CN102241801B - Acrylic acid(AA)/sodium 2-acrylamide-2-methylpro panesulfonic acid(AMPS-Na)/diisocyanate-modified allyl cyclodextrin (MACD) copolymer - Google Patents
Acrylic acid(AA)/sodium 2-acrylamide-2-methylpro panesulfonic acid(AMPS-Na)/diisocyanate-modified allyl cyclodextrin (MACD) copolymer Download PDFInfo
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Abstract
The invention relates to acrylic acid(AA)/sodium 2-acrylamide-2-methylpro panesulfonic acid(AMPS-Na)/diisocyanate-modified allyl cyclodextrin (MACD) copolymer. The copolymer can effectively adsorb organic molecules in wastewater and has higher fluid loss effect. The technical scheme is that: the copolymer is prepared by polymerizing three monomers, namely acrylic acid (AA), sodium 2-acrylamide-2-methylpro panesulfonic acid (AMPS-Na) and diisocyanate-modified allyl cyclodextrin (MACD); and the copolymer comprises 0.7 molar percent of AA, 15 to 50 molar percent of AMPS-Na and 49.3 to 84.3 molar percent of MACD. A preparation method comprises the following steps of: adding an aqueous solution of AA, a solution of AMPS-Na and a solution of MACD; adding disodium ethylene diamine tetraacetate, potassium peroxydisulfate and sodium hydrogensulfite; and uniformly stirring and mixing, and reacting at the temperature of between 30 and 70DEG C for 5 to 8 hours under the protection of nitrogen to obtain the AA/AMPS-Na/MACD copolymer. The copolymer has good decontamination effect when treating the organic molecules in the wastewater, has good fluid loss effect in drilling fluid and can resist temperature higher than 250DEG C.
Description
Technical field
The present invention relates to a kind of AA/AMPS-Na/MACD multipolymer, the multipolymer of this invention, the ratio according to change monomer in preparation process is applied in the processing Pollutants in Wastewater, and is applied in the oil and gas industry drilling fluid.
Background technology
Organic compound is on the rise to the pollution of water body in recent years, and water pollutes has become global problem, and its pollution level and healthy effect research more and more come into one's own.At present difficult task is exactly how to remove those organic molecules typical and most compounds avidity is not strong from water.For this problem, traditional Technology has filtration, precipitates, solidifies, disinfection by chlorine and gac etc.But various treatment process are not very effective for the organism of removing the stubbornness in the waste water, for example to the aromaticity organic molecule, such as toluene, phenol.The present invention synthesizes with the branched cyclodextrin polymkeric substance by unique emulsion polymerisation process, and these cyclodextrins are for toluene, and the organic molecules such as phenol have very strong adsorptive power.The adsorption test of high-enriched organics solution has proved this high absorption capacity.
Drilling stratum is increasingly sophisticated in the Process of Oil Well Drilling, and exceptional well, ultra deep well and Holes of Complicated Wells quantity increase year by year, and is higher to the requirement of drilling fluid, for this problem, is carrying out a series of activities aspect the high temperature resistant drilling fluids treatment agent.But the increase along with oil well depth, just must increase the consumption for the treatment of agent, but increased again the viscosity of drilling fluid along with the raising of its consumption, particularly in the high situation of content of calcium and magnesium, the Properties Control of drilling fluid is just more difficult, and therefore existing additive for drilling fluid can not well satisfy the drilling well demand.On the basis of molecular designing; not only to satisfy the requirement of heat and salinity tolerance according to treatment agent; particularly anticalcium, magnesium pollution capacity are eager to excel; can't have and increase glutinous effect this purpose; the present invention adopts the monomer copolymerizations such as vinylformic acid AA, 2-acryl-2-methyl propane sulfonic acid sodium AMPS-Na and modification allyl group cyclodextrin MACD; the terpolymer that has synthesized a kind of low relative molecular mass; it has the stronger leak-off effect of falling and temperature resistance, anti-salt, anticalcium ability, and has shown preferably over-all properties.
Summary of the invention
The objective of the invention is: in order to solve the Organic Pollutants in Wastewater molecule, and the Oil/gas Well shaft bottom is under high temperature, high salt condition, after treatment dosage increases, and the difficult control problem of drilling fluid character, the spy provides a kind of AA/AMPS-Na/MACD multipolymer.
For achieving the above object, the present invention is by the following technical solutions: a kind of AA/AMPS-Na/MACD multipolymer is characterized in that: this multipolymer is by vinylformic acid code name AA, 2-acrylamido-2-methyl propane sulfonic acid sodium code name AMPS-Na and vulcabond modification allyl group cyclodextrin three kinds of monomer polymerizations of code name MACD and get; The molar percentage of used monomer and partial properties are: the molar percentage of AA is 0.7%; The molar percentage of AMPS-Na is 15-50%, is the NaOH solution titration 2-acrylamido-2-methyl propane sulfonic acid AMPS of 4.0g/L with concentration, to pH7-8, namely gets AMPS-Na; The molar percentage of MACD is 49.3-84.3%, the 0.1g vulcabond is made into the solution that concentration is 5.0g/L, and adding 0.5g sodium lauryl sulphate, making tensio-active agent uses, it is stand-by that 0.1g allyl group cyclodextrin is added in the 2.0mL deionized water wiring solution-forming, more above-mentioned two kinds of solution mixed under ul-trasonic irradiation, pours into behind the 2min in the single port bottle, 60 ℃ of lower reactions 12 hours, obtain vulcabond modification allyl group cyclodextrin monomer; In the multipolymer preparation, the sequestrant disodium ethylene diamine tetraacetate, consumption is the 0.15%-0.25% of reaction monomers total mass, and oxygenant Potassium Persulphate, consumption are 0.25%-0.5%, and reductive agent sodium bisulfite, consumption are 0.25%-0.5%.The structural formula of this multipolymer is as follows:
Wherein the molar percentage of X is 0.7%, the molar percentage of Y is 15-50%, (according to the molar percentage of the difference control Y of application direction),
Symbolic representation cyclodextrin structure unit.
A kind of preparation method of AA/AMPS-Na/MACD multipolymer: be in the 0.01g/mL vulcabond modification allyl group cyclodextrin MACD aqueous solution in 100mL concentration first, adding concentration is the vinylformic acid AA 8.1-9.5mL of 0.1g/mL and the 2-acrylamido that concentration is 0.5g/mL-2-methyl propane sulfonic acid sodium AMPS-Na 5-15mL, and AA, AMPS-Na and MACD three's mol ratio is followed successively by 0.7:15-50:49.3-84.3; And then to add successively concentration be that 0.3g/mL disodium ethylene diamine tetraacetate 1.0mL, concentration are that Potassium Persulphate 1.0mL and the concentration of 0.5g/mL is 1.0g/mL sodium bisulfite 0.5mL; After mixing mentioned solution evenly at last, inflated with nitrogen 30-50min deoxygenation at 30-70 ℃ of lower reaction 5-8h, makes the AA/AMPS-Na/MACD multipolymer.
Compared with prior art, the present invention has following beneficial effect: the preparation method of ⑴ AA/AMPS-Na/MACD multipolymer is simple and feasible, and reaction conditions is gentle; ⑵ can by the molar percentage of control monomer, obtain the different application aspect of multipolymer according to this characteristic of vulcabond modification allyl group cyclodextrin; ⑶ when increased when vulcabond modification allyl group cyclodextrin MACD molar percentage, the multipolymer that obtains can adsorb the organic pollutants such as benzene, toluene effectively, formed the supramolecule adsorbing sphere; When strengthening 2-acrylamido-2-methyl propane sulfonic acid sodium AMPS-Na molar percentage, the multipolymer of the method preparation can with drilling fluid in the materials such as tensio-active agent organically combine, form the super molecule inclusion compound film, after 200 ℃ of rollings are aging, still can control preferably the filter loss of drilling fluid, embody good temperature resistant antisalt ability.
Embodiment
The present invention is further described below by embodiment.
Embodiment 1The preparation method of AA/AMPS-Na/MACD multipolymer sewage-treating agent
Be that 0.01g/mL vulcabond modification allyl group cyclodextrin MACD aqueous solution 150mL joins in the 250mL beaker with the concentration for preparing, add again concentration and be 0.1g/mL vinylformic acid AA aqueous solution 8.5mL, concentration and be the 2-acrylamido of 0.5g/mL-2-methyl propane sulfonic acid sodium AMPS-Na aqueous solution 5ml; And then to add successively concentration be that 0.3g/mL disodium ethylene diamine tetraacetate 1mL, concentration are that Potassium Persulphate 1mL and the concentration of 0.5g/mL is 1.0g/mL sodium bisulfite 0.5mL; Fully stir mixed evenly rear inflated with nitrogen 40min deoxygenation on magnetic stirring apparatus, 60 ℃ of lower reaction 6h get transparent gluey product A A/AMPS-Na/MACD multipolymer.
Press the intrinsic viscosity of the described standard test AA/AMPS-Na/MACD of GB12005.1-89 multipolymer, again according to the molecular weight of GB/T12005.10-92 standard test multipolymer, the molecular-weight average that records the AA/AMPS-Na/MACD multipolymer is M=2.59 * 10
6
Embodiment 2The clean effect of AA/AMPS-Na/MACD multipolymer
In order to estimate the clean effect of AA/AMPS-Na/MACD multipolymer, having done adsorption test proves.The product that obtains is immersed in the sewage that contains organic molecule, and detailed process is as follows: at first prepare the by volume mixing solutions of 90:10 of deionized water and ethanol, after toluene and phenol mixing solutions 10ml are added in the above-mentioned mixing solutions; Again the above-mentioned product A A/AMPS-Na/MACD that makes is made into the aqueous copolymers solution of 10-100mg/L; The mixing solutions that to produce above at last joins in the aqueous solutions of polymers, through behind the 24h, under the whizzer of 5000r/min, separate 10min, measure adsorption equilibrium concentration by the visible spectrophotometer method, prove that the AA/AMPS-Na/MACD multipolymer that this invention makes has preferably clean effect to the waste water that contains the organic solvents such as benzene, toluene.
Embodiment 3The preparation method of AA/AMPS-Na/MACD copolymer fluid loss agent
Be that 0.01g/mL vulcabond modification allyl group cyclodextrin MACD aqueous solution 100mL joins in the 250mL beaker with the concentration for preparing, add again concentration and be 0.1g/mL vinylformic acid AA aqueous solution 8.5mL, concentration and be the 2-acrylamido of 0.5g/mL-2-methyl propane sulfonic acid sodium AMPS-Na aqueous solution 10mL; And then to add successively concentration be that 0.3g/mL disodium ethylene diamine tetraacetate 1mL, concentration are that Potassium Persulphate 1mL and the concentration of 0.5g/mL is 1.0g/mL sodium bisulfite 0.5mL; Fully stir mixed evenly rear inflated with nitrogen 40min deoxygenation on magnetic stirring apparatus, 35 ℃ of lower reaction 5h get gel product A A/AMPS-Na/MACD multipolymer.
Press the intrinsic viscosity of the described standard test AA/AMPS-Na/MACD of GB12005.1-89 polymkeric substance, again according to the molecular weight of GB/T12005.10-92 standard test polymkeric substance, the molecular-weight average that records the AA/AMPS-Na/MACD polymkeric substance is M=3.23 * 10
6
Example 4The AA/AMPS-Na/MACD multipolymer filtration effect falls
Under comparatively high temps filtration effect falls in order to estimate the AA/AMPS-Na/MACD polymkeric substance, at first according to GB/T16783-1997 national standard preparation base slurry.Namely in the 200mL of high-speed stirring deionized water, add 0.5g anhydrous sodium carbonate, 10g wilkinite and 8g and estimate soil, the airtight 24h that leaves standstill behind the continuation stirring 20min gets the fresh water-based slurry.Equally, in the 200mL of high-speed stirring deionized water, add 0.7g anhydrous sodium carbonate, 14g wilkinite and 20g and estimate soil, the airtight 24h that leaves standstill behind the continuation stirring 20min gets brine mud; In the 200mL of high-speed stirring deionized water, add 0.9g anhydrous sodium carbonate, 18g wilkinite and 30g and estimate soil and 50g sodium-chlor, the airtight 24h that leaves standstill behind the continuation stirring 20min gets the water base slurry of saturated salt; In the 200mL of high-speed stirring deionized water, add 0.9g anhydrous sodium carbonate, 14g calcium bentonite and 30g and estimate soil and 50g sodium-chlor, the airtight 24h that leaves standstill behind the continuation stirring 20min gets compound salt-water basic slurry.
Table 1 is the filtration effect that falls of AA/AMPS-Na/MACD polymkeric substance.As can be seen from Table 1, polymkeric substance of the present invention is at fresh water, and salt solution in saturated brine and the composite salt aqueous systems, all has preferably temperature resistance, anti-salt and falls filtration effect.
Filtration effect falls in the room temperature after table 1 AA/AMPS-Na/MACD polymkeric substance is aging
Claims (3)
1. AA/AMPS-Na/MACD multipolymer, it is characterized in that: this multipolymer is to be formed by vinylformic acid code name AA, 2-acrylamido-2-methyl propane sulfonic acid sodium code name AMPS-Na and three kinds of monomer polymerizations of vulcabond modification allyl group cyclodextrin code name MACD; The molar percentage of used monomer and partial properties are: the molar percentage of AA is 0.7%; The molar percentage of AMPS-Na is 15-50%, is the NaOH solution titration 2-acrylamido-2-methyl propane sulfonic acid AMPS of 4.0g/L with concentration, to pH7-8, namely gets AMPS-Na; The molar percentage of MACD is 49.3-84.3%, the 0.1g vulcabond is made into the solution that concentration is 5.0g/L, and adding 0.5g sodium lauryl sulphate, making tensio-active agent uses, it is stand-by that 0.1g allyl group cyclodextrin is added in the 2.0mL deionized water wiring solution-forming, more above-mentioned two kinds of solution mixed under ul-trasonic irradiation, pours into behind the 2min in the single port bottle, 60 ℃ of lower reactions 12 hours, obtain vulcabond modification allyl group cyclodextrin monomer; Sequestrant disodium ethylene diamine tetraacetate, consumption are the 0.15%-0.25% of reaction monomers total mass, and oxygenant Potassium Persulphate, consumption are 0.25%-0.5%, and reductive agent sodium bisulfite, consumption are 0.25%-0.5%.
2. multipolymer according to claim 1, it is characterized in that: this Application of copolymer is: clean effect, prepare first the by volume mixing solutions of 90:10 of deionized water and ethanol, after toluene and phenol mixing solutions 10ml are added in the above-mentioned mixing solutions; The AA/AMPS-Na/MACD that will make above again is made into the aqueous copolymers solution of 10-100mg/L; At last mixing solutions is joined in the aqueous copolymers solution, through behind the 24h, under the whizzer of 5000r/min, separate 10min, measure adsorption equilibrium concentration by the visible spectrophotometer method, prove that this multipolymer has preferably clean effect to the waste water that contains benzene, toluene; Filtration effect falls, first in the 200mL of high-speed stirring deionized water, add 0.5g anhydrous sodium carbonate, 10g wilkinite and 8g and estimate soil, the airtight 24h that leaves standstill behind the continuation stirring 20min, get the fresh water-based slurry, with same method pickle making base slurry, the water base slurry of saturated salt, compound salt-water basic slurry, again AA/AMPS-Na/MACD multipolymer of the present invention is added respectively in fresh water, salt solution, saturated brine and the composite salt aqueous systems, test-results shows: all have preferably temperature resistance, anti-salt and fall filtration effect.
3. described multipolymer according to claim 1, it is characterized in that: employed vulcabond is a kind of of isoflurane chalcone diisocyanate or tolylene diisocyanate or hexamethylene diisocyanate; Used allyl group cyclodextrin is a kind of of allyl group alpha-cylodextrin or allyl group beta-cyclodextrin or allyl group γ-cyclodextrin.
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| CN 201110131647 CN102241801B (en) | 2011-05-20 | 2011-05-20 | Acrylic acid(AA)/sodium 2-acrylamide-2-methylpro panesulfonic acid(AMPS-Na)/diisocyanate-modified allyl cyclodextrin (MACD) copolymer |
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| CN104531101B (en) * | 2014-12-31 | 2016-02-17 | 北京培康佳业技术发展有限公司 | Fluid loss additive for boring fluid and preparation method thereof and application |
| CN105879840A (en) * | 2016-04-21 | 2016-08-24 | 苏州云舒新材料科技有限公司 | Organic-inorganic compound and application thereof in water treatment |
| WO2018038186A1 (en) * | 2016-08-23 | 2018-03-01 | ダイキン工業株式会社 | Polymer material |
| CN107418585B (en) * | 2017-07-24 | 2020-11-10 | 天津市德宇生物工程技术有限公司 | Saline-alkali soil conditioner |
| CN109607633A (en) * | 2018-12-27 | 2019-04-12 | 长江大学 | A kind of technique removing neopelex in aqueous solution containing HPAM |
| CN110746949B (en) * | 2019-10-22 | 2021-09-14 | 卫辉市化工有限公司 | Oil well cement polymer fluid loss agent and preparation method thereof |
| CN116655829A (en) * | 2023-05-10 | 2023-08-29 | 乐凯华光印刷科技有限公司 | Modified cyclodextrin, and treatment-free thermosensitive plate precursor, treatment-free thermosensitive plate and application containing modified cyclodextrin |
Citations (1)
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| US3806367A (en) * | 1972-06-01 | 1974-04-23 | Bitz Lab Inc | Acrylamido-sulfonic acid polymers and their use as rust and tubercle removing agents |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3806367A (en) * | 1972-06-01 | 1974-04-23 | Bitz Lab Inc | Acrylamido-sulfonic acid polymers and their use as rust and tubercle removing agents |
Non-Patent Citations (2)
| Title |
|---|
| 孙焕泉等.NaCl存在下SDBS与超高相对分子质量AM-AA-AMPS三元共聚物的相互作用.《石油学报( 石油加工)》.2011,第27卷(第1期),第85-90页. * |
| 杨小华等.AMPS 聚合物及钻井液体系研究与应用.《石油与天然气化工》.2001,第30卷(第3期),第138-140页. * |
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