ≥ 2000mg/l) from Liaohe oilfield at 60 deg.C for 1 hr, the contacted oil-water interface was observed according to SY/T5797-93 method, oil-water separation was then performed, the oil content in the obtained aqueous phase was measured according to SY/T5797-93 method, and the appearance of the aqueous phase was observed, with the results shown in Table 1 below.
TABLE 1
From the test results, the bio-based amphoteric polymer prepared in example 2 has better demulsification and deoiling effects on the Liaohe crude oil sewage, and is obviously better than the cationic polyacrylamide and the cationic polymer prepared in comparative example 1.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A bio-based amphoteric polymer is polymerized from lignosulfonate, itaconic acid, and at least one selected from methacryloyloxyethyltrimethyl ammonium chloride, acryloyloxyethyltrimethyl ammonium chloride, and dimethyldiallylammonium chloride.
2. The polymer of claim 1, wherein the lignosulfonate is present in an amount of 2.7 to 58.8 parts by weight; the weight part of the itaconic acid is 5.4-62.5; the weight portion of the methacryloyloxyethyl trimethyl ammonium chloride is more than or equal to 0, the weight portion of the acryloyloxyethyl trimethyl ammonium chloride is more than or equal to 0, the weight portion of the dimethyl diallyl ammonium chloride is more than or equal to 0, and the sum of the weight portions of the methacryloyloxyethyl trimethyl ammonium chloride, the acryloyloxyethyl trimethyl ammonium chloride and the dimethyl diallyl ammonium chloride is 20-89.3.
3. A process for the preparation of a polymer as claimed in claim 1 or 2, which comprises the steps of:
s1, mixing lignosulfonate, an initiator 1 and a solvent, and then adding at least one of methacryloyloxyethyltrimethyl ammonium chloride, acryloyloxyethyltrimethyl ammonium chloride and dimethyldiallylammonium chloride and the initiator 2 to start to react;
s2, mixing the 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, precipitating and drying to obtain brown solid of the polymer; or cooling the product solution obtained in the step S2 to obtain the aqueous solution of the polymer.
4. The process of claim 3, wherein initiator 1 and initiator 2 are each independently selected from CaCl2-H2O2Initiation System, Fe2+-H2O2One or more of an initiating system and a peroxide initiating system; preferably, the initiator 1 and the initiator 2 are each independently selected from CaCl2-H2O2Initiating system, ferrous sulfate-H2O2One or more of an initiation system, potassium persulfate, and ammonium persulfate; further preferably, the initiator 1 is selected from CaCl2-H2O2Initiating system and/or ferrous sulfate-H2O2An initiating system, wherein the initiator 2 is selected from potassium persulfate and/or ammonium persulfate; more preferably, the weight portion of the initiator 1 is 0-30 parts and is not 0;and/or the initiator 2 is 0-1.5 parts by weight and is not 0.
5. The method according to claim 3 or 4, wherein 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 10 wt% to 50 wt%.
6. The method according to any one of claims 3 to 5, wherein in step S2, the pH value of the itaconic acid solution is 6-7; preferably, the itaconic acid solution is dropwise added to the reaction system in the step S1 within 20-60 minutes; further preferably, the time of the reaction is at least 6 hours;
and/or in step S3, precipitating with absolute ethanol or acetone.
7. Use of a polymer according to claim 1 or 2 or a polymer prepared by a process according to any one of claims 3 to 6 in the treatment of crude oil wastewater.
8. A method for treating crude oil wastewater, which comprises contacting the crude oil wastewater with a polymeric flocculant comprising the polymer according to claim 1 or 2 or the polymer produced by the method according to any one of claims 3 to 6, thereby obtaining treated crude oil wastewater;
preferably, the contact temperature is 40-60 ℃, preferably 50-55 ℃; the contact time is 0.5 to 4 hours, preferably 1 to 3 hours.
9. The method according to claim 8, wherein the concentration of the polymer in the polymeric flocculant is 0.5-30 wt%; preferably, the amount of the polymer in the polymeric flocculant is 10-200 mg, and more preferably 50-150 mg, relative to 1L of crude oil wastewater.
10. The method of claim 8 or 9, wherein the polymeric flocculant further comprises other flocculants; the other flocculant is selected from one or more of a cationic surfactant prepared by reacting epichlorohydrin and a polyamine, a dithiocarbamate, a diallyldimethylammonium chloride homopolymer and a cationic polyacrylamide.
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