CN105647511A - Acidification additive and preparation method thereof - Google Patents
Acidification additive and preparation method thereof Download PDFInfo
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- CN105647511A CN105647511A CN201610212891.6A CN201610212891A CN105647511A CN 105647511 A CN105647511 A CN 105647511A CN 201610212891 A CN201610212891 A CN 201610212891A CN 105647511 A CN105647511 A CN 105647511A
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Abstract
The invention provides an acidification additive. The acidification additive has a structure shown in the formula I, and in the formula I, the ratio of X to Y to Z is (0.4-0.7):(30-40):(60-70). The acidification additive has good compatibility and a good slow-release property and cannot generate precipitates in the use process. Besides, the thermal stability and the heat-resisting performance of the acidification additive are better. The invention provides a preparation method of the acidification additive. The preparation method comprises steps as follows: acrylamide, hexadecyl dimethyl allyl ammonium chloride and methyl acrylyl ethyl trimethyl ammonium chloride have a polymerization reaction under the action of an initiator, and the acidification additive is obtained and has the structure shown in the formula I, wherein acrylamide has a structure shown in the formula II, hexadecyl dimethyl allyl ammonium chloride has a structure shown in the formula III, and methyl acrylyl ethyl trimethyl ammonium chloride has a structure shown in the formula IV.
Description
Technical field
The present invention relates to petroleum gas technical field of operation, particularly relate to a kind of acidifying additive and preparation method thereof.
Background technology
At present, China has exploited totally in main Thief zone oil field, and the recovery ratio therefore improving low pressure and low permeability stratum is extremely urgent, and the transformation on low pressure and low permeability stratum generally adopts mechanism of acidification measure. Acidification technique is well production increment, stable yields, and water injection well is surely noted, one of the main technique measure of augmented injection. Acidification technique utilizes acid solution to remove producing well, the shaft bottom of water injection well is polluted, and in the permeability of renwing stratum or corrosion stratum, rock cement is to improve the volume increase of in-place permeability. Acidification technique can be divided into pickling, matrix acidifying (or hole acidifying) and fracture acidizing by technical process, in the process of conventional acid acidifying, acid-rock reaction speed is generally very fast, and penetration range is short, near wellbore zone biology injury can only be eliminated, it is impossible to reach the effect of deep acidification.
In order to reduce the response speed of acid rock, develop different retarded acids with conventional acid for reaction acid, as: gel acid, emulsified acid, active acid, foamed acid, change mucic acid etc. Wherein, gel acid is also referred to as viscous acid, and viscous acid improves the viscosity of acid by adding thickening agent. Viscous acid is a kind of macromolecule acid solution, and the thickening agent of employing mainly has cellulose family, acrylic amide and biopolymer class etc., and its advantage is for can effectively stop H+Diffusion rate, thus reduce acid rock response speed; But this retarded acid viscosity is big, injecting stratum difficulty, the property sheared is sensitive, broken glue difficulty in residual acid, it is easy to reservoir is caused secondary injury.
Emulsified acid is under the effect of emulsifying agent and co-emulsifier, by oil and acid according to the Water in Oil emulsion of certain proportions, it is common to use the emulsion be oil being foreign minister. Emulsified acid is after entering stratum, oil phase just separates acid solution and rock, thus having delayed the reaction of acid solution and rock, it forms oil film by emulsion at rock surface, acid solution will not directly contact with crag, it is necessary to just can react to reach slow effect through oil film interface.Emulsified acid leak-off is little, viscosity is high, it is adaptable to fracture acidizing, can form long and wide crack, but emulsified acid construction friction is higher, causes operation pressure high, and discharge capacity is low, and relatively costly.
Active acid is also called chemically retarded acid, refers to addition surfactant in acid solution, or adds and can generate CO with acid-rock reaction2Form the surfactant of stable foam. The mechanism of action of active acid be SURFACTANT ADSORPTION at formation fracture wall, to reach to delay the effect of acid-rock reaction speed. It is poor that active acid controls leak-off, it is adaptable to acid-rock reaction speed, by the low temperature dolomite stratum of granule surface contral, combines with multi-stage alternate injection technique and just can be used for middle temperature dolostone reservoirs.
Foamed acid technique is air, N2Or CO2Deng inflation or the technique making the foam system that acid solution is formed carry out formation acidizing that gasifies. Foamed acid is made up of acid solution, gas, foaming agent, foam stabilizer, water-soluble polymer etc. Foamed acid has that liquid content is low, apparent viscosity is high, filter loss is little, can effectively slow down acid-rock reaction speed the advantage such as the row of returning rapidly, but under the high temperature conditions, the stability of foamed acid reduces, and acid liquid loss amount increases, thus affecting retarded acidizing effect.
Become the novel acid fluid system of one that mucic acid is current carbonate reservoir acid fracturing, to controlling, acid liquid loss is extremely effective, become mucic acid and both there is the superperformance of viscous acid, can under equal conditions reduce again the filter loss (more than 50%) of acid solution, thus reaching the leak-off level of non-reacted fluid, but the acid that becomes sticky is more sensitive to hydrogen sulfide, and range of application is restricted.
In sum, the retarded acid that prior art provides there is compatibility and slow property is poor, the shortcoming in use producing precipitation.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of acidifying additive and preparation method thereof, the acidifying additive that method provided by the invention prepares has good compatibility and slow property, and does not in use produce precipitation.
The invention provides a kind of acidifying additive, there is the structure shown in Formulas I:
Wherein, X:Y:Z is (0.4��0.7): (30��40): (60��70).
Preferably, X:Y:Z is (0.6��0.7): (30��35): (65��70).
Acidifying additive provided by the invention has good compatibility and slow property, and does not in use produce precipitation. Additionally, the heat stability of acidifying additive provided by the invention and heat-resisting property are better.
The preparation method that the invention provides a kind of acidifying additive, including:
Under the effect of initiator, acrylamide, cetyl allyl dimethyl ammonium chloride and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride being carried out polyreaction, obtain acidifying additive, described acidifying additive has the structure shown in Formulas I:
In Formulas I, X:Y:Z is (0.4��0.7): (30��40): (60��70);
Described acrylamide has the structure shown in Formula II:
Described cetyl allyl dimethyl ammonium chloride has the structure shown in formula III:
Described MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride has the structure shown in Formulas I V:
The mol ratio of described acrylamide, cetyl allyl dimethyl ammonium chloride and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is (60��70): (0.4��0.7): (30��40).
Preferably, described initiator is azo-initiator.
Preferably, the quality of described initiator is the 0.1%��0.5% of acrylamide, cetyl allyl dimethyl ammonium chloride and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride gross mass.
Preferably, the quality of described initiator is the 0.2%��0.3% of acrylamide, cetyl allyl dimethyl ammonium chloride and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride gross mass.
Preferably, the temperature of described polyreaction is 50 DEG C��70 DEG C.
Preferably, the temperature of described polyreaction is 55 DEG C��65 DEG C.
Preferably, the time of described polyreaction is 2 hours��9 hours.
Preferably, the time of described polyreaction is 7 hours��8 hours.
The acidifying additive that method provided by the invention prepares has good compatibility and slow property, and does not in use produce precipitation. Additionally, the heat stability of acidifying additive for preparing of method provided by the invention and heat-resisting property are better. It addition, acidifying additive preparation method technique provided by the invention is simple, raw material sources scope is wide, and reaction condition is gentle, and productivity is high.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, the accompanying drawing used required in embodiment or description of the prior art will be briefly described below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skill in the art, under the premise not paying creative work, it is also possible to obtain other accompanying drawing according to the accompanying drawing provided.
Fig. 1 is the infrared spectrum of the acidifying additive that the embodiment of the present invention 1 prepares;
Fig. 2 is the temperature resistance of the acidifying additive that the embodiment of the present invention 1 prepares and slow property test result;
Fig. 3 is the temperature resistance of the acidifying additive that the embodiment of the present invention 2 prepares and slow property test result;
Fig. 4 is the temperature resistance of the acidifying additive that the embodiment of the present invention 3 prepares and slow property test result.
Detailed description of the invention
Technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments. Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention.
The invention provides a kind of acidifying additive, there is the structure shown in Formulas I:
In Formulas I, X:Y:Z is (0.4��0.7): (30��40): (60��70).
Acidifying additive provided by the invention has the structure shown in Formulas I. In the present invention, in described Formulas I, X:Y:Z is (0.4��0.7): (30��40): (60��70), it is preferably (0.6��0.7): (30��35): (65��70), being more preferably 0.6:30:70, now the slow effect of acidifying additive is better.
The preparation method that the invention provides a kind of acidifying additive, including:
Under the effect of initiator, acrylamide, cetyl allyl dimethyl ammonium chloride and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride being carried out polyreaction, obtain acidifying additive, described acidifying additive has the structure shown in Formulas I:
In Formulas I, X:Y:Z is (0.4��0.7): (30��40): (60��70);
Described acrylamide has the structure shown in Formula II:
Described cetyl allyl dimethyl ammonium chloride has the structure shown in formula III:
Described MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride has the structure shown in Formulas I V:
The mol ratio of described acrylamide, cetyl allyl dimethyl ammonium chloride and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is (60��70): (0.4��0.7): (30��40).
Acrylamide, cetyl allyl dimethyl ammonium chloride and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, under the effect of initiator, are carried out polyreaction, obtain acidifying additive by the present invention. In the present invention, the temperature of described polyreaction is preferably 50 DEG C��70 DEG C, more preferably 55 DEG C��65 DEG C, more preferably 58 DEG C��62 DEG C, it is most preferred that be 60 DEG C. In the present invention, the time of described polyreaction is preferably 2 hours��9 hours, it is preferred to 7 hours��8 hours, more preferably 8 hours.
The present invention adds in acrylamide after preferably MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and cetyl allyl dimethyl ammonium chloride being mixed, and obtains mixture; In described mixture, add initiator carry out polyreaction, obtain acidifying additive.
In the present invention, described initiator is preferably azo-initiator, more preferably azo-bis-isobutyrate hydrochloride. In the present invention, described acrylamide (AM) has the structure shown in Formula II, has the amide group of good polymerizability and adsorptivity, and source is wide, and cost is low. In the present invention, described acrylamide preferably participates in polyreaction with the form of acrylamide aqueous solution. In the present invention, described cetyl allyl dimethyl ammonium chloride has the structure shown in formula III. In the present invention, described MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride has the structure shown in Formulas I V.
Acrylamide, cetyl allyl dimethyl ammonium chloride, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride are preferably reacted by the present invention in aqueous. In the present invention, described acrylamide, cetyl allyl dimethyl ammonium chloride and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride are preferably 15%��35% in the mass concentration of aqueous solution, it is more preferably 18%��30%, more preferably 20%��25%, it is most preferred that be 20%.
The source of described initiator, acrylamide, cetyl allyl dimethyl ammonium chloride and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is not had special restriction by the present invention, can be bought by market and obtain.
In the present invention, the mol ratio of described acrylamide, cetyl allyl dimethyl ammonium chloride and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is preferably (60��70): (0.4��0.7): (30��40), it is more preferably (65��70): (0.6��0.7): (35��40), it is most preferred that for 70:0.6:30. In the present invention, the Functionality, quality and appealing design of described initiator elects the 0.1%��0.5% of acrylamide, cetyl allyl dimethyl ammonium chloride and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride gross mass as, more preferably 0.2%��0.3%, it is most preferred that be 0.2%.
In the present invention, after described polyreaction completes, the present invention dries after preferably the polymerizate washing obtained being purified, pulverizes, and obtains acidifying additive. In the present invention, the reagent that described washing purifies is preferably ethanol, more preferably dehydrated alcohol. In the present invention, the number of times that described washing purifies is preferably 3��5 times. In the present invention, described dry temperature is preferably 45 DEG C��55 DEG C, more preferably 50 DEG C.
In the present invention, described acidifying additive has the structure shown in Formulas I, consistent with acidifying additive described in technique scheme, does not repeat them here.
Acidifying additive provided by the invention can be directly added into for formation acidizing in acid fluid system, and described acid fluid system is preferably hydrochloric acid system. In the present invention, the addition of described acidifying additive is preferably the 0.5%��1% of acid fluid system.In the present invention, described hydrochloric acid system preferably includes concentrated hydrochloric acid, corrosion inhibitors for acidic media, ferrous stability, anti-clayswelling agent and cleanup additive. In the present invention, the mass concentration of described concentrated hydrochloric acid is preferably 15%��25%, more preferably 20%. In the present invention, described corrosion inhibitors for acidic media is preferably the FL4-2 product that Chengdu Fei Er trick development corporation, Ltd. provides. In the present invention, described corrosion inhibitors for acidic media mass concentration in hydrochloric acid system is preferably 1%��1.5%, more preferably 1.2%��1.3%. In the present invention, described ferrous stability is preferably the FL4-7 product that Chengdu Fei Er trick development corporation, Ltd. provides. In the present invention, described ferrous stability mass content in hydrochloric acid system is preferably 0.8%��1.2%, more preferably 1%. In the present invention, described anti-clayswelling agent is preferably the mixture of triethylamine hydrochloride and ammonium chloride. In the present invention, the mass ratio of described triethylamine hydrochloride and ammonium chloride is preferably 1:1. In the present invention, described anti-clayswelling agent mass content in hydrochloric acid system is preferably 0.6%��0.9%, more preferably 0.7%��0.8%. In the present invention, described cleanup additive is preferably the FC-117 product that Shanghai Jian Hong Industrial Co., Ltd. provides. In the present invention, described cleanup additive mass content in hydrochloric acid system is preferably 0.08%��0.12%, more preferably 0.1%.
Acidifying additive provided by the invention is carried out infrared spectrum detection, and testing result is, acidifying additive provided by the invention has the structure shown in Formulas I.
Test the compatibility of acidifying additive provided by the invention by the following method:
Acidifying additive provided by the invention is joined in the concentrated hydrochloric acid that mass concentration is 20%, and add FL4-2 (corrosion inhibitors for acidic media), FL4-7 (ferrous stability), mass ratio are the triethylamine hydrochloride of 1:1 and the mixture (anti-clayswelling agent) of ammonium chloride and FC-117 (cleanup additive), obtain retarded acid working solution system; Described corrosion inhibitors for acidic media mass concentration in retarded acid working solution system is 1.2%, ferrous stability mass concentration in retarded acid working solution system is 1%, anti-clayswelling agent mass concentration in retarded acid working solution system is 0.8%, and cleanup additive mass concentration in retarded acid working solution system is 0.1%.
Each material in above-mentioned retarded acid working solution system does not produce precipitation hierarchical phenomenon after complete dissolution, it can be seen that acidifying additive provided by the invention has good compatibility.
According to the standard of SY/T5886-2012 " the acid-rock reaction static experiment in retarded acid method of evaluating performance ", test heat-resisting property and the retardative property of acidifying additive provided by the invention:
Prepare retarded acid working solution system according to the method described above;
Take the above-mentioned retarded acid working solution system of 30mL and be heated to 75 DEG C, the retarded acid working solution system after heating is carried out acid-rock reaction with marble sample contacts, gathers the CO generated2Volume, the preparation method of described marble sample is:
It is 5cm that marble is made floor space2Cylinder rock sample, then with epoxy resin, this rock sample is wrapped up, obtains marble sample, finally make marble only have a bottom surface and contact with acidifying additive outside.
Test result is, along with the CO that the carrying out of 75 DEG C of acid-rock reaction generates2Volume is gradually increased, but the speed increased is slow; It can be seen that acidifying additive provided by the invention slowly effective, temperature resistance ability is stronger.
The problem that the present invention is directed to deep acidification difficulty, from the slow principle of acid solution, it is provided that acidifying additive can effectively be adsorbed on the surface of rock, control H in acid solution+With the speed of rock surface, and in acid solution good fluidity, easily inject, without obvious tackified phenomenon, also there is the easily row of returning simultaneously, reduce the secondary injury that reservoir is caused.In acidifying additive molecule provided by the invention, main chain connects with C-C chain, at high temperature not easy fracture and degrade, rigid structure is strong, has good heat-resisting property; In the molecular structure of acidifying additive provided by the invention, there is amide group and the cation group of stronger adsorptivity so that polymer molecule can effectively be adsorbed on the surface of rock, such that it is able to form adsorbed film to delay acid-rock reaction speed.
Raw material used in following example of the present invention is commercial goods, the product of the AR specification that acrylamide used provides for Chengdu Ke Long chemical reagent factory, the product of the AR specification that MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride used provides for Chengdu Shunda profit polymer company limited, the product of the AR specification that azo diisobutyl amidine hydrochlorate used provides for her Jim Press Science and Technology Ltd., the product of the AR specification that dehydrated alcohol used provides for Chengdu Ke Long chemical reagent factory, the product of the AR specification that calcium carbonate used provides for Chengdu Ke Long chemical reagent factory, the product of the AR specification that hydrochloric acid used provides for Chengdu Ke Long chemical reagent factory.
Embodiment 1
Weigh the acrylamide (AM) of 5.00g in the beaker of 100mL, add the distilled water stirring and dissolving of 25.4g, obtain acrylamide aqueous solution; Take the beaker of a 50mL to weigh 6.26g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) and add in the distilled water of 15g and dissolve, obtain MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution; Take the beaker of the 3rd 50mL to weigh cetyl allyl dimethyl ammonium chloride (DMAAC-16) of 0.19g and add 5.00g water dissolution, obtain cetyl allyl dimethyl ammonium chloride aqueous solution; MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride solution and cetyl allyl dimethyl ammonium chloride aqueous solution are poured in acrylamide aqueous solution beaker, and it is added thereto to the azo diisobutyl amidine hydrochlorate of 0.0444g so as to dissolve, it is placed in the water-bath at 70 DEG C of temperature and reacts 5h, obtain gelatinous product, purify 3 times with absolute ethanol washing again, after temperature is dry 24h in 50 DEG C of baking ovens, pulverizes, obtain acidifying additive.
The acidifying additive that the embodiment of the present invention 1 is prepared carries out infrared spectrum detection, and testing result is as it is shown in figure 1, the infrared spectrum of acidifying additive that Fig. 1 is the embodiment of the present invention 1 to be prepared, as shown in Figure 1, and 3128cm-1For amide groups CONH2In N H antisymmetric stretching vibration absworption peak, 1675cm-1For the stretching vibration characteristic absorption peak of amidocarbonylation C=O, 1737cm in AM-1For the carbonylic stretching vibration characteristic absorption peak of ester bond, 1392cm-1And 951cm-1Respectively CH2��N(CH3)3The bending vibration absworption peak of methylene and the absworption peak of quaternary ammonium group, be the characteristic absorption peak of DMC, 1128cm-1Characteristic absorption peak for cetyl allyl dimethyl ammonium chloride (DMAAC-16) long chain alkyl group, it is known that, acidifying additive provided by the invention has the structure shown in Formulas I, and wherein X:Y:Z is 0.55:30:70.
Method described in technique scheme, the compatibility of the acidifying additive that the test embodiment of the present invention 1 prepares, test result is, the acidifying additive that the embodiment of the present invention 1 prepares has good compatibility.
Method described in technique scheme, the temperature resistance of the acidifying additive that the test embodiment of the present invention 1 prepares and slow property, the acidifying additive that the embodiment of the present invention 1 prepares mass content in retarded acid working solution system is 0.3%, test result is as shown in Figure 2, Fig. 2 is the temperature resistance of the acidifying additive that the embodiment of the present invention 1 prepares and slow property test result, as shown in Figure 2, along with the CO that the carrying out of 75 DEG C of acid-rock reaction generates2Volume is gradually increased, but the speed increased is slow;It can be seen that the embodiment of the present invention 1 preparation acidifying additive slowly effective, temperature resistance ability is stronger.
Embodiment 2
Weigh the acrylamide (AM) of 5.00g in the beaker of 100mL, add the distilled water stirring and dissolving of 25.4g, obtain acrylamide aqueous solution; Take the beaker of a 50mL to weigh 6.26g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) and add in the distilled water of 15g and dissolve, obtain MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution; Take the beaker of the 3rd 50mL to weigh cetyl allyl dimethyl ammonium chloride (DMAAC-16) of 0.22g and add 5.00g water dissolution, obtain cetyl allyl dimethyl ammonium chloride aqueous solution; MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride solution and cetyl allyl dimethyl ammonium chloride aqueous solution are poured in acrylamide aqueous solution beaker, and it is added thereto to the azo diisobutyl amidine hydrochlorate of 0.0392g so as to dissolve, it is placed in the water-bath at 70 DEG C of temperature and reacts 5h, obtain gelatinous product, purify 3 times with absolute ethanol washing again, after temperature is dry 24h in 50 DEG C of baking ovens, pulverizes, obtain acidifying additive.
The acidifying additive that the embodiment of the present invention 2 is prepared carries out infrared spectrum detection, and testing result is that the acidifying additive that the embodiment of the present invention 2 prepares has the structure shown in Formulas I, and wherein X:Y:Z is 0.64:30:70.
Method described in technique scheme, the compatibility of the acidifying additive that the test embodiment of the present invention 2 prepares, test result is, the acidifying additive that the embodiment of the present invention 2 prepares has good compatibility.
Method described in technique scheme, the temperature resistance of the acidifying additive that the test embodiment of the present invention 2 prepares and slow property, the acidifying additive that the embodiment of the present invention 2 prepares mass content in retarded acid working solution system is 0.4%, test result is as shown in Figure 3, Fig. 3 is the temperature resistance of the acidifying additive that the embodiment of the present invention 2 prepares and slow property test result, from the figure 3, it may be seen that the CO generated along with the carrying out of 75 DEG C of acid-rock reaction2Volume is gradually increased, but the speed increased is slow; It can be seen that the embodiment of the present invention 2 preparation acidifying additive slowly effective, temperature resistance ability is stronger.
Embodiment 3
Weigh the acrylamide (AM) of 5.00g in the beaker of 100mL, add the distilled water stirring and dissolving of 25.4g, obtain acrylamide aqueous solution; Take the beaker of a 50mL to weigh 6.26g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) and add in the distilled water of 15g and dissolve, obtain MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution; Take the beaker of the 3rd 50mL to weigh cetyl allyl dimethyl ammonium chloride (DMAAC-16) of 0.23g and add 5.00g water dissolution, obtain cetyl allyl dimethyl ammonium chloride aqueous solution; MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride solution and cetyl allyl dimethyl ammonium chloride aqueous solution are poured in acrylamide aqueous solution beaker, and it is added thereto to the azo diisobutyl amidine hydrochlorate of 0.0341g so as to dissolve, it is placed in the water-bath at 70 DEG C of temperature and reacts 5h, obtain gelatinous product, purify 3 times with absolute ethanol washing again, after temperature is dry 24h in 50 DEG C of baking ovens, pulverizes, obtain acidifying additive.
The acidifying additive that the embodiment of the present invention 3 is prepared carries out infrared spectrum detection, and testing result is that the acidifying additive that the embodiment of the present invention 3 prepares has the structure shown in Formulas I, and wherein X:Y:Z is 0.67:30:70.
Method described in technique scheme, the compatibility of the acidifying additive that the test embodiment of the present invention 3 prepares, test result is, the acidifying additive that the embodiment of the present invention 3 prepares has good compatibility.
Method described in technique scheme, the temperature resistance of the acidifying additive that the test embodiment of the present invention 3 prepares and slow property, the acidifying additive that the embodiment of the present invention 3 prepares mass content in retarded acid working solution system is 0.5%, test result is as shown in Figure 4, Fig. 4 is the temperature resistance of the acidifying additive that the embodiment of the present invention 3 prepares and slow property test result, from the figure 3, it may be seen that the CO generated along with the carrying out of 75 DEG C of acid-rock reaction2Volume is gradually increased, but the speed increased is slow; It can be seen that the embodiment of the present invention 3 preparation acidifying additive slowly effective, temperature resistance ability is stronger.
By embodiment 1��3 it can be seen that along with the carrying out of acid-rock reaction, the CO of generation2Volume is being gradually increased, when the different dosage of acidifying additive, and the CO of generation2Volume is different, and 0.4% acidifying additive reaction is the rapidest, and generates CO2Volume is many, then it represents that it is swift in response, and corrosion rate is more of a relatively high, and 0.3% and 0.5% reaction is more mild.
Embodiment 4��9
Weigh a certain amount of AM in beaker, add appropriate distilled water stirring and dissolving, obtain the AM aqueous solution that mass concentration is 20%; Take another beaker weigh a certain amount of DMC add distilled water dissolve, obtain the DMC aqueous solution that mass concentration is 20%; Take the 3rd beaker to weigh a certain amount of DMAAC-16 and add water and dissolve at a certain temperature, obtain the DMAAC-16 aqueous solution that mass concentration is 20%, by DMAAC-16 aqueous solution and DMC aqueous solution, and it is added thereto to a certain amount of azo diisobutyl amidine hydrochlorate, quality is AM, DMC and DMAAC-16 gross mass the 0.3% of described azo diisobutyl amidine hydrochlorate, in thermostat water bath, after synthesis, add the reaction that AM aqueous solution carries out 8 hours at 60 DEG C, obtain gelatinous product; The product absolute ethanol washing obtained is purified 3��5 times, until precipitation occurs, pulverizes after temperature is dry in 50 DEG C of baking ovens, obtain acidifying additive.
By standby after calcium carbonate washes clean, drying; The calcium carbonate taking about 6.00 grams is placed in the beaker of 150mL; The acidifying additive of 30mL is taken with graduated cylinder, it is poured slowly in the beaker filling calcium carbonate, and quickly stir with Glass rod to acid solution calcium carbonate is all infiltrated, with a small amount of distilled water flushing Glass rod front end, then seal beaker mouth with preservative film, be then placed in thermostat water bath, start timing, after reaction 15min, weighing and calculate corrosion rate after being dried by remaining calcium carbonate wash clean, the computing formula of described corrosion rate is:
According to The Ideal-Gas Equation:
NRT=PV
P pressure, Pa;
V gas volume, L/mol;
N molal weight, mol;
T absolute temperature, K;
R gas constant, Pa L/ (mol K);
CO2The gas that reaction produces can fully be condensed to 25 DEG C by gas collecting device, can calculate the molar volume of gas of 25 DEG C according to perfect condition equation, owing to all gas R value is all identical:
In formula: V0Ideal gas molal volume 22.4L/mol;
T0Ideal gas absolute temperature 273.15K;
V1Molar volume of gas when 25 DEG C, L/mol;
T1Absolute temperature 298.15K when 25 DEG C;
Can release molar volume of gas when 25 DEG C is:
Determine when 25 DEG C after molar volume of gas, determining acid rock erosion rate and residual acid concentration according to hydrochloric acid and marmorean reaction principle.
As follows by the erosion rate computational methods in the acid-rock reaction principle unit interval:
In formula: u acid rock erosion rate, (g/cm2Min);
n2The CO produced in unit interval2Molal weight;
V2The CO produced in unit interval2Volume, mL;
S acid-rock reaction contact area, cm2;
V1Molar volume of gas when 25 DEG C;
T unit erosion time.
The corrosion rate that AM in embodiment 4��9, the mol ratio of DMC and DMAAC-16 and final test obtain is as shown in table 1, and table 1 is reaction condition and the corrosion rate of the embodiment of the present invention 4��9.
Table 1 is reaction condition and the corrosion rate of the embodiment of the present invention 4��9
As shown in Table 1, as monomer ratio n (AM): n (DMC); When n (DMAAC-16) is for 70:30:0.6, reacting calcium carbonate is remaining at most, and the slow effect of acidifying additive is best.
Embodiment 10��14
Weigh a certain amount of AM in beaker, add appropriate distilled water stirring and dissolving, obtain the AM aqueous solution that mass concentration is 20%; Take another beaker weigh a certain amount of DMC add distilled water dissolve, obtain the DMC aqueous solution that mass concentration is 20%; Take the 3rd beaker to weigh a certain amount of DMAAC-16 and add water and dissolve at a certain temperature, obtain the DMAAC-16 aqueous solution that mass concentration is 20%, by DMAAC-16 aqueous solution and DMC aqueous solution, and it is added thereto to a certain amount of azo diisobutyl amidine hydrochlorate, described AM, DMC and DMAAC-16 mol ratio be 70:30:0.6, in thermostat water bath, after synthesis, add the reaction that AM aqueous solution carries out 8 hours at 60 DEG C, obtain gelatinous product; The product absolute ethanol washing obtained is purified 3��5 times, until precipitation occurs, pulverizes after temperature is dry in 50 DEG C of baking ovens, obtain acidifying additive.
Method described in embodiment 4 calculates corrosion rate.
The corrosion rate that in embodiment 10��15, the consumption of azo diisobutyl amidine hydrochlorate and final test obtain is as shown in table 2, and table 2 is reaction condition and the corrosion rate of the embodiment of the present invention 10��15.
The reaction condition of table 2 embodiment of the present invention 10��15 and corrosion rate
As shown in Table 2, when the quality of added initiator is AM, DMC and DMAAC-16 gross mass 0.2%, reacting calcium carbonate is remaining at most, and the slow effect of acidifying additive is best.
Embodiment 15��19
Weigh a certain amount of AM in beaker, add appropriate distilled water stirring and dissolving, obtain the AM aqueous solution that mass concentration is 20%; Take another beaker weigh a certain amount of DMC add distilled water dissolve, obtain the DMC aqueous solution that mass concentration is 20%; Take the 3rd beaker to weigh a certain amount of DMAAC-16 and add water and dissolve at a certain temperature, obtain the DMAAC-16 aqueous solution that mass concentration is 20%, by DMAAC-16 aqueous solution and DMC aqueous solution, and it is added thereto to a certain amount of azo diisobutyl amidine hydrochlorate, described AM, DMC and DMAAC-16 mol ratio be 70:30:0.6, quality is AM, DMC and DMAAC-16 gross mass the 0.2% of described azo diisobutyl amidine hydrochlorate, in thermostat water bath, after synthesis, add the reaction that AM aqueous solution carries out 8 hours under uniform temperature, obtain gelatinous product; The product absolute ethanol washing obtained is purified 3��5 times, until precipitation occurs, pulverizes after temperature is dry in 50 DEG C of baking ovens, obtain acidifying additive.
Method described in embodiment 4 calculates corrosion rate.
The corrosion rate that in embodiment 15��19, reaction temperature and final test obtain is as shown in table 3, and table 3 is reaction condition and the corrosion rate of the embodiment of the present invention 15��19.
The reaction condition of table 3 embodiment of the present invention 15��19 and corrosion rate
As shown in Table 3, when reaction temperature is 60 DEG C, reacting calcium carbonate is remaining at most, and the slow effect of acidifying additive is best.
Embodiment 20��24
Weigh a certain amount of AM in beaker, add appropriate distilled water stirring and dissolving, obtain AM aqueous solution; Take another beaker weigh a certain amount of DMC add distilled water dissolve, obtain DMC aqueous solution; Take the 3rd beaker to weigh a certain amount of DMAAC-16 and add water and dissolve at a certain temperature, obtain DMAAC-16 aqueous solution, by DMAAC-16 aqueous solution and DMC aqueous solution, and it is added thereto to azo diisobutyl amidine hydrochlorate, described AM, DMC and DMAAC-16 mol ratio be 70:30:0.6, quality is AM, DMC and DMAAC-16 gross mass the 0.2% of described azo diisobutyl amidine hydrochlorate, in thermostat water bath, after synthesis, add the reaction that AM aqueous solution carries out 8 hours at 60 DEG C, obtain gelatinous product; The product absolute ethanol washing obtained is purified 3��5 times, until precipitation occurs, pulverizes after temperature is dry in 50 DEG C of baking ovens, obtain acidifying additive.
Method described in embodiment 4 calculates corrosion rate.
The corrosion rate that in embodiment 20��24, the mass concentration of AM aqueous solution, DMC aqueous solution and DMAAC-16 aqueous solution and final test obtain is as shown in table 4, and table 4 is reaction condition and the corrosion rate of the embodiment of the present invention 20��24.
The reaction condition of table 4 embodiment of the present invention 20��24 and corrosion rate
As shown in Table 4, when the mass concentration of polymerization single polymerization monomer solution is 20%, reacting calcium carbonate is remaining at most, and the slow effect of acidifying additive is best.
Embodiment 25��32
Weigh a certain amount of AM in beaker, add appropriate distilled water stirring and dissolving, obtain the AM aqueous solution that mass concentration is 20%; Take another beaker weigh a certain amount of DMC add distilled water dissolve, obtain the DMC aqueous solution that mass concentration is 20%; Take the 3rd beaker to weigh a certain amount of DMAAC-16 and add water and dissolve at a certain temperature, obtain the DMAAC-16 aqueous solution that mass concentration is 20%, by DMAAC-16 aqueous solution and DMC aqueous solution, and it is added thereto to azo diisobutyl amidine hydrochlorate, described AM, DMC and DMAAC-16 mol ratio be 70:30:0.6, quality is AM, DMC and DMAAC-16 gross mass the 0.2% of described azo diisobutyl amidine hydrochlorate, in thermostat water bath, after synthesis, add AM aqueous solution at 60 DEG C carry out the reaction of certain time, obtain gelatinous product; The product absolute ethanol washing obtained is purified 3��5 times, until precipitation occurs, pulverizes after temperature is dry in 50 DEG C of baking ovens, obtain acidifying additive.
Method described in embodiment 4 calculates corrosion rate.
The corrosion rate that in embodiment 25��32, response time and final test obtain is as shown in table 5, and table 5 is reaction condition and the corrosion rate of the embodiment of the present invention 25��32.
The reaction condition of table 5 embodiment of the present invention 25��32 and corrosion rate
From table 1��table 5, the optimum synthesis condition of acidifying additive provided by the invention is: monomer ratio is n (AM): n (DMC): n (DMAAC-16) is 70:30:0.6, initiator content is the 0.2% of AM, DMC and DMAAC-16 gross mass, the mass concentration of monomer solution is 20%, reaction temperature is 60 DEG C, and the response time is 8 hours.
As seen from the above embodiment, the invention provides a kind of acidifying additive, have the structure shown in Formulas I, in Formulas I, X:Y:Z is (0.4��0.7): (30��40): (60��70). The preparation method that the invention provides a kind of acidifying additive, including: under the effect of initiator, acrylamide, cetyl allyl dimethyl ammonium chloride and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride are carried out polyreaction, obtains acidifying additive. Acidifying additive provided by the invention has good compatibility and slow property, and does not in use produce precipitation. Additionally, the heat stability of acidifying additive provided by the invention and heat-resisting property are better.
Claims (10)
1. an acidifying additive, has the structure shown in Formulas I:
Wherein, X:Y:Z is (0.4��0.7): (30��40): (60��70).
2. acidifying additive according to claim 1, it is characterised in that X:Y:Z is (0.6��0.7): (30��35): (65��70).
3. a preparation method for acidifying additive, including:
Under the effect of initiator, acrylamide, cetyl allyl dimethyl ammonium chloride and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride being carried out polyreaction, obtain acidifying additive, described acidifying additive has the structure shown in Formulas I;
Described acrylamide has the structure shown in Formula II:
Described cetyl allyl dimethyl ammonium chloride has the structure shown in formula III:
Described MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride has the structure shown in Formulas I V:
In Formulas I, X:Y:Z is (0.4��0.7): (30��40): (60��70);
The mol ratio of described acrylamide, cetyl allyl dimethyl ammonium chloride and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride is (60��70): (0.4��0.7): (30��40).
4. method according to claim 3, it is characterised in that described initiator is azo-initiator.
5. method according to claim 3, it is characterised in that the quality of described initiator is the 0.1%��0.5% of acrylamide, cetyl allyl dimethyl ammonium chloride and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride gross mass.
6. method according to claim 5, it is characterised in that the quality of described initiator is the 0.2%��0.3% of acrylamide, cetyl allyl dimethyl ammonium chloride and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride gross mass.
7. method according to claim 3, it is characterised in that the temperature of described polyreaction is 50 DEG C��70 DEG C.
8. method according to claim 7, it is characterised in that the temperature of described polyreaction is 55 DEG C��65 DEG C.
9. method according to claim 3, it is characterised in that the time of described polyreaction is 2 hours��9 hours.
10. method according to claim 9, it is characterised in that the time of described polyreaction is 7 hours��8 hours.
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| CN110483689A (en) * | 2019-08-21 | 2019-11-22 | 西南石油大学 | A kind of acidification steering polymer, preparation method, acidified diverting agent |
| CN114380946A (en) * | 2020-10-22 | 2022-04-22 | 中国石油天然气股份有限公司 | Self-tackifying steering acid liquid thickener and preparation method and application thereof |
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| CN114380946A (en) * | 2020-10-22 | 2022-04-22 | 中国石油天然气股份有限公司 | Self-tackifying steering acid liquid thickener and preparation method and application thereof |
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