CN102816277B - The preparation method of polyhydroxy polycarboxylic acid for acidifying - Google Patents
The preparation method of polyhydroxy polycarboxylic acid for acidifying Download PDFInfo
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Abstract
The present invention relates to the preparation method of acidifying polyhydroxy polycarboxylic acid. Be made up of following steps: (1) raw material by weight percentage, mix acrylic acid, maleic acid and PBTCA in airtight container, wherein acrylic acid accounts for that 20-40%, maleic acid account for 30-40%, PBTCA accounts for 30-40%; (2) will in container, pass into high pure nitrogen, container is positioned in water, and water-bath control reaction temperature is 50 DEG C to 60 DEG C; (3) by weight percentage, under the condition of continuous stirring, in 1～5h, slowly add to system the initator azodiisobutyronitrile that accounts for 3 kinds of sour gross weight 1-3%, add after initator, temperature can rise, and stops dripping when temperature arrives 80 DEG C, treat that temperature declines, continue again to drip initator, repeat above-mentioned steps and treat that temperature no longer rises, add initator; (4) continue to stir end after 4 hours. The polyhydroxy polycarboxylic acid acid fluid system that the present invention prepares can realize acidification deep penetration, effectively suppresses the generation of various secondary precipitations, and can effectively solve fouling, the antiscale problem of oil well.
Description
Technical field
The present invention relates to the preparation method of novel polyhydroxy polycarboxylic acid (PA) acid solution in the de-plugging process of sandstone oil reservoir.
Technical background
Sandstone matrix acidifying technology is the important technology of de-plugging of well and volume increase, and hydrochloric acid-hydrofluoric acid system is sandstone matrixThe acid fluid system that acidifying is the most frequently used. But hydrofluoric acid and the too fast acid solution penetration range that causes of clay reaction are short, hydrofluoric acid and clayMineral reaction production secondary precipitation easily causes formation damage. Existing various slow acid solution addresses these problems in trial, stillThese systems can not overcome the huge contrast of hydrofluoric acid and clay and quartzy interfacial reaction speed, and secondary precipitation problem does not have yetBe well solved. On to the basis of various acid fluid system researchs, a kind of novel sandstone reservoir acidifying place is proposedReason liquid---polyhydroxy polycarboxylic acid acid fluid system. By laboratory experiment and theory analysis, further investigate the characteristic of polyhydroxy polycarboxylic acid,Set forth polyhydroxy polycarboxylic acid slow and suppress the mechanism of secondary precipitation, set up sandstone reservoir polyhydroxy polycarboxylic acid model of acidification, andAnd the successful Application in conjunction with polyhydroxy polycarboxylic acid acid fluid system at Jiangsu oilfield.
Comparatively speaking various retarded acids and mud acid, have obtained good acidizing effect, and it is heavy still still not solveThe problem that shallow lake is stopped up. This is because aluminosilicate mineral and hydrofluoric acid in sandstone reservoir will generate various fluosilicates, villiaumiteSediment, these sediments are difficult to be dissolved in acid solution, have the ability on very high potential obstruction stratum, thereby have affected acidifying effectReally. Current acid liquid performance and treatment effect can't fully meet the needs of oil field development and production, therefore each oil field justPetroleum Engineer be devoted to sour research work for acidifying always.
Summary of the invention
In sandstone matrix acidifying, react the too fast acid solution penetration range that causes in order to overcome existing hydrochloric acid-hydrofluoric acid systemShort, hydrofluoric acid reacts production secondary precipitation with clay mineral easily causes the various deficiencies of formation damage, the invention provides a kind of acidChange the preparation method with polyhydroxy polycarboxylic acid, the polyhydroxy polycarboxylic acid acid fluid system of preparing can realize acidification deep penetration, hasEffect suppresses the generation of various secondary precipitations, and can effectively solve fouling, the antiscale problem of oil well, is processing loose sand storageLayer aspect has unique advantage.
The technical solution adopted for the present invention to solve the technical problems is that the preparation method of polyhydroxy polycarboxylic acid for acidifying, shouldMethod is made up of following steps: (1) raw material by weight percentage, by acrylic acid, maleic acid and PBTCA at airtight containerMiddle mixing, wherein acrylic acid accounts for that 20-40%, maleic acid account for 30-40%, PBTCA accounts for 30-40%; (2) High Purity Nitrogen will be passed in containerGas, container is positioned in water, and water-bath control reaction temperature is 50 DEG C to 60 DEG C; (3) by weight percentage, in continuous stirringUnder condition, in 1～5h, slowly add to system the initator azodiisobutyronitrile that accounts for 3 kinds of sour gross weight 1-3%, add initiationAfter agent, temperature can rise, and stops dripping when temperature arrives 80 DEG C, treats that temperature declines, then continues to drip initator, repeats above-mentioned stepSuddenly treat that temperature no longer rises, add initator; (4) continue to stir end after 4 hours.
The beneficial effect that the present invention reaches is as follows:
One. because the hydrogen ion concentration of polyhydroxy polycarboxylic acid is all to present the trend of slow increase along with temperature raises, this isBecause acid solution is when the temperature rise, polyhydroxy polycarboxylic acid solution ionizes out more hydrogen ion. The hydrogen ion of polyhydroxy polycarboxylic acid acid solutionThe ascendant trend of concentration after temperature is higher than 60 DEG C is more obvious. Experiment shows, polyhydroxy polycarboxylic acid, can under reservoir conditionsIonize out gradually H+, sufficient H can be provided+React with polyhydroxy polycarboxylic acid, generate HF.
Unlike limestone matrix acidifying, sandstone acidizing is considered to surface reaction controlling instead of diffusion mass transfer control. WarpResearch finds, control acid solution the reaction speed of sandstone reservoir kind because have: temperature, acid strength, liquid flowing rate, pressure,Acid rock surface to volume ratio, rock mechanical strength, secondary precipitation; In addition, the specific area of sandstone mineral and solubility be also one importantInfluence factor. Polyhydroxy polycarboxylic acid acid fluid system is to generate HF by polyhydroxy polycarboxylic acid and villiaumite reaction, in fact with sandstone reservoirThe material of reaction remains HF. Polyhydroxy polycarboxylic acid progressively ionizes out hydrogen ion and reacts with villiaumite (MF), slowly generates HF and carboxylic acidSalt, shown in ionization process establishes an equation as follows.
Wherein, RH5Represent polyhydroxy polycarboxylic acid, R represents polyhydroxy polycarboxylic acid group. Can find out from ionization indexes at different levels, poly-It is from high to low that polybasic carboxylic acid ionizes hydrionic ability, and the essence that polyhydroxy polycarboxylic acid reacts with villiaumite is exactly the hydrogen ionizing outIon and villiaumite generation hydrogenation, generate HF. Reaction equation is as follows.
(1.1)
Because this polyhydroxy polycarboxylic acid can ionize out hydrogen ion gradually, therefore control and reacted the speed that generates HF with villiaumiteDegree. Under low pH value environment, the hydrionic concentration that polyhydroxy polycarboxylic acid ionizes out will keep lower level, and therefore, HF's is denseDegree also just keeps lower level. And polyhydroxy polycarboxylic acid and villiaumite have formed a buffering regulation system. When HF and rock ore depositWhen thing reaction consumes a part, the balance of equation (1.1) is broken, and reaction will be carried out towards positive direction, the hydrogen ion in solutionConcentration reduces, and polyhydroxy polycarboxylic acid is also just also broken Ionization Equation balance, and polyhydroxy polycarboxylic acid will discharge part hydrogen ion, oneUntil solution re-establishes new balance. Therefore,, as long as the concentration of solution is enough large, in acid solution, the concentration of HF keeps permanent substantiallyFixed, the reaction speed of acid solution and rock forming mineral is constant.
Two. polyhydroxy polycarboxylic acid has slow effect to acid solution to the corrosion reaction of clay mineral. It is anti-that polyhydroxy polycarboxylic acid suppressesAnswer the reaction mechanism of speed and control clay dissolution rate to comprise chemisorbed and physisorption. The no matter static of rock surfacePolarity how, and polyhydroxy polycarboxylic acid can be adsorbed on rock. Physical absorption is main relevant with the surface area of rock. For sandstoneStratum, polyhydroxy polycarboxylic acid is more easily adsorbed on surface of clay. Table 1-2 has listed the specific area of various mineral. Data from tableCan find out, clay specific area maximum, far away higher than other mineral, therefore, polyhydroxy polycarboxylic acid will be adsorbed on the clay of rockSurface.
The specific area of the various mineral of table 1-2
| Mineral | Composition | Electrically (pH < 1) | Specific area (cm2/g) |
| Quartz | SiO2 | + | 185 |
| Montmorillonite | Al4Si8O20(OH)4 | - | 750×106 |
| Kaolinite | Al4Si4O10(OH)8 | + | 22×106 |
| Feldspar | KAlSi3O8 | + | 29×106 2 --> |
| Illite | (H3,O,K)y(Al4Fe4Mg4)(Si8-yAlyO20(OH)4 | + | 113×106 |
| Chlorite | (Mg,Fe2+,Fe3+)ALSi3O10(OH)8 | + | 29×106 |
Three. except physisorption, chemisorbed is also easy to act on the clay that calcic, iron, aluminium component are higher and fills outFill on thing. Now, polyhydroxy polycarboxylic acid reacts " thin layer " that generate alumo-silicate at surface of clay with clay. Scanning electron microscopic observationThe thickness of this " thin layer " is no more than 1 micron, and the solubility in weak acid (HF acid, carbonic acid) and water is little, but dissolves in HCLHurry up, in organic acid, dissolution velocity is very fast. This thin layer can stop reacting of clay and acid solution, reduces the solubility of clay.Dynamic solubility test shows that the solubility of clay is directly proportional to the specific area of clay to a certain extent. Due at clay tableThe thin layer that face forms is acid-soluble, therefore can adjust with a small amount of hydrochloric acid or formic acid the solubility of clay, reachesAcidifying optimal design.
Four. the corrosion experimental study of polyhydroxy polycarboxylic acid and clay shows, polyhydroxy polycarboxylic acid is because physical absorption and chemistry are inhaledThe attached surface of clay that acts on forms one deck " thin layer ", and this thin layer can slow down the reaction speed of acid solution and clay mineral, therebyReach slow object. The complexing power that polyhydroxy polycarboxylic acid has polyvalent metal ion in solution, and polyhydroxy polycarboxylic acid canWith under the concentration very low by the polyvalent metal ion " chelating " of the stoichiometry respective amount far above according to chelating mechanism in moltenIn liquid, thereby the metal ion that makes some easily generate precipitation keeps solution state. Therefore, molten what have polyhydroxy polycarboxylic acid to existIn pendular ring border, Ca2+、Na+、K+、NH4+And so on ion be just difficult to have an opportunity and F-、SiF6 2-Form villiaumite precipitation and fluorine siliconHydrochlorate precipitation. The two is exactly that polyhydroxy polycarboxylic acid suppresses the mechanism that secondary precipitate generates. Core flow test and poly-polynary carboxylicAcid test show, polyhydroxy polycarboxylic acid can be obtained good acidification effect, permeability ratio is all greater than 4.0. Poly-polynary carboxylicThe wetability experiment of acid shows, polyhydroxy polycarboxylic acid itself is hygroscopicity matter, and the mixture of polyhydroxy polycarboxylic acid and mud acid is same is alsoHygroscopicity matter. The compatibility of itself and various additives is good, simultaneously also fine with the compatibility of fluoboric acid, and this shows poly-polynaryCarboxylic acid can be combined use with fluoboric acid. The flow effect evaluation experimental of polyhydroxy polycarboxylic acid shows, polyhydroxy polycarboxylic acid acid fluid systemThere is good acidizing effect, established experiment basis for successfully realizing oil well production increasing.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment 1
Each raw material by mass percentage, acrylic acid: 20%; Maleic acid: 40%; PBTCA:40%; Initator: 1%; SternlyLattice add at first acrylic acid, maleic acid, PBTCA according to reinforced order in reactor. Pass into after high pure nitrogen protection water-bath controlReaction temperature processed is 55 DEG C; Under the condition of continuous stirring, in 1～5h, slowly add and account for 3 kinds of sour gross weights 1% to systemInitator azodiisobutyronitrile, adds after initator, and temperature can rise, and observes after temperature arrives 80 DEG C and stops dripping, and treats temperatureThere is decline, then continue to drip initator, repeat above-mentioned steps and treat that temperature no longer rises, add initator; (4) in course of reactionIn must keep oxygen-free environment, continue to stir after 5h and finish; Obtain polyhydroxy polycarboxylic acid.
The performance test of embodiment 1 polyhydroxy polycarboxylic acid
Hydrogen ion determination
The hydrogen ion concentration of polyhydroxy polycarboxylic acid is all to present the trend of slow increase along with temperature raises, and this is due to acid solutionIn the time of temperature rise, polyhydroxy polycarboxylic acid solution ionizes out more hydrogen ion. The hydrogen ion concentration of acid solution in temperature higher than 60 DEG CAscendant trend is afterwards more obvious. Experiment shows, under reservoir conditions, can ionize out gradually H+, sufficient H can be provided+, generate HF.
Slow experiment
Design four kinds of acid solutions and reacted with clay, investigated in different time acid solution the corrosion rate to clay, and finalCorrosion rate, the slow mechanism of research polyhydroxy polycarboxylic acid acid fluid system. It is Anqiu soil that Weifang, Shandong produces that experiment adopts clay, peaceThe main component of mound soil is bentonite, and chemical composition is mainly montmorillonite, therefore hereinafter referred to as imvite. 80 DEG C of experimental temperatures.These four kinds of acid solutions are respectively:
1# mud acid 12%HCL+3%HF
2# fluoboric acid 12%HCL+5%HBF4
3#4%PA+6%MF+8%CH3COOH
4#3%PA+3%MF+8%HCL
Experimental result shows, mud acid and clay reaction rate are the fastest, and corrosion rate is the highest; Next is add hydrochloric acid poly-polynaryCarboxylic acid system; Fluoboric acid system again; What corrosion rate was minimum is to add organic acid polyhydroxy polycarboxylic acid system. Polyhydroxy polycarboxylic acidAfter adding organic acid in system, corrosion rate significantly declines; Reduce by 28.9% than mud acid corrosion rate; Than adding the poly-polynary of hydrochloric acidThe corrosion rate of carboxylic acid system reduces by 22.4%; Simultaneously low by 17.4% than the final corrosion rate of fluoboric acid system. Two kinds of polyhydroxy polycarboxylic acidsAcid fluid system is lower than mud acid to the corrosion rate of clay, and therefore, polyhydroxy polycarboxylic acid can suppress the speed of reacting of acid solution and imviteRate. Experimental result also shows, by regulating the formula in polyhydroxy polycarboxylic acid acid fluid system, can adjust the corrosion of acid solution to clayRate and reaction speed.
Corrosion experimental study
Precipitation experiment
Carry out the various conditions of simulated oil gas field formation acidizing with salt water test, investigation polyhydroxy polycarboxylic acid precipitates fluorideInhibitory action. Salt solution is by mass percentage by 2%KCL+2%NaCL+0.2%CaCL2+ 2%MgCL+ distilled water composition, at twiceHeighten the pH value of solution with sodium carbonate, observation precipitation situation, 50 DEG C of test temperatures. React contrast test by various acid solutions,
Experimental design step is as follows:
(1) acid solution is prepared with plastic bottle, and salt solution is prepared by above concentration;
(2) test is carried out under visual condition, and each example reaction is measured pH value for one hour;
(3) in various acid solutions, add the sodium carbonate of equivalent, every liter of acid solution adds 12g sodium carbonate;
(4) measure the pH value of each acid solution;
(5) add the sodium carbonate of extra equivalent, every liter of acid solution adds 12g sodium carbonate;
(6) measure the pH value of each acid solution.
The inhibitory action of table 1-3 polyhydroxy polycarboxylic acid to fluoride precipitation
Remarks:
1# system 12%HCL+3%HF
2# system 9%HCL+2.0%MF+2%PA
3# system 10%HCL+2.0%MF+5%PA
Result of the test is listed in table, can find out from test data result, and mud acid is after adding sodium carbonate for the first time, moltenLiquid has just produced turbid phenomenon, and two kinds of polyhydroxy polycarboxylic acid acid fluid system are after heightening pH value for the first time, and solution does not all go outExisting muddy. Although in these three kinds of acid fluid system, the pH value of mud acid system is the level that keeps minimum all the time, mud acid suppressesThe ability of fluoride precipitation is not as polyhydroxy polycarboxylic acid system. Although use two kinds of polyhydroxy polycarboxylic acid PA and HF acid solution pH value alwaysHeight, but precipitation do not produced to heightening for the second time pH value yet. Experimental result shows, polyhydroxy polycarboxylic acid acid fluid system has betterThe performance of inhibition fluoride precipitation.
Two, the real face of silicate precipitates
Above experiment does not comprise aluminium salt and silicate, and the two is the product of dissolve clays, therefore below designExperiment observe the Precipitation of alumino-silicate in various acid solutions. With the CaCL of running water preparation 100mg/L2, 40mg/L'sMgCL2, the A1C1 of 40mg/L3, the NaHCO of 100mg/L3Salt solution. Acid solution is mixed with salt solution equal-volume, in one hourGradation adds silica containing sodium silicate solution 1ml. Experimental procedure is as follows:
(1) acid solution is prepared with plastic bottle, and salt solution is prepared by above concentration;
(2) test is carried out under visual condition, mixes equal-volume (50mL+50mL) salt solution and acid solution;
(3) reaction one hour;
(4) slowly add 1m ~ 6ml sodium silicate solution, observe precipitation situation.
The inhibitory action acid solution of polyhydroxy polycarboxylic acid to silicate precipitates
Remarks:
1# system 12%HCL+3%HF
2# system 9%HCL+2.0%MF+2%PA
3# system 10%HCL+2.0%MF+5%PA
Experimental result is in Table, and 2# system and 3# system are to generate HF by hydrolysis to reach slow object, result tableBright polyhydroxy polycarboxylic acid has best inhibitory action to silicate precipitates, and mud acid takes second place.
Polyhydroxy polycarboxylic acid acid fluid system flow effect evaluation experimental
Oil field rock core flowing experiment
At Jiangsu oilfield coring sample, at the indoor core flow test that carries out. Core flow test has adopted sandstone acidizingConventional acid fluid system, as mud acid system and fluoboric acid system, and novel acid solution polyhydroxy polycarboxylic acid system.
Mix acid liquor series
In the core flow test of mix acid liquor system, employing be that two kinds of acid solutions of fluoboric acid and mud acid are injected successivelyTwo kinds of acid solutions process acid solutions. The rock core numbering that test adopts is 9# and 10#, core diameter be respectively as 2.512cm and2.498cm, it is 4.300cm and 5.825cm that rock core is respectively length, rock porosity is respectively 17.26% and 12.34%. ProcessLiquid 1 mud acid system, treatment fluid 2 is hydrofluoboric acid systems, prepad fluid and after pad adopt hydrochloric acid+additive, base fluid and positive groupLiquid and anti-base fluid are 4%NH4C1. Core flow test carries out under formation temperature conditions, records final permeability ratio K/K0 and approaches1.0, acidification effect is undesirable.
Rock core flowing experiment
Fluoboric acid system
The rock core numbering of first group of fluoboric acid core flow test employing is 4#, and diameter is 2.520cm, and rock core length is5.409cm, rock porosity is 13.65%. Treatment fluid is 8%HCl ten 6%HBF4+ additive, prepad fluid and after pad adopt saltAcid ten additives, base fluid and positive base fluid and anti-base fluid are 4%NH4C1. Core flow test records under formation temperature conditionsWhole permeability ratio K4/K0 is 1.21, and acidification effect is not good enough. Second group of rock core numbering that fluoboric acid core flow test adoptsBe 7#, under core flow test formation temperature conditions, recording final permeability ratio K4/KO is 1.17, and acidification effect is not good enough.
Rock core flowing experiment
Polyhydroxy polycarboxylic acid series
The rock core numbering of first group of polyhydroxy polycarboxylic acid core flow test employing is 3#, and diameter is 2.543cm, rock core lengthBe 5.850cm, rock porosity is 14.96%. Treatment fluid is to adopt polyhydroxy polycarboxylic acid system 8%HCl+6%PA+4%MF+ to addAgent, prepad fluid and after pad adopt hydrochloric acid+additive, and base fluid and positive base fluid and anti-base fluid are 4%NH4CL. Core flow testUnder formation temperature conditions, recording final permeability ratio K4/K0 is 4.28, and acidification is respond well. Second group of polyhydroxy polycarboxylic acidThe rock core numbering that core flow test adopts is 1#, and diameter is 2.512cm, and rock core length is that 5.453cm rock porosity is14.57%. It is that 4.17 acidification effects are good that core flow test records final permeability ratio K/K0 under formation temperature conditionsGood. The rock core of the 3rd group of polyhydroxy polycarboxylic acid core flow test is numbered 8#, and diameter is 2.529cm, and rock core length is5.390cm, rock porosity is 13.11%. Core flow test records final permeability ratio K4/K0 under formation temperature conditionsBe 4.35, acidification is respond well.
Rock core flowing experiment
Core flow test shows, not good with mud acid fluoboric acid mixed system and fluoboric acid system treatment effect; PermeabilityRatio is in 1.0 left and right. Three groups of tests of polyhydroxy polycarboxylic acid all show, polyhydroxy polycarboxylic acid can be obtained good acidification effectReally, permeability ratio is all greater than 4.0.
Polyhydroxy polycarboxylic acid and quartz dissolution test
This experiment corrosion reaction to polyhydroxy polycarboxylic acid acid fluid system and quartz reaction by the PA investigating at variable concentrationsAffect rule. Polyhydroxy polycarboxylic acid acid formula is 3%PA+6%MF+3%HCL. Experimental temperature is 70 DEG C, under atmospheric pressureTest data is in shown in Table.
Variable concentrations PA system and quartz reaction data
Can be found by experimental result, in polyhydroxy polycarboxylic acid system the concentration of PA in 4% acid fluid system to quartzCorrosion ability is the strongest, and corrosion rate reaches 9.97%, 8.46% when being 15% higher than PA concentration.
The dissolved corrosion test of many hydracids and actual rock core
In conjunction with the actual rock core in oil field, investigate various acid fluid system and polyhydroxy polycarboxylic acid acid fluid system different formulations to actual oilThe corrosion rate of field rock core, rock dust sampling is from Bohai Bay Oil BZ34-2, test temperature is 80 DEG C, 4 hours reaction time, pressureCondition is atmospheric pressure.
Carry out dissolved corrosion test according to above experimental procedure, investigated the polyhydroxy polycarboxylic acid acid solution of hydrochloric acid, mud acid, various formulasThe corrosion rate that system is reacted with rock dust, experimental result is in Table. Be numbered 1# and all added additive to the acid solution of 6#.
Core corrosion rate result
Can find out from the corrosion result of table, the corrosion rate of 8%HCL+4%PA+6%MF+ additive is a little more than 8%HCL+2%PA+6%MF+ additive; And polyhydroxy polycarboxylic acid acid fluid system is in the situation that HCL is identical with PA concentration, the concentration of MF is6% time, corrosion rate is higher, reaches 27.64%, is greater than 21.05% of mud acid.
Compatibility
Test will be investigated the compatibility of polyhydroxy polycarboxylic acid acid fluid system and various additives, and experimental temperature is 70 DEG C, atmospherePress strip part. The rock dust that experiment adopts is the actual rock core of certain well in oil field in Bohai Sea, and experimental result is in Table 3-7. Polyhydroxy polycarboxylic acid acid solutionAlso showing with the experiment of fluoboric acid acid solution compatibility of system, the compatibility of polyhydroxy polycarboxylic acid acid fluid system and fluoboric acid acid solution is goodGood, all do not find precipitation and lamination, these two kinds of acid fluid system can be combined use.
The experiment of polyhydroxy polycarboxylic acid system compatibility
At Jiangsu oilfield, obtain at the oil well of taking polyhydroxy polycarboxylic acid acidifying on the basis of good result and courageously break through, poly-Polybasic carboxylic acid Acidizing Process Technique is the oil layer blocking injury causing for organic deposition pollution, bacterial product obstruction, inorganic scale etc.,Remove organic deposition by saponification and emulsifying manner and stop up, remove inorganic scale by chelating cation mode and stop up, then to gather polynary carboxylicThe cationic combination of acid anion and rock surface has formed one deck polyhydroxy polycarboxylic acid overlay film temporarily, has slowed down acid-rock reaction speedDegree, makes acid solution advance to oil reservoir deep, thereby reaches the acidifying of oil reservoir deep. In addition, can realize point owing to containing multiple hydrogen ionsLevel discharges, therefore this technology have that operating radius is large, corrosion ability strong, without features such as secondary precipitations. According to this technologyPrinciple and Jiangsu oilfield are obtained on the basis of good result on oil well, through detailed feasibility analysis, meticulously select well, 2011At the beginning of years 9 months, first selected three mouthfuls after conventional acidifying, fracturing methods the not good enough water injection well of effect test. Process of the testIn, polyhydroxy polycarboxylic acid blockages relieving fluid, oxidant, diverting agent and mutual solvent performance to its use are tested, and to operation pressure,Discharge capacity, concentration and consumption are supervised, and have guaranteed the smooth enforcement of this engineering test. This technology is applied to water filling in good timeWell de-plugging, by October 9,40 cubic metres of 3 mouthfuls of service shaft day augmented injections of enforcement, 1274 cubic metres of accumulative total augmented injections, measure effectSignificantly.
Embodiment 2
Each raw materials by weight is divided meter, acrylic acid: 30%; Maleic acid: 40%; PBTCA:30%; Initator: 2%; SternlyLattice add at first acrylic acid according to reinforced order in reactor, maleic acid, and PBTCA. passes into after high pure nitrogen protection, water-bath controlReaction temperature processed is 55 DEG C; Under the condition of continuous stirring, in 1～5h, slowly add and account for 3 kinds of sour gross weights 1% to systemInitator azodiisobutyronitrile, adds after initator, and temperature can rise, and observes after temperature arrives 80 DEG C and stops dripping, and treats temperatureThere is decline, then continue to drip initator, repeat above-mentioned steps and treat that temperature no longer rises, add initator; (4) in course of reactionIn must keep oxygen-free environment, continue to stir after 5h and finish; Obtain polyhydroxy polycarboxylic acid.
Embodiment 3
Each raw materials by weight is divided meter, acrylic acid: 40%; Maleic acid: 30%; PBTCA:30%; Initator: 3%;In reactor, add at first acrylic acid in strict accordance with reinforced order, maleic acid, PBTCA. passes into after high pure nitrogen protection, water-bathControlling reaction temperature is 55 DEG C; Under the condition of continuous stirring, in 1～5h, slowly add and account for 3 kinds of sour gross weights 1% to systemInitator azodiisobutyronitrile, add after initator, temperature can rise, and observes temperature and arrives after 80 DEG C and stop dripping, and treats temperatureDegree has decline, then continues to drip initator, repeats above-mentioned steps and treats that temperature no longer rises, and adds initator; (4) reactingIn journey, must keep oxygen-free environment, continue to finish after stirring 5h. Obtain polyhydroxy polycarboxylic acid.
Embodiment 4
Each raw materials by weight is divided meter, acrylic acid: 20%; Maleic acid: 40%; PBTCA:40%; Initator: 1%;In reactor, add at first acrylic acid in strict accordance with reinforced order, maleic acid, PBTCA. passes into after high pure nitrogen protection, water-bathControlling reaction temperature is 55 DEG C; Under the condition of continuous stirring, in 1～5h, slowly add and account for 3 kinds of sour gross weights 1% to systemInitator azodiisobutyronitrile, add after initator, temperature can rise, and observes temperature and arrives after 80 DEG C and stop dripping, and treats temperatureDegree has decline, then continues to drip initator, repeats above-mentioned steps and treats that temperature no longer rises, and adds initator; (4) reactingIn journey, must keep oxygen-free environment, continue to finish after stirring 5h; Obtain polyhydroxy polycarboxylic acid.
Embodiment 5
Each raw materials by weight is divided meter, acrylic acid: 35%; Maleic acid: 35%; PBTCA:30%; Initator: 2%; SternlyLattice add at first acrylic acid, maleic acid, PBTCA according to reinforced order in reactor. Pass into after high pure nitrogen protection water-bath controlReaction temperature processed is 55 DEG C; Under the condition of continuous stirring, in 1～5h, slowly add and account for 3 kinds of sour gross weights 2% to systemInitator azodiisobutyronitrile, adds after initator, and temperature can rise, and observes after temperature arrives 80 DEG C and stops dripping, and treats temperatureThere is decline, then continue to drip initator, repeat above-mentioned steps and treat that temperature no longer rises, add initator; (4) in course of reactionIn must keep oxygen-free environment, continue to stir after 5h and finish; Obtain polyhydroxy polycarboxylic acid.
Claims (1)
1. a preparation method for polyhydroxy polycarboxylic acid for acidifying, is characterized in that: the method is made up of following steps: (1) raw materialBy weight percentage, acrylic acid, maleic acid and PBTCA are mixed in airtight container, wherein acrylic acid accounts for 20-40%, horseCome the sour 30-40% of accounting for, PBTCA and account for 30-40%; (2) will in container, pass into high pure nitrogen, container is positioned in water, and water-bath control is anti-Answering temperature is 50 DEG C to 60 DEG C; (3), under the condition of continuous stirring, in 1～5h, slowly add to system by weight percentage,The initator azodiisobutyronitrile that enters to account for 3 kinds of sour gross weight 1-3%, adds after initator, and temperature can rise, when temperature arrives 80DEG C stop dripping, treat that temperature declines, then continue to drip initator, repeat above-mentioned steps and treat that temperature no longer rises, add initiationAgent; (4) continue to stir end after 4 hours.
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| CN1752175A (en) * | 2004-09-24 | 2006-03-29 | 中国石油化工股份有限公司 | Oil well acidification composition |
| CN1752174A (en) * | 2004-09-24 | 2006-03-29 | 中国石油化工股份有限公司 | Acidification composition for oil well |
| CN101133135A (en) * | 2005-03-04 | 2008-02-27 | 巴斯福股份公司 | Use of water-soluble alkane sulfonic acids for increasing the permeability of underground petroliferous and/or gas-bearing carbonate rock formations and for dissolving carbonate contaminants and/or co |
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