CN104194759A - Neutral blockage removing agent composition used for oil recovery formation in oilfield and preparation method thereof - Google Patents
Neutral blockage removing agent composition used for oil recovery formation in oilfield and preparation method thereof Download PDFInfo
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- CN104194759A CN104194759A CN201410489270.3A CN201410489270A CN104194759A CN 104194759 A CN104194759 A CN 104194759A CN 201410489270 A CN201410489270 A CN 201410489270A CN 104194759 A CN104194759 A CN 104194759A
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Abstract
The invention relates to a neutral blockage removing agent composition used for an oil recovery formation in an oilfield. The neutral blockage removing agent composition is prepared from the following raw materials in parts by weight: 30-36 parts of disodium polyepoxysuccinicate, 18-25 parts of sodium gluconate, 2-3 parts of polyethylene glycol, 2-4 parts of triethanolamine, 9-12 parts of ethyl lactate, 7-10 parts of fatty alcohol polyoxyethylene ether sodium sulfate, 8-12 parts of amino acid sodium, 10-15 parts of activated attapulgite, 0.1-0.2 part of vanadium pentoxide, 5-7 parts of lipase, 5-8 parts of sorbitan fatty acid ester, 15-18 parts of P-hydroxy sodium sulfonate, 3-7 parts of tert-butyl hydroperoxide and 0.1-0.3 part of diethylene glycol monolaurate. The neutral blockage removing agent composition has high blockage removing speed, is neutral, is free of corrosion and can quickly dissolve material scales, asphalt sediment scales, carbonate scales, silicate scales and the like generated by an ASP flooding system; waste liquid for blockage removal can be degraded and does not need to be discharged onto the ground to be subjected to sewage treatment, the formation in the oilfield is cleaned to remove the blockage, no corrosion, dead angle, precipitation or secondary well blockage is generated, and the blockage removal time does not exceed 24 hours.
Description
Technical field
The present invention relates to the neutral unblocking agent composition of the auxiliary agent that a kind of oil extraction in oil field uses, particularly a kind of oil extraction in oil field stratum, the invention still further relates to the preparation method of the neutral unblocking agent composition in oil extraction in oil field stratum.
Background technology
The first, the proposition of problem
1, many oil fields both domestic and external are all perplexed by fouling injury to some extent in water flooding recovery, especially enter stage intermediary and later stages in exploitation, and along with the increase of Water Content in Oil amount, it is more general and serious that scale problems becomes.Because oil-field water fouling causes oil reservoir injury, producing well pit shaft, water injection well pit shaft and oil extraction pump and device systems stop up, thereby cause too early oil well, oil extraction pump and equipment scrapping.These problems have improved cost for oil production greatly, have a strong impact on the normal production of oil gas.In order to solve better the scale problems of oil field stratum and oil extraction pump and equipment, the fouling solving in oilfield water extraction injures this technical barrier, need to use unblocking agent product.
2, oil is the strategic goods and materials that are related to China's economic lifeline, in China, middle and high infiltration oil reservoir development stable yields technology is relatively ripe, but how to realize old well continuously steady production for hypotonic, extra-low permeability oil reservoirs, and obtain higher ultimate recovery factor and economic benefit, be a major challenge that domestic many oil fields face.Therefore, how to improve tertiary oil recovery technology level, increase the recovery ratio of existing oil reservoir, there is important economic worth and strategic importance.The application of alkaline surfactant polymer flooding oil-field technology, has greatly delayed the speed of domestic each elephant production rate decline, has become the major measure that field output is taken over.Along with the use of three-component compound system, gathering of alkali consumption, the skeleton to reservoir rock and cementing matter have serious injury, also cause the injury to oil reservoir, reduce reservoir permeability, injection pressure declines, and oil and water well fouling is serious, to sulfonated petro-leum conventional in tertiary oil recovery, the precipitation occurring in multivalent cation aqueous solution etc. is had to impact and injury to a certain degree, therefore,, to the producing well of application three-component compound system, need to carry out eliminate the harmful effect with de-plugging scale removal product.
When the application of alkaline surfactant polymer flooding oil-field technology, produce salt cause for scaling as follows: local water fouling is subject matter inevitable in field produces and that will face.The unfavorable chemical reaction producing between the change of local water pH value and alkali and reservoir rock, produces fouling precipitation and becomes more and more outstanding, and fouling throw out is mainly carbonate scale, silicate scale and sulfate scale.
For the equilibrium interfacial tension that makes alkali/Surfactant/Polymer ternary system can reach 10 orders of magnitude, must add a large amount of alkali, particularly highly basic NaOH.And adding of alkaline agent has serious injury to reservoir rock skeleton and cementing matter.With this, must damage oil reservoir, injection pressure declines, or oil and water well fouling, must shut down, and serious meeting causes oil reservoir to cave in, and particularly near oil reservoir Injection Well caves in, and even stops up.In three-component compound system, contain 0.8%～1.5% high concentration alkali, particularly highly basic Na
2cO
3and NaOH, the pH value of solution, in 12～14 scope, therefore, must damage reservoir rock mineral, and even grievous injury produces dirt, causes the obstruction on stratum.
The injury of tensio-active agent to oil reservoir and to stop up the dirty analysis of causes as follows in three-component compound system: generate divalence sulfonated petro-leum (calcium, magnesium) because the sulfonated petro-leum adding in three-component compound system (sodium) and these polyvalent cations in local water react.Divalence sulfonated petro-leum is under certain temperature condition, and the solubleness in water is limited.Result of study shows, when containing certain density Ca in local water
2+and Mg
2+time, will there is divalence sulfonated petro-leum precipitation.This deposited phenomenon of tensio-active agent, by on it, the Damage for Detention in pore media has vital role and impact, there is divalence sulfonated petro-leum precipitation, not only seriously stop up oil reservoir, and can accelerate the spending rate of tensio-active agent, the displacement of reservoir oil effect premature failure of the alkali that makes to inject, tensio-active agent, polymer ternary combination flooding.
The second, traditional de-plugging means
At present, Oilfield using acidification to dispel block, biological plugging releasing and solvent de-plugging, mainly adopt acidification to dispel block.Acidification to dispel block is by means of mineral acid (hydrochloric acid, hydrofluoric acid, also useful sulfuric acid), also can use the chemical corrosion of organic acid (formic acid, acetic acid etc.) to formation rock, tamper, and the hydraulic action of acidifying pressure, improve stratum permeability, realize the engineering measure of oil well production increasing, intensified injection of wells.In order to complete acidifying engineering objective, in acidizing fluid, except host acid, also need to add inhibiter, Fe stabilizer etc.
Hydrochloric acid and mud acid that acidifying is used are strong acid, especially hydrochloric acid is exceedingly fast with reacting of carbonate, easily cause the excessive acidifying in stratum at nearly well position, and deep-section can not get abundant acidifying, this phenomenon is larger on the high temperature deep well impact of low permeability formation, is the major cause that causes acidification failure.In acidization, acidification corrosion inhibitor is subject to formation temperature, pressure and iron ion impact and lost efficacy, once acidification corrosion inhibitor lost efficacy, will cause the heavy corrosion of producing well, oil well pump and oil transporting appliance, and therefore acidification to dispel block exists potential great risk.
Prior art acidifying hydrochloric acid and hydrofluoric acid reacts acutely with formation rock ore deposit, consume fast, and solution cavity is large and de-plugging operating range is short, and de-plugging area is little and not thorough, is difficult to reach the object of deep acidifying, affects acidizing effect.
The neutral unblocking agent of the present invention can reach the object of removing clog in deep reservoir, neutral blockages relieving fluid motion is carried out with certain speed, make the neutral blockages relieving fluid of q.s enter oil reservoir depth position, open deep oil flow channel, for the extraction of reservoir fluid forms good passage, reduce additional capillary pressure, improve the relative permeability of crude oil, and improve tar productivity.
4, de-plugging waste liquid is easily degraded, need not the row's of returning floor treatment
Because all components of the neutral unblocking agent of the present invention is all made up of the complexing agent of easily degrading, emulsifying agent, dispersion agent and oxygenant, react with the dirt cleaning in oil field stratum, generate the easily small molecules salt of degraded, can reach quality and the environmental requirement of oilbearing stratum to water quality.With this unblocking agent to oil field stratum chemical plugging removal after, oil field stratum cleans the waste liquid row of returning earthward of de-plugging, has reduced liquid waste disposal operation and expense after cleaning de-plugging, has reduced the pollution to environment.
Summary of the invention
The object of the present invention is to provide the neutral unblocking agent composition in fast, the neutral free from corrosion oil extraction in oil field of a kind of de-plugging speed stratum; This unblocking agent can dissolve material dirt, pitch settling dirt, carbonate scale, silicate scale and the sulfate scale that ternary composite displacement system produces fast.The second object of the present invention is to provide the preparation method of the neutral unblocking agent composition in oil extraction in oil field stratum.
Realize the technical scheme that the object of the invention takes as follows: the neutral unblocking agent composition in a kind of oil extraction in oil field stratum, raw material by following portions by weight is made: 30～36 parts of polyepoxy sodium succinates, 18～25 parts of Sunmorl N 60Ss, 2～3 parts of polyoxyethylene glycol, 2～4 parts of trolamines, 9～12 parts of ethyl lactates, 7～10 parts of polyoxyethylenated alcohol sodium sulfate, 8～12 parts, amino acid sodium, 10～15 parts, active attapulgite soil, 0.1～0.2 part of Vanadium Pentoxide in FLAKES, 5～7 parts, lipase, 5～8 parts of sorbitan carboxylic esterses, to 15～18 parts, hydroxyl sulfoacid sodium, 0.1～0.3 part of 3～7 parts of t-butyl hydroperoxides and two ethylene glycol laurate.
The preparation method who the raw material of above-mentioned parts by weight is prepared into the neutral unblocking agent composition in oil extraction in oil field stratum comprises the steps:
A, by 9～12 parts of 30～36 parts of polyepoxy sodium succinates, 18～25 parts of Sunmorl N 60Ss, 2～3 parts of polyoxyethylene glycol, 2～4 parts of trolamines, ethyl lactate and 4～6 parts, active attapulgite soil, carry out fragmentation with shredder, after crossing 20 mesh sieves, stir, make the first powder; The first powder is as the main component of unblocking agent;
B, by 8～12 parts of 7～10 parts of polyoxyethylenated alcohol sodium sulfate, amino acid sodium and 5～7 parts, active attapulgite soil, stir 1 hour to evenly with taper mixing and blending machine, polyoxyethylenated alcohol sodium sulfate and amino acid sodium are fully adsorbed by active attapulgite soil carrier, make the second powder after then pulverizing 20 mesh sieves; The second powder is solvay-type supporting surfactant as unblocking agent;
C, by 5～7 parts of 0.1～0.2 part of Vanadium Pentoxide in FLAKESs, lipase and 1～2 part, active attapulgite soil, stir 40 minutes to evenly with taper mixing and blending machine, cross 40 mesh sieves and make the 3rd powder; The 3rd powder is as catalyzer absorption powder;
D, by 5～8 parts of sorbitan carboxylic esterses, to 3～7 parts, 15～18 parts, hydroxyl sulfoacid sodium, t-butyl hydroperoxide and 0.1～0.3 part of two ethylene glycol laurate, stir 40 minutes to evenly with tapered mixing and blending machine, 20 mesh sieves make the 4th powder; The 4th powder is as the auxiliary agent of complexing and inhibition;
E, the first powder making, the second powder, the 3rd powder and the 4th powder mixing and stirring are made to the neutral unblocking agent in oil extraction in oil field stratum.
The neutral unblocking agent composition in oil extraction in oil field provided by the invention stratum, its outward appearance is colourless or light yellow powder shape, and particle size diameter is for being less than 20 orders, and water content is less than 6%, and bulk specific gravity is 1.03～1.12g/cm
3, pH is 6～7, when oil field stratum de-plugging, the aqueous solution that is mixed with mass percent concentration 2～5% according to oil field stratum dirt chocking-up degree water uses.The present invention applies in Daqing oil field two factories of recovering the oil, the present invention is made to the aqueous solution of mass percent concentration 2～5%, be injected in oil extraction in oil field stratum by 10Mpa high-pressure pump, under oil field stratum temperature 45 C condition, there is chemical reaction with calcium carbonate, carbonic acid magne-scale and ternary composite driving polymer material dirt in stratum etc., within 24 hours, complete stratum and clean de-plugging, after de-plugging, oil extraction in oil field rate has reached the designed capacity of producing well.
The present invention is not containing mineral acid and organic acid, and also, not containing harmful ions such as hydrogen ion, chlorion and sulfate radicals, corrosion rate is less than 0.1g/ (m
2h), reach corrosion-free safe de-plugging.
The neutral unblocking agent in oil extraction in oil field provided by the invention stratum uses the method for infiltration, solubilising, oxidation, chain rupture and conversion, make various types of dirts and this unblocking agent generation chemical reaction in stratum be converted into water soluble salt, adopt after the de-plugging of this unblocking agent, carbonate scale, silicate scale and sulfate scale that calcium, magnesium metal ion are produced dissolve in de-plugging scavenging solution.The active group of neutral unblocking agent, can be converted into water-soluble cpds by carbonate scale and sulfate scale.For use the divalence sulfonated petro-leum throw out dirt and polyacrylamide polymers material dirt and the iron oxide precipitation dirt that produce in alkaline surfactant polymer flooding oil-field at oil recovery process, react with polycarboxylic acid amine salt in this unblocking agent etc., generate solubility micromolecular compound, and there is degradation property, in bituminous matter dirt in oil field stratum and other polymer scales and this agent-the molten dirty synergistic effects of group generation such as OH ,-ONa, reaction chain rupture generates small molecules polymkeric substance soluble in water, remove polymer material dirt and bituminous matter dirt to reach, realize the object to the neutral de-plugging of oil field stratum.
Neutrality of the present invention is corrosion-free, be used for cleaning oil field stratum de-plugging, can single stage method complete the de-plugging of oil field stratum, can dissolve fast the material dirt that ternary composite displacement system produces, pitch settling dirt, carbonate scale, silicate scale and sulfate scale, cleaning that the waste liquid of de-plugging has can self-degradation, need not carry out sewage disposal in the row of returning ground, have corrosion-free, without dead angle, do not produce precipitation and secondary precipitate particulate and stop up capillary phenomenon and the advantages such as stifled well, the de-plugging treatment time is no more than 24 hours, reach corrosion-free safe de-plugging, than traditional acidification to dispel block, biological plugging releasing and solvent de-plugging safety and reliability.
The present invention is also applicable in oil extraction in oil field process, can solve the cleaning de-plugging of oil field stratum and the etching problem of oil production equipment, effectively controls unblocking agent and sandstone speed of response, and generate mashed prod, the rate of permeation that improves stratum, prevents formation contaminant, improves oil recovery factor.
main Function and the application mechanism of the each component of the present invention are as described below:
1, polyepoxy sodium succinate: the polyepoxy sodium succinate using as the main component of unblocking agent in this unblocking agent, it is made up of the compound of five to six rings, after de-plugging, can not cause environmental accumulation, polluted-water, biological degradability is good, is that we are by the complexing of metal ion agent of a large amount of molten dirty test and Selection.We prove through de-plugging research evaluation result: when polyepoxy sodium succinate and metal ion generate complex compound, conventionally form multiple complexing rings.The more, the stability of complex compound is higher for number in a complex molecules, and the more, the complex compound that ligand and complexing of metal ion form is just more stable for the complexing ring forming when ligand and complexing of metal ion.Polyepoxy sodium succinate has multiple complexing rings, and can be simultaneously with many metal ions as Ca
2+, Mg
2+, Fe
3+, Fe
2+, Ba
2+and Sr
2+plasma produces Complex effect, generate the stable complex compound with higher solubility, stop these particles to be combined with corresponding acid group, prevent precipitation, thereby effectively stoped kapillary and the trunnion of the secondary precipitate obstruction oil field stratum after the molten dirt of unblocking agent.And; polyepoxy sodium succinate also has good corrosion inhibition; Sauerstoffatom in its molecular polarity group; there is not share electron pair; can become adsorption center adsorbing metal and metal and form five-membered cyclic compound; and be adsorbed in metallic surface, form the protective membrane of one deck densification along metallic surface, thereby play the effect of inhibition protection oil production equipment.
2, Sunmorl N 60S: be a kind of multi-hydroxy carboxy acid's type scale remover, in solvay-type clean-out system, calcium, iron, magnesium, barium, strontium plasma are had to fabulous coordination ability, and corresponding carbonate, silicates and the Sulfates of these ions are had to good complexing cleansing power, also there is good corrosion mitigating effect simultaneously, and present synergistic effect, in carboxylate salt complexing unblocking agent formula, can strengthen complexing effect.
3, polyoxyethylene glycol: polyoxyethylene glycol is that molecular-weight average is the general name of 200～6000 ethylene glycol superpolymer, due to the difference of its molecular weight, character is also variant, through our experimental study, the molecular weight of final selected polyoxyethylene glycol is 1500～2000 o'clock, can significantly improve wetting ability and the wettability of unblocking agent.
4, trolamine: in the time that oil field stratum cleans de-plugging, have good solubilizing effect, can well absorb carbonic acid gas and the hydrogen sulfide on stratum.Oil field stratum medium pitch shape colloid is had to very strong cleansing power.Use trolamine can make deep that unblocking agent enters polymkeric substance fast to form flushing channel, make unblocking agent bituminous matter expand gradually, softening, finally form the colloid aqueous solution soluble in water.
5, lactic acid second fat: be important aromatic series intermediate and Organic Chemicals, as medical, agriculture intermediate, and can be used as solvent, clean-out system, lubricant etc.It has good temperature expression range, can with water and organic system compatibility, readily biodegradable, can replace most of Halogens and poisonous solvent.Foodstuff additive and medical material etc. that lactic acid second fat is recommended to the utmost by U.S. FDA.
6, polyoxyethylenated alcohol sodium sulfate and amino acid sodium: we draw through up to a hundred research: anion surfactant polyoxyethylenated alcohol sodium sulfate mixes use with zwitterionics amino acid sodium, owing to interacting between the negative charge of anion surfactant and zwitterionics center positive charge, thereby form complex compound.And the emulsifying property of this complex compound, wettability, dispersiveness, perviousness make the not available composite performance of single component.Hydrophilic and lipophilicity is all better than original anion surfactant and zwitter-ion surfactivity.Adopt in the present invention the polyoxyethylenated alcohol sodium sulfate of 1.0:1.2 mole to mix with amino acid sodium, its dissociation constant shows with relative adsorptive power data results, these two kinds of tensio-active agents can form complex compound quantitatively, in the time of lower concentration, its surface tension is very low, surfactivity is very large, has good synergistic effect.
7, active attapulgite soil: active attapulgite soil is a kind of silicate crystal mineral containing Shuifu County's magnesium, it can be effective as the carrier of tensio-active agent.Attapulgite after overactivation and modification as carrier, to utilize organic coupling agent to process attapulgite, coupling agent is with chemical bonds, polyoxyethylenated alcohol sodium sulfate and amino acid natrium surfactant and vanadium pentoxide catalyst are adsorbed on the many micropore surfaces of Attapulgite, combine with active attapulgite soil surface in modes such as coverings, reach surface and improve the object of physics and chemistry performance at interface, and the solvent in adsorbable agent of active attapulgite soil, to make this product of solid powdery.
8, Vanadium Pentoxide in FLAKES: Vanadium Pentoxide in FLAKES in this agent as catalyzer, in oil field stratum and oil well pipe laying, the deposition of divalence sulfonate dirt reacts with the polycarboxylic acid amine salt in this unblocking agent, under the effect of the catalyzer of Vanadium Pentoxide in FLAKES, generate metal carboxylate micromolecular compound soluble in water.
9, lipase: lipase is a kind of biological catalyst, the protein being produced by biological activity cell forms, in order to prevent lipase segregation, select carrier that specific surface area is large to keep its stability, experimental study selects active attapulgite soil best as the carrier effect of this kind of enzyme.Under the effect of biological enzyme, easily there is biological degradation in polymer material dirt, becomes oligopolymer and monomer, is decomposed into water-soluble oligopolymer, reduces viscosity, makes the easily degraded of polymer material dirt.
10, sorbitan carboxylic esters: be a kind of well emulsifying agent, in molecule, contain hydrophilic and tensio-active agent lipophilicity group simultaneously, can be in the time that oil field stratum cleans de-plugging, at noodle oriented adsorption, play stable, emulsifying effect, unblocking agent liquid dispersion is arrived to stratum micropore and kapillary deep.In the present invention, sorbitan carboxylic esters is many-sided as the effect of tensio-active agent, its major function has the effects such as emulsification, lubricated, adjusting viscosity, also have germ resistance concurrently, improve the surface tension between oil reservoir and unblocking agent, make it to form uniform decomposer or emulsion, and calcium and magnesium metal ion are had to cleanup action and biodegradability.
11, to hydroxyl sulfoacid sodium: because containing hydroxy functional group, be a kind of well complexing agent, iron, copper, calcium, magnesium ion are had to very strong complexing action and corrosion inhibition; And the divalence sulfonic acid salt crust in ternary displacement system is had to good solvency action, strengthen cleansing power.
12, t-butyl hydroperoxide: t-butyl hydroperoxide is to the deliquescent oxygenant of polymer material dirt in oil field stratum, it in this unblocking agent, is the introducing agent as oxide group, can drive to ternary in oil field stratum that polymer material is oxidized and chain rupture, reaction generates micromolecular compound soluble in water.
13, two ethylene glycol laurates: as defoamer, during due to cleaning de-plugging, the kinds of surface promoting agent of interpolation can produce foam, cause entrainment, and affect plugging removal effect, therefore add this product in the time cleaning de-plugging, effectively to eliminate the foam causing due to tensio-active agent.
We utilize modern science and technology principle from eco-friendly viewpoint, adopt HUMAN HEALTH, and new raw material, new reaction, new process and novel method that ecotope is harmless, realize the aim that patented product of the present invention and Ecological harmony develop.Patent of the present invention is used Green Chemistry Theory and technology exactly, selects nontoxic development of raw materials green synthesis process, the production process of the friendly type of create environment, and patented product of the present invention is in the time of oil field stratum de-plugging, nontoxic to operator and oil field environment.Association mechanism of the present invention is as follows with development main technical requirements of the present invention:
1, the neutral unblocking agent mechanism of oilfield chemistry
In oil extraction process, because Oil extraction is used the local water of different sources and mixing of ground injected water, the cooling in local water extraction process, the heating in oil water separation process, just can produce incrustation scale.To stratum injected water or alkali aqueous solution, also can produce scale formation in order to improve oil recovery factor.In oil field, modal dirt is calcium carbonate scale, Calucium Silicate powder dirt, calcium sulfate scale, strontium sulfate scale and barium sulfate scale etc., conventionally the high salt of content solubleness high, that easily separate out in some metallic corrosion products and some oil-field water is also included within dirt.Fouling mainly occurs in the formation rock surface that current pass through, the surface of line equipment, causes the obstruction of stratum, pipeline, and the corrosion of pipeline and equipment, affects normal oil production, even causes the possible permanent damage of oil reservoir.Need to take measures to prevent dirty generation for this reason, remove in time the dirt of tying in line equipment.
The precipitation process of fouling and wax is similar, and the generation of dirt is through the growth of dirty nucleus formation, dirty nucleus and the deposition three phases of dirt.Dirt is grown on some active site of solid surface, forms dirty particle.Owing to there being multiple positive and negative ion in oil-reservoir water, injected water, dirt is made up of multiple inorganics often.Dirt is dissolving, the ionization equilibrium of multiple inorganics with the balance of water, and its equilibrium conditions and equilibrium composition are determined by solubility product, ionic product, ionization equilibrium relational expression, ionic strength and the various ionic activity Relationship of Coefficients formulas etc. that form each dirty composition.Water ion and solid surface material generation chemical reaction under certain conditions, the such as dissolving of corrosion, water ion pair rock composition or water ion be in the deposition of rock surface etc., therefore dirt separate out also relevant with the equilibrium constant of these chemical reactions.
The present invention considers from pore texture angle, according to complex scheme, improves and recovers reservoir permeability as object taking expandable pores venturi.This neutral unblocking agent system is dissolved dirt with oxidation, chain rupture and complexing, reaction generates mashed prod more gently, can avoid producing particle because of precipitation, this without injuring de-plugging for medium-high permeable reservoir, the maintenance of pore texture is relatively good, and the negative effect of bringing is relatively very little, for low permeability reservoir, de-plugging safety coefficient is high, and success ratio is also high.If employing acidification to dispel block, once acidifying failure, those are insoluble to sour throw out and flow and stop up the pore constriction on stratum with particulate form, and the difficulty that makes reservoir again increase production transformation increases greatly.Neutral unblocking agent provided by the invention is dredged pore constriction, recovery reservoir permeability as object taking de-plugging, acid-soluble to the carbonate in reservoir, silicates and metal oxide etc. non-shale is stopped up to material and be dissolved as mashed prod.Adopt neutral unblocking agent de-plugging provided by the invention, do not injure reservoir skeleton, it is also more easy to control that potential throw out is dissolved in complexing, therefore, to reservoir without injury.
Neutral complexing de-plugging is a kind of method that uses chemosmosis, solubilising, oxidation, chain rupture and conversion, make dirty type generation chemical reaction be converted into water-soluble salt, therefore under neutrallty condition, dirt is had to good solubility, between dirty structure, there is very strong penetration power, can enter dirty intergranule, dirt is dissolved completely, the carbonate scale of calcium, magnesium, barium and strontium and sulfate scale are dissolved in water, generate solubility calcium, magnesium, barium and strontium salt; With the active group of neutral unblocking agent, sulfate scale can be converted into water miscible compound; The divalence sulfonic acid salt crust depositing in oil reservoir, oil well pipe laying reacts with the polycarboxylic acid amine salt in this agent etc., under the effect of vanadium pentoxide catalyst, generates the micromolecular Sulfonates water solubles.In its stratum medium pitch dirt and other polymer scale and this agent-OH(alcoholic extract hydroxyl group and phenolic hydroxyl group) ,-group generation synergistic effects such as ONa, reaction chain rupture generates small molecules polymkeric substance soluble in water, to reach the object of thorough removing superpolymer material dirt and pitch dirt.In oil field stratum, polymer material dirt is under the effect of this unblocking agent, by removing of random depolymerization, side group and low-molecular material etc., can cause the chain-breaking reaction that the molecular weight of polyacrylamide polymers material dirt reduces, and polymkeric substance is easily degraded.
2, select the technical requirements of the neutral unblocking agent of oil field stratum
The neutral unblocking agent in oil field, by multiple complexing agent, permeate agent, wetting agent and kinds of surface promoting agent is composite forms, we are in the time of the prescription of the neutral unblocking agent of research the present invention, each selected component is neutrality or meta-alkalescence material, each component can not produce corrosion to metallic substance, and its compatibleness of various ingredients used, mutual solubility, preservative property, wettability and stability are all fine, in unblocking agent, do not contain H
+, Cl
-, S
2-, SO
4 2-in the easy ion that produces corrosive medium.Material used is all nontoxic, tasteless, corrosion-free or meta-alkalescence material, and is easy to degrade in stratum, free from environmental pollution.This unblocking agent has good oxidation, chain rupture, coordination, complexing, infiltration and solvency action to carbonate, silicate, phosphoric acid salt and phosphatic calcium, magnesium ion, chemical cleaning speed is fast, silicate scale and sulfate scale are also had to good scavenging(action), in oil field complexing de-plugging process, owing to not containing H in this agent
+and Cl
-producing well equipment and oil recovery bar and well are not produced to corrosion, without dead angle, in stratum, do not produce precipitation, do not cause the stifled well of secondary of cleaning materials precipitation, can be under normal temperature to 100 DEG C condition, the descaling and blockage relieving time is about 24 hours, the more important thing is and really reach corrosion-free safe chemistry de-plugging, than traditional pickling de-plugging, biological plugging releasing and solvent de-plugging safety and reliability.
3, the safe reliability of neutral unblocking agent
The neutral unblocking agent of the present invention is not containing mineral acid, organic acid, highly basic and cleaning inhibiter, pH is 6～7, by multiple pharmacy intermediate, neutral complexing agent, oxygenant, tensio-active agent, defoamers etc. are composite to be formed, fast in oil field stratum de-plugging speed, to bituminous matter dirt, sulfosalt surfactant dirt, polyacrylamide material dirt, various calcium magnesium salts dirts have very strong solvency action, in cleaning de-plugging process, really reach corrosion-free matting de-plugging, than traditional chemical cleaning mineral acid, organic acid, highly basic safety and reliability, while thoroughly having eliminated because of use acidifying strata, inhibiter lost efficacy, the corrosion of burst factor to oil production equipment such as inhibiter emulsification inequality or misoperation, in oil field stratum de-plugging process, can replace the acidification to dispel block processing of hydrochloric acid and hydrofluoric acid completely.
Details are as follows for the neutral unblocking agent major technique of the present invention effect:
1, single stage method can complete the de-plugging of oil field stratum
The present invention is mainly by polyepoxy sodium succinate, Sunmorl N 60S, form kinds of surface promoting agents such as hydroxyl sulfoacid sodium, ethyl lactate, lipase, sorbitan carboxylic esters, Vanadium Pentoxide in FLAKES and polyoxyethylenated alcohol sodium sulfate and amino acid sodium, the pH of unblocking agent is 6～7, not containing mineral acid and organic acid, also not containing harmful ions such as hydrogen ion, chlorion and sulfate radicals, corrosion rate is less than 0.1g/ (m
2h), reach corrosion-free safe de-plugging.Use this neutral unblocking agent in oil field stratum de-plugging process, can be under normal temperature to 100 DEG C condition, single stage method completes the chemical cleaning de-plugging to all kinds of incrustation scales, without neutralizing treatment and Passivation Treatment, saves the chemical plugging removal time, improves de-plugging efficiency.
2, remove polymer material dirt and the bituminous matter dirt that stratum ternary composite driving produces
The compound dirt that the present invention generates precipitations such as the divalence sulfonated petro-leum precipitation dirt, polyacrylamide polymers material dirt and the ferric oxide dirts that are produced by tensio-active agent in ternary compound oil drive system oil recovery process, in 24 hours, under free from corrosion cleaning working condition, complete the chemically neutral descaling and blockage relieving of oil field stratum.This unblocking agent can dissolve the tamper of oil field stratum studies on asphaltene dirt fast, make the permeate agent adding enter fast the inside of organic polymer material dirt, unblocking agent is contacted rapidly with organic polymer material dirt, make bituminous matter dirt and polymer material dirt expand, transform, finally form soluble in the small molecules solution of water.
3, protection stratum support and kapillary can safe de-pluggings
The neutral unblocking agent of the present invention; with de-plugging dredging pore constriction, recovery reservoir permeability is object, the de-plugging of the polymer material dirt to carbonate scale, silicate scale, sulfate scale, sulfonate surfactant dirt; there is good complexing, perviousness and solvability; can be penetrated into the deep of oil field stratum, de-plugging area is large, and reaction residue becomes pasty state; do not produce the phenomenon such as residue and secondary precipitate particulate; make reservoir exempt from acid infringement, kapillary is had to reaming effect, protection stratum support.
Embodiment
The molecular weight of the polyoxyethylene glycol that embodiment uses is 1500～2000.
Embodiment 1, takes raw material: polyepoxy sodium succinate 35kg, Sunmorl N 60S 20kg, polyoxyethylene glycol 2kg, trolamine 2kg, ethyl lactate 9kg, polyoxyethylenated alcohol sodium sulfate 9kg, amino acid sodium 11kg, active attapulgite soil 14kg, Vanadium Pentoxide in FLAKES 0.2kg, lipase 5kg, sorbitan carboxylic esters 6kg, to hydroxyl sulfoacid sodium 15kg, t-butyl hydroperoxide 4kg and two ethylene glycol laurate 0.2kg.
In the steps below above-mentioned raw materials is prepared into the neutral unblocking agent composition in oil extraction in oil field stratum:
1, by polyepoxy sodium succinate 35kg, Sunmorl N 60S 20kg, polyoxyethylene glycol 2kg, trolamine 2kg, ethyl lactate 9kg and active attapulgite soil 5kg, carry out fragmentation with shredder, cross after 20 mesh sieves and stir 40 minutes to evenly with stirrer, make the first powder.
2, by polyoxyethylenated alcohol sodium sulfate 9kg, amino acid sodium 11kg and active attapulgite soil 7kg, stir 1 hour to evenly with taper mixing and blending machine, polyoxyethylenated alcohol sodium sulfate and amino acid sodium are fully adsorbed by active attapulgite soil carrier, make the second powder after then pulverizing 20 mesh sieves.
3, by Vanadium Pentoxide in FLAKES 0.2kg, lipase 5kg and active attapulgite soil 2kg, use taper mixing and blending machine to stir 40 minutes to evenly, cross 40 mesh sieves and make the 3rd powder.
4, by sorbitan carboxylic esters 6kg, to hydroxyl sulfoacid sodium 15kg, t-butyl hydroperoxide 4kg and two ethylene glycol laurate 0.2kg, stir 40 minutes to evenly with tapered mixing and blending machine, 20 mesh sieves make the 4th powder.
5, the first powder making, the second powder, the 3rd powder and the 4th powder mixing and stirring are made to the neutral unblocking agent in oil extraction in oil field stratum.
Embodiment 2, takes raw material: polyepoxy sodium succinate 33kg, Sunmorl N 60S 18kg, polyoxyethylene glycol 3kg, trolamine 3kg, ethyl lactate 10kg, polyoxyethylenated alcohol sodium sulfate 7kg, amino acid sodium 8.5kg, active attapulgite soil 10kg, Vanadium Pentoxide in FLAKES 0.15kg, lipase 6kg, sorbitan carboxylic esters 8kg, to hydroxyl sulfoacid sodium 16kg, t-butyl hydroperoxide 6kg and two ethylene glycol laurate 0.16kg.
In the steps below above-mentioned raw materials is prepared into the neutral unblocking agent composition in oil extraction in oil field stratum:
1,, by polyepoxy sodium succinate 33kg, Sunmorl N 60S 18kg, polyoxyethylene glycol 3kg, trolamine 3kg, ethyl lactate 10kg and active attapulgite soil 4kg, carry out fragmentation with shredder; All the other are with embodiment 1.
2, by polyoxyethylenated alcohol sodium sulfate 7kg, amino acid sodium 8.5kg and active attapulgite soil 5kg, use taper mixing and blending machine to stir 1 hour to even, all the other are with embodiment 1.
3, by Vanadium Pentoxide in FLAKES 0.15kg, lipase 6kg and active attapulgite soil 1kg, with the stirring of taper mixing and blending machine, all the other are with embodiment 1.
4, by sorbitan carboxylic esters 8kg, to hydroxyl sulfoacid sodium 16kg, t-butyl hydroperoxide 6kg and two ethylene glycol laurate 0.16kg, with tapered mixing and blending machine stirring, all the other are with embodiment 1.
5, with embodiment 1.
Embodiment 3, takes raw material: polyepoxy sodium succinate 30kg, Sunmorl N 60S 23kg, polyoxyethylene glycol 2.5kg, trolamine 2.5kg, ethyl lactate 12kg, polyoxyethylenated alcohol sodium sulfate 10kg, amino acid sodium 12kg, active attapulgite soil 13kg, Vanadium Pentoxide in FLAKES 0.1kg, lipase 7kg, sorbitan carboxylic esters 5kg, to hydroxyl sulfoacid sodium 18kg, t-butyl hydroperoxide 3kg and two ethylene glycol laurate 0.1kg.
In the steps below above-mentioned raw materials is prepared into the neutral unblocking agent composition in oil extraction in oil field stratum:
1,, by polyepoxy sodium succinate 30kg, Sunmorl N 60S 23kg, polyoxyethylene glycol 2.5kg, trolamine 2.5kg, ethyl lactate 12kg and active attapulgite soil 5.5kg, carry out fragmentation with shredder; All the other are with embodiment 1.
2, by polyoxyethylenated alcohol sodium sulfate 10kg, amino acid sodium 12kg and active attapulgite soil 5.5kg, use taper mixing and blending machine to stir 1 hour to even, all the other are with embodiment 1.
3, by Vanadium Pentoxide in FLAKES 0.1kg, lipase 7kg and active attapulgite soil 2kg, with the stirring of taper mixing and blending machine, all the other are with embodiment 1.
4, by sorbitan carboxylic esters 5kg, to hydroxyl sulfoacid sodium 18kg, t-butyl hydroperoxide 3kg and two ethylene glycol laurate 0.1kg, with tapered mixing and blending machine stirring, all the other are with embodiment 1.
5, with embodiment 1.
Embodiment 4, takes raw material: polyepoxy sodium succinate 36kg, Sunmorl N 60S 24kg, polyoxyethylene glycol 3kg, trolamine 4kg, ethyl lactate 11kg, polyoxyethylenated alcohol sodium sulfate 8kg, amino acid sodium 9.6kg, active attapulgite soil 15kg, Vanadium Pentoxide in FLAKES 0.2kg, lipase 7kg, sorbitan carboxylic esters 7kg, to hydroxyl sulfoacid sodium 17kg, t-butyl hydroperoxide 7kg and two ethylene glycol laurate 0.3kg.
In the steps below above-mentioned raw materials is prepared into the neutral unblocking agent composition in oil extraction in oil field stratum:
1,, by above-mentioned polyepoxy sodium succinate, Sunmorl N 60S, polyoxyethylene glycol, trolamine, ethyl lactate and 6kg active attapulgite soil, carry out fragmentation with shredder; All the other are with embodiment 1.
2, by above-mentioned polyoxyethylenated alcohol sodium sulfate, amino acid sodium and 7kg active attapulgite soil, use taper mixing and blending machine to stir 1 hour to even, all the other are with embodiment 1.
3,, by above-mentioned Vanadium Pentoxide in FLAKES, lipase and 2kg active attapulgite soil, with the stirring of taper mixing and blending machine, all the other are with embodiment 1.
4, by above-mentioned sorbitan carboxylic esters, to hydroxyl sulfoacid sodium, t-butyl hydroperoxide and two ethylene glycol laurate, with tapered mixing and blending machine stirring, all the other are with embodiment 1.
5, with embodiment 1.
Embodiment 5, takes raw material: polyepoxy sodium succinate 32kg, Sunmorl N 60S 25kg, polyoxyethylene glycol 3kg, trolamine 3kg, ethyl lactate 10kg, polyoxyethylenated alcohol sodium sulfate 8.5kg, amino acid sodium 10.2kg, active attapulgite soil 15kg, Vanadium Pentoxide in FLAKES 0.15kg, lipase 6.5kg, sorbitan carboxylic esters 7kg, to hydroxyl sulfoacid sodium 16kg, t-butyl hydroperoxide 5kg and two ethylene glycol laurate 0.25kg.
In the steps below above-mentioned raw materials is prepared into the neutral unblocking agent composition in oil extraction in oil field stratum:
1,, by above-mentioned polyepoxy sodium succinate, Sunmorl N 60S, polyoxyethylene glycol, trolamine, ethyl lactate and 6kg active attapulgite soil, carry out fragmentation with shredder; All the other are with embodiment 1.
2, by above-mentioned polyoxyethylenated alcohol sodium sulfate, amino acid sodium and 7kg active attapulgite soil, use taper mixing and blending machine to stir 1 hour to even, all the other are with embodiment 1.
3,, by above-mentioned Vanadium Pentoxide in FLAKES, lipase and 2kg active attapulgite soil, with the stirring of taper mixing and blending machine, all the other are with embodiment 1.
4, by above-mentioned sorbitan carboxylic esters, to hydroxyl sulfoacid sodium, t-butyl hydroperoxide and two ethylene glycol laurate, with tapered mixing and blending machine stirring, all the other are with embodiment 1.
5, with embodiment 1.
Claims (3)
1. the neutral unblocking agent composition in oil extraction in oil field stratum, it is characterized in that: the raw material by following portions by weight is made: 30～36 parts of polyepoxy sodium succinates, 18～25 parts of Sunmorl N 60Ss, 2～3 parts of polyoxyethylene glycol, 2～4 parts of trolamines, 9～12 parts of ethyl lactates, 7～10 parts of polyoxyethylenated alcohol sodium sulfate, 8～12 parts, amino acid sodium, 10～15 parts, active attapulgite soil, 0.1～0.2 part of Vanadium Pentoxide in FLAKES, 5～7 parts, lipase, 5～8 parts of sorbitan carboxylic esterses, to 15～18 parts, hydroxyl sulfoacid sodium, 0.1～0.3 part of 3～7 parts of t-butyl hydroperoxides and two ethylene glycol laurate.
2. the neutral unblocking agent composition in a kind of oil extraction in oil field as claimed in claim 1 stratum, is characterized in that: the molecular weight of polyoxyethylene glycol is 1500～2000.
3. a preparation method for the neutral unblocking agent composition in the oil extraction in oil field stratum described in claim 1 or 2, is characterized in that comprising the steps:
A, by 9～12 parts of 30～36 parts of polyepoxy sodium succinates, 18～25 parts of Sunmorl N 60Ss, 2～3 parts of polyoxyethylene glycol, 2～4 parts of trolamines, ethyl lactate and 4～6 parts, active attapulgite soil, carry out fragmentation with shredder, after crossing 20 mesh sieves, stir, make the first powder;
B, by 8～12 parts of 7～10 parts of polyoxyethylenated alcohol sodium sulfate, amino acid sodium and 5～7 parts, active attapulgite soil, stir 1 hour to evenly with taper mixing and blending machine, polyoxyethylenated alcohol sodium sulfate and amino acid sodium are fully adsorbed by active attapulgite soil carrier, make the second powder after then pulverizing 20 mesh sieves;
C, by 5～7 parts of 0.1～0.2 part of Vanadium Pentoxide in FLAKESs, lipase and 1～2 part, active attapulgite soil, stir 40 minutes to evenly with taper mixing and blending machine, cross 40 mesh sieves and make the 3rd powder;
D, by 5～8 parts of sorbitan carboxylic esterses, to 3～7 parts, 15～18 parts, hydroxyl sulfoacid sodium, t-butyl hydroperoxide and 0.1～0.3 part of two ethylene glycol laurate, stir 40 minutes to evenly with tapered mixing and blending machine, 20 mesh sieves make the 4th powder;
E, the first powder making, the second powder, the 3rd powder and the 4th powder mixing and stirring are made to the neutral unblocking agent in oil extraction in oil field stratum.
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