CN102453178A - synthesis process of biopolymer scale inhibitor with obviously enhanced antiscaling effect - Google Patents
synthesis process of biopolymer scale inhibitor with obviously enhanced antiscaling effect Download PDFInfo
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- CN102453178A CN102453178A CN2010105508873A CN201010550887A CN102453178A CN 102453178 A CN102453178 A CN 102453178A CN 2010105508873 A CN2010105508873 A CN 2010105508873A CN 201010550887 A CN201010550887 A CN 201010550887A CN 102453178 A CN102453178 A CN 102453178A
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- scale inhibitor
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- antiscaling effect
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Abstract
The invention discloses a synthesis process of biopolymer scale inhibitor with obviously enhanced antiscaling effect. The biopolymer scale inhibitor synthesis process capable of obviously enhancing antiscaling effect comprises the following steps: carrying out a reaction of an alkene monomer and acrylamide to obtain a mixture of polymerization reaction products; cooling so that the prepared polymerization reaction products are precipitated, filtering at vacuum to separate precipitate, washing and drying so as to obtain the product; and the like. According to the invention, the antiscaling effect can be obviously enhanced through controlling the proportion of the monomers; and the synthesis process has the advantages of simple process flow, high synthesis efficiency and low synthesis cost.
Description
Technical field
The present invention relates to a kind of synthesis technique, specifically be meant a kind of synthesis technique of copolymer scale inhibitor of remarkable enhancing antiscaling effect.
Background technology
In the crude oil production process, fouling is a kind of ubiquitous phenomenon.There is the down-hole oil tube fouling in many oil fields; When water content in crude oil is higher, the fouling in the collection transfer device of extraction liquid; Fouling in WIW and support equipment in the water flood recovery; High-temperature-hot-water, high-temperature-hot-water fouling in process furnace, waterflood-transmission line are annotated in viscous oil recovery; In complex oil displacing, the fouling on oil pipe and oil production equipment of extraction liquid; And so on.
Fouling has bigger influence to the ordinary production of oil well, and dirt deposition can stop up formation pore, crack on the stratum, causes permeability reduction, and crude production rate descends, when serious even cause oil well to stop production, to the lower oil reservoir influence of rate of permeation more very; When dirt deposition is on equipment such as pit shaft, oil pipe, oil well pump, waterflood system, gathering system, heating system; Can cause equipment not run well; Heat transfer efficiency reduces; Cause throughput to descend, and fouling also can cause the corrosion of equipment and pipeline, cause serious economy loss to the oil field.
To the various fouling situations in oil field, the way of two types of solutions is arranged: the one, scale removal; The 2nd, antiscale.Scale removal is a kind of remedial measures, and during scale removal, it has produced the underproduction and corrosion on Equipment, has caused bigger financial loss, therefore, prevents that the generation of dirt is only a kind of good measure.In the method for antiscale, be simple, effective, convenient, the economic method that people generally acknowledge with the chemical agent antiscale.Therefore each oil field all is directed against the chemical scale inhibition agent of block characteristics research adaptation different condition separately.And develop the just common objective generally pursued of each oil field especially of scale inhibitor efficiently.
The modal dirty type in oil field has lime carbonate, terra alba, calcium sulfate, permanent white and Strontium Sulphate.And the Strontium Sulphate of trace often is present in a large amount of permanent white, is difficult to separate them.
The major cause of fouling is 5 water intermingling because pressure or temperature change, evaporation or two kinds mismatch, and makes the inorganic salt that originally are present in the aqueous solution with ionic condition reach hypersaturated state, has surpassed their solubleness and crystallizes out dirt.
Be prone in the scaling salts at above several kinds, no matter under what temperature, the solubleness of permanent white and Strontium Sulphate is all very little, and permanent white is one of the most insoluble material in the oil field.The solubleness of permanent white increases along with the rising of temperature and pressure, but the amplitude of this influence is very little.For example, in the time of 25 ℃, the solubleness of permanent white is 2.3mg/L, and when temperature was brought up to 94 ℃, solubleness only was increased to 3.9mg/L.The influence of pressure is insignificant especially.Saltiness has bigger influence to permanent white solubleness in the water, when NaCl in the water when 1g/L is increased to 100g/L, solubleness increases by 10～15 times.Has only Ba in the oil field flood pattern
2+And SO
4 2-These two kinds of ions will generate barium sulfate scale.In many cases, Ba
2+And Sr
2+Together deposition forms barium and strontium sulfate, generally speaking, contains Strontium Sulphate 1.2%～15.9% in the barium sulfate scale approximately.So, in the water filling stratum, sulfate scale mainly be injection water and the stratum Ca that is rich in
2+, Ba
2+And Sr
2+Mixing back generation chemical reaction generation deposition causes.
The antiscale mechanism more complicated of scale inhibitor, along with the big quantity research of precipitation process kinetics, the dirty predictive model of one-tenth and various preventing foulings, making into the research of dirty mechanism and the control of fouling has had big progress.It is generally acknowledged between dirty material and the solution and have running balance, scale inhibitor can be adsorbed onto on the dirty material, and the growth and the dissolved running balance of influence dirt.
The antiscale mechanism of scale inhibitor mainly contains following several kinds:
(1) lattice distortion
When the lime carbonate crystallite is grown up according to certain lattice arrangement, compact crystallization and hard.After adding scale inhibitor, scale inhibitor is adsorbed on the crystal and is entrained in the dot matrix of lattice, and the crystallization of inorganic scale has been formed interference, crystal is distorted, or make the inner stress increase of macrocrystal, thereby make crystal be easy to break, and has hindered dirty growth.
(2) complexing solubilising
The complexing solublization is that scale inhibitor can form stable soluble chelating thing with barium, strontium ion in water, more barium, strontium ion is stabilized in the water, thereby increased the solubleness of barium, strontium salt, suppressed dirty deposition.
(3) cohesion and dispersion
The anionic scale inhibitor, the physical and chemical adsorption phenomenon can take place in the negatively charged ion of the generation of in water, dissociating when colliding with the lime carbonate crystallite, make the surface of microcrystallite form electrostatic double layer, makes it electronegative.Because of the crystallite of the adsorbable a plurality of identical charges of chain-like structure of scale inhibitor, electrostatic repulsion can stop crystallite to collide each other, thereby has avoided the formation of macrocrystal.Meet other Scale inhibitors in adsorbed product and divide the period of the day from 11 p.m. to 1 a.m, the crystal that has adsorbed is shifted in the past, the uniform crystal particles dispersion phenomenon occurs, thereby hindered the collision of intercrystalline and crystal grain and metallic surface, reduced the nucleus number in the solution, lime carbonate is stabilized in the solution.
(4) regenerate-gather from the release film hypothesis
The acrylic acid or the like Scale inhibitors can form a kind of on the metal heat transfer surface and the film coprecipitation of mineral crystal particle, after this film is increased to certain thickness, on heat-transfer surface, breaks, and opens heat-transfer surface with a certain size dirty leafing.Because the continuous formation of this film and breaking is suppressed the growth of dirt layer.
(5) Effect of Electric Double Layer mechanism
For the antiscale mechanism of organic phosphine acids scale inhibitor, people such as Gill have proposed Effect of Electric Double Layer mechanism.Think that the effect of scale inhibitor is enrichment near the diffusion boundary layer the growth nucleus, form electrostatic double layer and hinder dirty lewis' acid bunch coalescence in the metallic surface.They think, combining between Scale inhibitors and the nucleus (or dirty matter molecular clustering) is unsettled.
(6) threshold effect
In water, add several kinds of Scale inhibitorss (order of magnitude is every liter several milligrams), can be with than being stabilized in the water by the much higher calcium ion of stoichiometric ratio.The reason that produces this phenomenon is that the huge legendary turtle of negatively charged ion and the metallic cation of Scale inhibitors merges is non-ly undertaken by stoichiometric ratio, is because CaCO
3After going up Scale inhibitors, crystallite absorption can suppress CaCO
3Crystalline is separated out.
More than several kinds of mechanism express the level of understanding of present people to scale effect; Because they all have supposition in various degree; Thereby people are when analyzing concrete scale problems; The compound action that often scale effect is summed up as multiple mechanism, this has reflected that current people are also quite general to the understanding of inhibitor mechanism.Because fouling itself is the process of a complicacy, the intervention of Scale inhibitors makes this process become complicated more.
In the technology of synthetic copolymer scale inhibitor, vinyl monomer is different with the acrylic amide proportioning, and each group proportion is different in the polymer macromolecule chain, and the polymkeric substance anti-scaling property is different.As far as scale inhibitor, when having only ratio when each group in the macromolecular chain suitable, polymkeric substance just has good antiscaling effect.
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art; A kind of synthesis technique of copolymer scale inhibitor is provided; The synthesis technique of this copolymer scale inhibitor is through the control monomer ratio; Thereby can significantly strengthen antiscaling effect, and flow process is simple, combined coefficient is high, synthetic cost is low.
The object of the invention is realized through following technical proposals: a kind of synthesis technique of copolymer scale inhibitor of remarkable enhancing antiscaling effect may further comprise the steps:
(a) in reaction vessel, vinyl monomer, acrylic amide are added dissolved in distilled water, the mol ratio of said vinyl monomer and acrylic amide is 4: 6～7: 3;
(b) add initiator, under constantly stirring, make vinyl monomer and acrylic amide copolymerization;
(c) be cooled to room temperature, obtain the polymeric reaction product mixture;
(d) in the polymeric reaction product mixed system, add an amount of ethanol, stir, leave standstill, make the polymeric reaction product deposition that makes, this reaction product deposition is the copolymer scale inhibitor.
In the said step (b), initiator is an ammonium persulphate.
After said step (d) finishes, the reaction product deposition is washed and drying.
The reaction product deposition is washed through absolute ethyl alcohol.
After the reaction product washing of precipitate, carry out drying through thermostat container.
In the said step (a), the mol ratio of vinyl monomer and acrylic amide is 6: 4.
In sum, the invention has the beneficial effects as follows: through the control monomer ratio, thereby can significantly strengthen antiscaling effect, and flow process is simple, combined coefficient is high, synthetic cost is low.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is done further detailed description, but embodiment of the present invention is not limited only to this.
Embodiment:
The synthesis technique of the copolymer scale inhibitor of a kind of remarkable enhancing antiscaling effect that the present invention relates to may further comprise the steps:
(a) in reaction vessel, vinyl monomer, acrylic amide are added dissolved in distilled water, the mol ratio of said vinyl monomer and acrylic amide is 4: 6～7: 3;
(b) add initiator, under constantly stirring, make vinyl monomer and acrylic amide copolymerization;
(c) be cooled to room temperature, obtain the polymeric reaction product mixture;
(d) in the polymeric reaction product mixed system, add an amount of ethanol, stir, leave standstill, make the polymeric reaction product deposition that makes, this reaction product deposition is the copolymer scale inhibitor.
In the said step (b), initiator is an ammonium persulphate.
After said step (d) finishes, the reaction product deposition is washed and drying.
The reaction product deposition is washed through absolute ethyl alcohol.
After the reaction product washing of precipitate, carry out drying through thermostat container.
In the said step (a), the mol ratio of vinyl monomer and acrylic amide is 6: 4.
In order to obtain best monomer ratio, the present invention has done the influence test of monomer ratio to antiscaling effect, and test-results is as shown in the table:
Visible by last table, when not adding vinyl monomer in the polymerization system, i.e. what polymerization obtained is SEPIGEL 305, and it has certain scale effect to barium, strontium dirt, but antiscaling effect is very low; Along with the continuous increase of vinyl monomer consumption, antiscaling rate is in continuous increase, and when the mol ratio of vinyl monomer and acrylic amide in the time of 6: 4, antiscaling rate reaches peak.Can learn that from the intrinsic viscosity of homopolymer vinyl monomer is than the difficult polymerization of acrylic amide, along with the consumption increase of vinyl monomer, the intrinsic viscosity of its polymkeric substance reduces, and reflects that the polymeric molecular weight is constantly reducing.The too big or too little antiscaling effect that all is unfavorable for scale inhibitor of molecular weight.The inhibitor mechanism of SEPIGEL 305 scale inhibitor is main with sequestering action simultaneously, and along with the increase of vinyl monomer consumption, the anti-scaling property group content increases in the multipolymer.From antiscaling effect, the present invention is decided to be 4: 6 with the mol ratio of vinyl monomer and acrylic amide～and 7: 3, and preferred 6: 4.
Above-mentioned synthesis technique passes through the control monomer ratio, thereby can significantly strengthen antiscaling effect, and flow process is simple, combined coefficient is high, synthetic cost is low.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction, and every foundation technical spirit of the present invention, any simple modification, equivalent variations to above embodiment did all fall within protection scope of the present invention.
Claims (6)
1. a synthesis technique that significantly strengthens the copolymer scale inhibitor of antiscaling effect is characterized in that, may further comprise the steps:
(a) in reaction vessel, vinyl monomer, acrylic amide are added dissolved in distilled water, the mol ratio of said vinyl monomer and acrylic amide is 4: 6～7: 3;
(b) add initiator, under constantly stirring, make vinyl monomer and acrylic amide copolymerization;
(c) be cooled to room temperature, obtain the polymeric reaction product mixture;
(d) in the polymeric reaction product mixed system, add an amount of ethanol, stir, leave standstill, make the polymeric reaction product deposition that makes, this reaction product deposition is the copolymer scale inhibitor.
2. the synthesis technique of the copolymer scale inhibitor of a kind of remarkable enhancing antiscaling effect according to claim 1 is characterized in that, in the said step (b), initiator is an ammonium persulphate.
3. the synthesis technique of the copolymer scale inhibitor of a kind of remarkable enhancing antiscaling effect according to claim 1 is characterized in that, after said step (d) finishes, the reaction product deposition is washed and drying.
4. the synthesis technique of the copolymer scale inhibitor of a kind of remarkable enhancing antiscaling effect according to claim 3 is characterized in that, the reaction product deposition is washed through absolute ethyl alcohol.
5. the synthesis technique of the copolymer scale inhibitor of a kind of remarkable enhancing antiscaling effect according to claim 3 is characterized in that, after the reaction product washing of precipitate, carries out drying through thermostat container.
6. the synthesis technique of the copolymer scale inhibitor of a kind of remarkable enhancing antiscaling effect according to claim 1 is characterized in that, in the said step (a), the mol ratio of vinyl monomer and acrylic amide is 6: 4.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107531532A (en) * | 2015-05-08 | 2018-01-02 | 皇家飞利浦有限公司 | The application and recovery of scale inhibitor in household electrical appliance |
-
2010
- 2010-10-25 CN CN2010105508873A patent/CN102453178A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107531532A (en) * | 2015-05-08 | 2018-01-02 | 皇家飞利浦有限公司 | The application and recovery of scale inhibitor in household electrical appliance |
| US11014841B2 (en) | 2015-05-08 | 2021-05-25 | Koninklijke Philips N.V. | Application and recovery of scale inhibitors in domestic appliances |
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Application publication date: 20120516 |