CN102702427A - Biopolymer MA (maleic anhydride)-AMPS (2-acrylamido-2-methyl propane sulfonic acid) water treatment agent and preparation method of biopolymer AM-AMPS water treatment agent - Google Patents
Biopolymer MA (maleic anhydride)-AMPS (2-acrylamido-2-methyl propane sulfonic acid) water treatment agent and preparation method of biopolymer AM-AMPS water treatment agent Download PDFInfo
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Abstract
The invention relates to a biopolymer MA (methyl acrylate)-AMPS (2-acrylamido-2-methyl propane sulfonic acid) and a preparation method of the biopolymer AM-AMPS. The biopolymer is a linear copolymer formed according to the steps that MA and AMPS are used as reactants to obtain polymerization monomers, and then, the polymerization reaction is carried out. The biopolymer AM-AMPS provided by the invention belongs to an oil field water treatment agent with excellent performance, in addition, the made product is phosphor-free, nontoxic and harmless, the environment is favorably protected, the product can be stably stored for a long time, and wide oil field industrial market application prospects are realized.
Description
Technical field
The present invention relates to a kind of oil-field water treatment agent and preparation method thereof, particularly a kind of copolymer MA-AMPS and preparation method thereof.
Background technology
In the oil production process, owing to inject water and the serious uncompatibility of local water and the rapid variation of oil recovery process pressure and temperature, the scale problems that causes becomes a great problem in the petroleum production engineering.When the temperature of waterflood system, pressure, pH value etc. change, possibly in subsurface reservoir, producing well pit shaft, ground oil-gas gathering and transportation equipment installation, form various dirts.In oil extraction system, well rod, oil pipe and sleeve pipe etc. locate to be prone to take place fouling; In surface gathering system, waterflood-transmission line, water jacket furnace egress filtering valve position, heating stone or metal plate for standing a stove on as a precaution against fire and pump are also easy common to have dirt to adhere to.Fouling makes the pipeline sectional area diminish, and frictional resistance increases, and the processing power of pump reduces, and heating installation thermo-efficiency reduces, and pipeline makes the pressure increase because of dirty thing stops up with corrosive pipeline when serious, pipeline burst occurs, causes adverse consequences.It is thus clear that fouling has become the subject matter that influences the oil field ordinary production.Therefore, in the face of in the oilfield development process, moisture continuous rising, the practical situation that fouling constantly increases the weight of, for raising the output, the stable yields that guarantees the oil field, rational and effective prevention oil field fouling has become one of important subject of petroleum industry.
For reducing the loss that the oil field fouling brings, adding Scale inhibitors becomes the direct mode that prevents or stop incrustation scale to generate.At present, the corrosion inhibiting and descaling agent that use in the oil field is to be main with organic phospho acid, i.e. ATMP (ATMP), HEDP (hydroxy ethylidene phosphonic acids).Because a large amount of uses of phosphorous Scale inhibitors are easy to cause the eutrophication of water surrounding, and the eubiosis is brought very big influence, are substituted by low-phosphorous, without phosphorus novel Scale inhibitors gradually in recent years.The notion refigure of Green Chemistry the developing direction of water conditioner, develop low-phosphorous, without phosphorus and the good Scale inhibitors of biodegradable performance also becomes in recent years the hot subject of corrosion inhibiting and descaling agent development aspect both at home and abroad.
Because nontoxic inhibition and the scale-inhibiting properties of having concurrently; Good water-solubility and utilize after can be efficiently and stably by mikrobe, fungus degrading final product for environmental sound; SAP 73 and poly-epoxy succinic acid are considered to a kind of environmentally friendly real green water conditioner; Have scale inhibition, inhibition dual function concurrently, see from the document of delivering at present, the inhibition of different molecular weight, scale-inhibiting properties have very big difference.Therefore, when studying polymerization process to its molecular weight and performance impact, the research to their verivates in recent years also begins to increase.
Mainly concentrate on research in disclosed SAP 73 and the poly-epoxy succinic acid patent to its scale-inhibiting properties; And it is less to the improved related patent U.S. Patent No. of polymers functionality on its synthetic basis; Limited the development of green polymer Scale inhibitors, therefore sought to develop green polymer Scale inhibitors significant.
Summary of the invention
One of the object of the invention is to provide a kind of oil-field water treatment agent copolymer MA-AMPS.This multipolymer is that reactant obtains polymerization single polymerization monomer with MALEIC ANHYDRIDE MA and 2-acrylic amide-2-methyl propane sulfonic acid AMPS, forms through polyreaction again.
Two of the object of the invention is to provide the preparation method of this multipolymer.
For realizing above-mentioned purpose, reaction mechanism of the present invention is:
N representes the integer of polymerization degree ， Wei ≧ 2 in the formula, and M is H, Na, K, NH
4 +Or its mixture.
According to above-mentioned mechanism, the present invention adopts technical scheme to be:
A kind of copolymer MA-AMPS; It is characterized in that this multipolymer is is that reactant obtains polymerization single polymerization monomer with maleic anhydride MA and 2-acrylic amide-2-methyl propane sulfonic acid AMPS; The linear random copolymer that forms through polyreaction again, wherein two-part mass ratio is 9.8 ~ 9.9:10.35 ~ 10.362.
A kind of method for preparing above-mentioned copolymer MA-AMPS is characterized in that the concrete steps of this method are:
(1) maleic anhydride and the 2-acrylic amide-2-methyl propane sulfonic acid mass ratio by 9.8 ~ 9.9:10.35 ~ 10.362 is dissolved in the deionized water, at 85 ℃ ~ 95 ℃ reaction 3 ~ 3.5h down;
(2) temperature is controlled at 40 ℃ ~ 55 ℃; And pH to 11 ~ 13 of regulating step a gained solution, be warmed up to 55 ~ 60 ℃, press 1.6 ~ 1.7% of maleic anhydride and 2-acrylic amide-2-methyl propane sulfonic acid total mass and add sodium wolframate; Behind reaction 0.5 ~ 1h; Slowly drip 76 ~ 78% hydrogen peroxide of maleic anhydride and 2-acrylic amide-2-methyl propane sulfonic acid total mass, epoxidation reaction 1.5 ~ 2h is carried out in regulator solution pH to 5 ~ 7 under 70 ~ 75 ℃;
(3) be warming up to 80 ~ 90 ℃, add 15% ~ 20% polymerizing agent Potassium Persulphate of monomer total mass, polyreaction 1 ~ 2h promptly makes copolymer MA-AMPS bullion, then through filter purify copolymer MA-AMPS.
The polymerization temperature of above-mentioned step (3) is controlled at 88 ~ 92 ℃;
Polymerizing agent Potassium Persulphate add-on is 19 ~ 19.4% of a monomer total mass in the above-mentioned step (3).
Compare with existing synthetic technology, the invention has the advantages that: polymerizing agent consumption, polymerization temperature and polymerization time after the optimization, can make raw material reaction more thorough, improved transformation efficiency; Suitable polymerization temperature and polymerization time had both been practiced thrift cost, save time again, and building-up process did not have any waste liquid and produce, and final product need not to separate once more, thereby reduces production costs, and realizes green production.
Copolymer MA-AMPS of the present invention is a kind of oil-field water treatment agent with premium properties, and the product of processing is without phosphorus, nontoxic, harmless, helps environment protection, can steady in a long-termly preserve, and has wide oil field industrial market application prospect.
Description of drawings
Fig. 1 various polymerization agent consumption is to the influence of scale inhibition effect
Fig. 2 various polymerization temperature is to the influence of scale inhibition effect
Fig. 3 various polymerization time is to the influence of scale inhibition effect
Fig. 4 modified poly-epoxy succinic acid infared spectrum.
Embodiment
Embodiment 1: in the four-hole boiling flask that spherical condensating tube, tap funnel and TM are housed, add 9.8g MALEIC ANHYDRIDE and 30ml deionized water, treat that MALEIC ANHYDRIDE dissolves fully after, add 10.35g 2-acrylic amide-2-methyl propane sulfonic acid; Be warming up to 90 ℃ then, react 3 h, after reaction finishes; Temperature is controlled at 40 ℃ ~ 50 ℃ slowly 50% the NaOH aqueous solution about adding 11ml, is warmed up to 55 ℃, press 3.5% of MALEIC ANHYDRIDE quality and add sodium wolframate; Behind the reaction 0.5h, slowly drip the hydrogen peroxide that mass ratio is a reaction-ure mixture 78%, use NaOH regulator solution pH to 6 ~ 6.5 simultaneously; Under 70 ℃, carry out epoxidation reaction 1.5h then, be warming up to 90 ℃ again, add polymerizing agent Potassium Persulphate 3.00g; Polyreaction 1h, behind the stopped reaction, the solution light yellow viscous liquid.
Embodiment 2: in the four-hole boiling flask that spherical condensating tube, tap funnel and TM are housed, add 9.8g MALEIC ANHYDRIDE and 30ml deionized water, treat that MALEIC ANHYDRIDE dissolves fully after, add 10.35g 2-acrylic amide-2-methyl propane sulfonic acid; Be warming up to 90 ℃ then, reacted 3 hours, after reaction finishes; Temperature is controlled at 40 ℃ ~ 50 ℃ NaOH aqueous solution that slowly add 11ml 50%, is warmed up to 55 ℃, press 3.5% of MALEIC ANHYDRIDE quality and add transition-metal catalyst; Behind the reaction 0.5h, slowly drip the hydrogen peroxide that mass ratio is a reaction-ure mixture 78%, use NaOH regulator solution pH to 6 ~ 6.5 simultaneously; Under 70 ℃, carry out epoxidation reaction 1.5h then, be warming up to 90 ℃ again, add polymerizing agent Potassium Persulphate 3.90g; Polyreaction 1h, behind the stopped reaction, the solution light yellow viscous liquid.
Embodiment 4:
In the four-hole boiling flask that spherical condensating tube, tap funnel and TM are housed, add 9.8g MALEIC ANHYDRIDE and 30ml deionized water, treat that MALEIC ANHYDRIDE dissolves fully after, add 2-acrylic amide-2-methyl propane sulfonic acid of 10.35 g; Be warming up to 90 ℃ then, react 3 h, after reaction finishes; Temperature is controlled at 40 ℃ ~ 50 ℃ 50% NaOH aqueous solution that slowly add 11ml, is warmed up to 55 ℃, press 3.5% of MALEIC ANHYDRIDE quality and add transition-metal catalyst; After reacting 0.5 h, slowly drip the hydrogen peroxide that mass ratio is a reaction-ure mixture 78%, use NaOH regulator solution pH to 6 ~ 6.5 simultaneously; Under 70 ℃, carry out epoxidation reaction 1.5 h then, be warming up to 90 ℃ again, add polymerizing agent Potassium Persulphate 4.10 g; Polyreaction 1 h, behind the stopped reaction, the solution light yellow viscous liquid.
Be the synthesis condition optimization experiment below, be primarily aimed at polymerization stage and carry out condition optimizing, with product to CaCO
3Scale inhibition performance is a standard:
(1) consumption of polymerizing agent Potassium Persulphate: after reaction got into polymerization stage, 90 ℃ of polymerization temperatures under the polymerization time 2h condition, were inquired into the influence of various polymerization agent consumption to the lime carbonate scale inhibition effect, and scale inhibition performance is seen Fig. 1 under the condition of each various polymerization agent dosage.Can be known that by Fig. 1 along with the increase gradually of polymerizing agent dosage, the scale inhibition performance of polymerisate begins to increase and increase gradually with polymerizing agent, when consumption reached 3.90 g, the polymerisate scale-inhibiting properties was best; When continuing to increase polymerizing agent, its scale-inhibiting properties is on a declining curve.Possibly be that the polymerizing agent consumption is very few, the polymerization degree of synthetic polymer is too little, and polymerizing agent is too much; Cause the polymerization degree of polymkeric substance too big again; And the polymerization degree of polymerisate is big or hour, its scale-inhibiting properties is all relatively poor, has only just to have scale-inhibiting properties preferably within the specific limits.
(2) temperature of polyreaction: after reaction gets into polymerization stage, under the polymerization time 2 h conditions, inquire into the influence of various polymerization agent temperature to the lime carbonate scale inhibition effect, scale inhibition performance is seen Fig. 2 under the condition of each various polymerization agent temperature.As shown in Figure 2, polymerization temperature also is an important factor that influences the product scale-inhibiting properties.The scale-inhibiting properties of product is relatively poor when polymerization temperature is lower than 80 ℃, and temperature rising scale-inhibiting properties increases; When temperature was higher than 80 ℃, the scale-inhibiting properties of product raise with temperature and descends on the contrary.This possibly be because the lesser temps polyreaction is too slow, and the hydrolysis rate of reaction monomers causes scale inhibition effect relatively poor greater than polymerization velocity at this moment; Along with temperature raises, polymerization velocity is gradually greater than hydrolysis rate, and scale inhibition effect strengthens thereupon; And the too high polymerization degree that causes of temperature is excessive, and the product scale-inhibiting properties descends.
(3) time of polyreaction: after reaction got into polymerization stage, 90 ℃ of polymerization temperatures were inquired into the influence of various polymerization agent time to the lime carbonate scale inhibition effect, and scale inhibition performance is seen Fig. 3 under the condition of each various polymerization agent throwing time.Can be known that by Fig. 3 experimental result polymerization time scale-inhibiting properties between 1 ~ 2h is better, be below or above this scope, performance is not good.Possibly be because polymerization time is too short, and the polymerization degree is less, and the overlong time polymerization degree is excessive, thereby all can causes negatively influencing the scale-inhibiting properties of polymerisate.
(4) orthogonal test: can confirm the scope of each condition by time 3 factors of the temperature of the consumption of above-mentioned polymerizing agent Potassium Persulphate, polyreaction and polyreaction, for the optimum synthesis condition that obtains reacting, with resistance CaCO
3The dirt performance has been carried out the orthogonal test of four factors, three levels as detecting index, and research polymerizing agent consumption, polymerization temperature and polymerization time are to the influence of product scale-inhibiting properties; Research is learnt, selects in the level of test, considers reaction efficiency, and the polymerizing agent consumption is chosen as 3.85 g ~ 3.95 g, and polymerization temperature is selected 70 ℃ ~ 90 ℃, and polymerization time is elected 0.5 h ~ 1.5 h as.
Test detected the rangeability of index when extreme difference R value reaction factor changed, and promptly extreme difference is big more, and this factor is big more to the influence of index.Can be drawn by the experimental study result, the importance of three factors is followed successively by polymerization temperature＞polymerization time＞polymerizing agent consumption, has also drawn the optimum value of each condition simultaneously.The scale inhibition performance that is drawn preferred plan by proof test is 71.75%.
Claims (5)
1. copolymer MA-AMPS; It is characterized in that this multipolymer is is that reactant obtains polymerization single polymerization monomer with maleic anhydride MA and 2-acrylic amide-2-methyl propane sulfonic acid AMPS; The linear random copolymer that forms through polyreaction again, wherein two-part mass ratio is 9.8 ~ 9.9:10.35 ~ 10.362.
2. method for preparing copolymer MA-AMPS according to claim 1 is characterized in that the concrete steps of this method are:
(1) maleic anhydride and the 2-acrylic amide-2-methyl propane sulfonic acid mass ratio by 9.8 ~ 9.9:10.35 ~ 10.362 is dissolved in the deionized water, at 85 ℃ ~ 95 ℃ reaction 3 ~ 3.5h down;
(2) temperature is controlled at 40 ℃ ~ 55 ℃; And pH to 11 ~ 13 of regulating step a gained solution, be warmed up to 55 ~ 60 ℃, press 1.6 ~ 1.7% of maleic anhydride and 2-acrylic amide-2-methyl propane sulfonic acid total mass and add sodium wolframate; Behind reaction 0.5 ~ 1h; Slowly drip 76 ~ 78% hydrogen peroxide of maleic anhydride and 2-acrylic amide-2-methyl propane sulfonic acid total mass, epoxidation reaction 1.5 ~ 2h is carried out in regulator solution pH to 5 ~ 7 under 70 ~ 75 ℃;
(3) be warming up to 80 ~ 90 ℃, add 15% ~ 20% polymerizing agent Potassium Persulphate of monomer total mass, polyreaction 1 ~ 2h promptly makes copolymer MA-AMPS bullion, then through filter purify copolymer MA-AMPS.
3. method according to claim 2 is characterized in that the polymerization temperature of described step (3) is controlled at 88 ~ 92 ℃.
4. method according to claim 2 is characterized in that polymerizing agent Potassium Persulphate add-on is 19 ~ 19.4% of a monomer total mass in the described step (3).
5. method according to claim 2 is characterized in that the polymerization time 1 ~ 1.2h in the described step (3).
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| CN2012102092070A CN102702427A (en) | 2012-06-25 | 2012-06-25 | Biopolymer MA (maleic anhydride)-AMPS (2-acrylamido-2-methyl propane sulfonic acid) water treatment agent and preparation method of biopolymer AM-AMPS water treatment agent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613703A (en) * | 2013-12-18 | 2014-03-05 | 东华大学 | Polyacrylonitrile copolymer and preparation method thereof |
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- 2012-06-25 CN CN2012102092070A patent/CN102702427A/en active Pending
Non-Patent Citations (1)
| Title |
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| 荆国华等: "《MA-AMPS共聚物的制备及其性能研究》", 《水处理技术》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613703A (en) * | 2013-12-18 | 2014-03-05 | 东华大学 | Polyacrylonitrile copolymer and preparation method thereof |
| CN103613703B (en) * | 2013-12-18 | 2016-01-06 | 东华大学 | A kind of polyacrylonitrile copolymer and preparation method thereof |
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Application publication date: 20121003 |