CN104194759B - Oil extraction in oil field stratum neutral de-plugging agent composition and preparation method thereof - Google Patents
Oil extraction in oil field stratum neutral de-plugging agent composition and preparation method thereof Download PDFInfo
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- CN104194759B CN104194759B CN201410489270.3A CN201410489270A CN104194759B CN 104194759 B CN104194759 B CN 104194759B CN 201410489270 A CN201410489270 A CN 201410489270A CN 104194759 B CN104194759 B CN 104194759B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
Abstract
A kind of oil extraction in oil field stratum neutral de-plugging agent composition, is made up of following portions by weight raw material：0.1～0.3 part of 30～36 parts of polyepoxy sodium succinate, 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 sodium sulfate of polyethenoxy ether of fatty alcohol, 8～12 parts of amino acid sodium, 10～15 parts of active attapulgite, 0.1～0.2 part of vanadic anhydride, 5～7 parts of lipase, 5～8 parts of sorbitan carboxylic esterses, 15～18 parts of p-hydroxy benzenyl sulfonate sodium, 3～7 parts of t-butyl hydroperoxide and double ethylene glycol laurates.Fast, neutral corrosion-free, the material dirt that can quickly dissolve ternary composite displacement system generation of De-plugging speed of the present invention, Pitch deposits dirt, carbonate scale, silicate scale etc., de-plugging waste liquid can be from degraded, sewage disposal is carried out without the row of returning ground, cleaning oil field stratum de-plugging, have corrosion-free, without dead angle, precipitation and secondary stifled well is not produced, de-plugging process time is less than 24 hours.
Description
Technical field
The present invention relates to the auxiliary agent that a kind of oil extraction in oil field is used, particularly a kind of oil extraction in oil field stratum neutral de-plugging agent combination
Thing, the invention further relates to the preparation method of oil extraction in oil field stratum neutral de-plugging agent composition.
Background technology
First, the proposition of problem
1st, many oil fields both domestic and external are all injured by fouling to some extent in water flooding recovery and are perplexed, especially in exploitation
Stage intermediary and later stages is entered, with the increase of Water Content in Oil amount, scale problems become more universal and serious.As oil field water is tied
Dirt causes reservoir injury, oil recovery well shaft, water filling well shaft and oil extraction pump and device systems blocking, so as to cause too early oil well,
Oil extraction pump and equipment scrapping.These problems substantially increase cost for oil production, have a strong impact on the normal production of oil gas.In order to preferably
The scale problems of oil field stratum and oil extraction pump and equipment are solved, the fouling in oilfield water extraction is solved and is injured this technology hardly possible
Topic, needs using de-plugging agent product.
2nd, oil is the strategic goods and materials for being related to China's economic lifeline, in China, middle and high infiltration oil reservoir development Steady product technique
Relatively ripe, but how old well continuously steady production is realized for low permeability and ultra-low permeability reservoirs, and obtain higher final harvesting
Rate and economic benefit, are a major challenge that domestic many oil fields face.Therefore, tertiary oil recovery technology level how is improved, is increased
The recovery ratio of existing oil reservoir, with important economic worth and strategic importance.The application of alkaline surfactant polymer flooding oil-field technology, greatly
The speed of domestic each elephant production decline is delayed, it has also become the major measure that field output is taken over.With ternary complex
The use of system, the accumulation of alkali consumption have serious injury to the skeleton and cement of reservoir rock, also result in the wound to oil reservoir
Evil, reduces reservoir permeability, injects pressure drop, and oil-water well fouling is serious, to the petroleum sulfonate that commonly uses in tertiary oil recovery,
There are a certain degree of impact and injury to precipitation of generation etc. in multivalent cation aqueous solution, therefore, to applying ternary complex
The producing well of system, needs to eliminate the harmful effect using de-plugging scale removal product.
It is as follows that salt cause for scaling is produced during alkaline surfactant polymer flooding oil-field technology application：Stratum water fouling is oil field production
In inevitable and subject matter to be faced.Unfavorableization produced between the change of stratum water pH value and alkali and reservoir rock
Reaction is learned, producing fouling precipitation becomes increasingly to project, and fouling sediment is mainly carbonate scale, silicate scale and sulfate
Dirt.
In order that the equilibrium interfacial tension of alkali/Surfactant/Polymer ternary system can reach 10 orders of magnitude, it is necessary to plus
Enter substantial amounts of alkali, particularly highly basic NaOH.And the addition of alkaline agent, there is serious injury to reservoir rock skeleton and cement.With
This, necessarily damages to oil reservoir, injects pressure drop, or oil-water well fouling, it is necessary to shut down, serious meeting causes oil reservoir to collapse
Collapse, particularly the oil reservoir near injection well caves in, or even blocking.High concentration containing 0.8%～1.5% in three-component compound system
Alkali, particularly highly basic Na2CO3And NaOH, therefore the pH value of solution, is necessarily made to reservoir rock mineral in the range of 12～14
Into injury, or even grievous injury, dirt is produced, the blocking on stratum is caused.
In three-component compound system, surfactant is as follows to the injury and the blocking dirt analysis of causes of oil reservoir：Due to tri compound
The petroleum sulfonate added in system（Sodium）React with these polyvalent cations in the water of stratum and generate divalence mahogany acid
Salt（Calcium, magnesium）., under the conditions of uniform temperature, the solubility in water is limited for divalence petroleum sulfonate.Result of study shows, local
Contain certain density Ca in layer water2+And Mg2+When, divalence petroleum sulfonate precipitation will occur.This of surfactant sinks
Damage for Detention on which in pore media is had important function and impact by shallow lake phenomenon, and divalence petroleum sulfonate precipitation occurs,
Not only Severe blockage oil reservoir, and can accelerate the depletion rate of surfactant, makes the alkali of injection, surfactant, polymer
The displacement of reservoir oil effect premature failure of ternary composite driving.
Second, traditional de-plugging means
At present, oil field is using acidifying de-plugging, biological plugging releasing and solvent de-plugging, main using acidifying de-plugging.Being acidified de-plugging is
By means of inorganic acid（Hydrochloric acid, hydrofluoric acid, also useful sulfuric acid）, it is also possible to use organic acid（Formic acid, acetic acid etc.）To formation rock, block up
The chemical corrosion of plug thing, and the hydraulic action of acidifying pressure, improve stratum permeability, realize that oil well production increasing, well increase
The engineering measure of note.In order to complete to be acidified engineering objective, in acidifying solution in addition to host acid, also need to add corrosion inhibiter, iron ion
Stabilizer etc..
Acidifying hydrochloric acid used and mud acid are strong acid, and especially hydrochloric acid is exceedingly fast with the reaction of carbonate, is easily caused nearly well
The stratum at position is excessively acidified, and deep-section fully cannot be acidified, high temperature deep well shadow of this phenomenon to low permeability formation
Ring more greatly, be the main cause for causing acidification failure.In acidization, acidification corrosion inhibitor easily receives formation temperature, pressure
Affect with iron ion and fail, once acidification corrosion inhibitor failure, will result in the serious corruption of producing well, oil well pump and oil transporting appliance
Erosion, therefore acidifying de-plugging have potential great risk.
Content of the invention
It is an object of the invention to provide a kind of fast, the neutral free from corrosion oil extraction in oil field stratum neutral de-plugging agent of De-plugging speed
Composition；The de-plugging agent can quickly dissolve the material dirt of ternary composite displacement system generation, Pitch deposits dirt, carbonate scale, silicon
Silicate dirt and sulfate scale.The second object of the present invention is the preparation side for providing oil extraction in oil field stratum neutral de-plugging agent composition
Method.
Realize that the technical scheme that the object of the invention is taken is as follows：A kind of oil extraction in oil field stratum neutral de-plugging agent composition, by
The raw material of following portions by weight is made：30～36 parts of polyepoxy sodium succinate, 18～25 parts of sodium gluconate, polyethylene glycol 2～3
Part, 2～4 parts of triethanolamine, 9～12 parts of ethyl lactate, 7～10 parts of sodium sulfate of polyethenoxy ether of fatty alcohol, amino acid sodium 8～12
Part, 10～15 parts of active attapulgite, 0.1～0.2 part of vanadic anhydride, 5～7 parts of lipase, sorbitan carboxylic esterses 5～
8 parts, 15～18 parts of p-hydroxy benzenyl sulfonate sodium, 0.1～0.3 part of 3～7 parts of t-butyl hydroperoxide and double ethylene glycol laurates.
The preparation method that the raw material of above-mentioned parts by weight is prepared into oil extraction in oil field stratum neutral de-plugging agent composition is included
Following step：
A, by 30～36 parts of polyepoxy sodium succinate, 18～25 parts of sodium gluconate, 2～3 parts of polyethylene glycol, triethanolamine
4～6 parts of 2～4 parts, 9～12 parts of ethyl lactate and active attapulgite, are crushed with grinder, and after crossing 20 mesh sieves, stirring is equal
Even, the first powder is obtained；Main component of first powder as de-plugging agent；
B, by 7～10 parts of sodium sulfate of polyethenoxy ether of fatty alcohol, 8～12 parts of amino acid sodium and active attapulgite 5～7
Part, 1 hour is stirred to uniform with cone blender, make sodium sulfate of polyethenoxy ether of fatty alcohol recessed by activity with amino acid sodium
Convex rod soil carrier fully adsorbs, and the second powder was obtained after then crushing 20 mesh sieves；Second powder is solvay-type as de-plugging agent
Supporting surfactant；
C, by 1～2 part of 0.1～0.2 part of vanadic anhydride, 5～7 parts of lipase and active attapulgite, mixed with taper
Mixer stirs 40 minutes to uniform, crosses 40 mesh sieves and the 3rd powder is obtained；3rd powder is used as Catalyst Adsorption powder；
D, by 5～8 parts of sorbitan carboxylic esterses, 15～18 parts of p-hydroxy benzenyl sulfonate sodium, t-butyl hydroperoxide 3～7
Part with 0.1～0.3 part of double ethylene glycol laurates, stir 40 minutes to uniform with tapered mixing and blending machine, cross 20 mesh sieves and be obtained
4th powder；4th powder is used as complexing and the auxiliary agent of inhibition；
E, obtained first powder, the second powder, the 3rd powder and the 4th powder mixing and stirring are made oil field
Producing formation neutral de-plugging agent.
The oil extraction in oil field stratum neutral de-plugging agent composition that the present invention is provided, its outward appearance are colourless or slight yellowish powder
Shape, particle size diameter are that water content is less than 6%, and bulk specific weight is 1.03～1.12g/cm less than 20 mesh3, pH is 6～7, oil field ground
During layer de-plugging, used according to the aqueous solution that oil field stratum dirt chocking-up degree water is configured to mass percent concentration 2～5%.This
Invention is applied in two factories of Daqing oil field oil recovery, and the aqueous solution that the present invention is made mass percent concentration 2～5% is used
10Mpa high-pressure pumps are injected in oil extraction in oil field stratum, under the conditions of oil field stratum temperature 45 C, with calcium carbonate, carbonic acid in stratum
There is chemical reaction in magne-scale and ternary composite driving polymer material dirt etc., complete formation cleanup de-plugging, after de-plugging within 24 hours
Oil extraction in oil field rate has reached the designed capacity of producing well.
The present invention does not contain the harmful ions such as hydrogen ion, chlorion and sulfate radical, rate of corrosion without inorganic acid and organic acid yet
It is less than 0.1g/ (m2H), corrosion-free safe de-plugging is reached.
Side of the oil extraction in oil field stratum neutral de-plugging agent that the present invention is provided using infiltration, solubilising, oxidation, chain rupture and conversion
Method, makes various types of dirts in stratum, with this de-plugging agent, chemical reaction occur and is converted into water soluble salt, using this de-plugging agent solution
After stifled, the carbonate scale, silicate scale and the sulfate scale that produce calcium, magnesium metal ion are dissolved in de-plugging cleaning fluid.Neutral
Carbonate scale and sulfate scale can be converted into water soluble compound by the active group of de-plugging agent.For using in oil recovery process
The divalence petroleum sulfonate sediment dirt produced in alkaline surfactant polymer flooding oil-field and polyacrylamide polymers material dirt and iron oxide sink
The reaction such as polybasic carboxylic acid amine salt formed sediment in dirt, with this de-plugging agent, generates soluble micromolecular compound, and there is degradability, oil
There is molten dirty cooperative effect, reaction in the asphalitine dirt and the group such as other polymers dirt and-OH ,-ONa in this agent in the layer of field
Chain rupture generates molecular weight polymers soluble in water, removes polymer material dirt and asphalitine dirt to reach, realizes to oil field stratum
The purpose of neutral de-plugging.
Of the invention neutral corrosion-free, for cleaning oil field stratum de-plugging, can one-step method complete the de-plugging of oil field stratum, can be fast
Material dirt, Pitch deposits dirt, carbonate scale, silicate scale and sulfate scale that instant solution ternary composite displacement system is produced, clearly
Wash de-plugging waste liquid have can self-degradation, carry out sewage disposal without the row of returning ground, with corrosion-free, without dead angle, do not produce
Precipitation and secondary precipitate particles holography capillarity and the advantages of stifled well, de-plugging process time was reached less than 24 hours
Corrosion-free safe de-plugging, than traditional acidifying de-plugging, biological plugging releasing and solvent de-plugging safety and reliability.
The present disclosure additionally applies for the cleaning de-plugging and the corrosion of oil production equipment of oil field stratum during oil extraction in oil field, can be solved
Problem, effective control de-plugging agent and sandstone reaction speed, and pastel is generated, the permeability on stratum is improved, is prevented dirty to stratum
Dye, improves oil recovery factor.
The Main Function and application mechanism of each component of the present invention is as described below：
1st, polyepoxy sodium succinate：The poly-epoxy succinic acid used as the main component of de-plugging agent in this de-plugging agent
Sodium, it by five to six rings compound group into, do not result in environmental accumulation, polluted-water after de-plugging, biological degradability is good, is me
Test the complexing of metal ion agent of selection by molten dirt in a large number.We are proved through de-plugging research evaluation result：Polycyclic oxygen amber
When Meticortene Solu-Delta-cortef generates complex compound with metal ion, multiple complexing rings are usually formed.Number in one complex molecules the more, network
The stability of compound is higher, the complexing ring formed when ligand and complexing of metal ion the more, ligand and complexing of metal ion
The complex compound of formation is just more stable.Polyepoxy sodium succinate has multiple complexing rings, and can such as with many metal ions simultaneously
Ca2+、Mg2+、Fe3+、Fe2+、Ba2+And Sr2+Plasma produces Complex effect, generates the stable complexing with higher solubility
Thing, is prevented these particles from being combined with corresponding acid group, prevents to precipitate, so as to effectively prevent two after the molten dirt of de-plugging agent
The capillary and trunnion of secondary clogging deposits oil field stratum.Also, polyepoxy sodium succinate also has good corrosion inhibition, its
Oxygen atom in molecular polarity group, with unshared electron pair, can become adsorption site adsorbing metal and form five with metal
Membered cyclic compound, and metal surface is adsorbed in, one layer of fine and close diaphragm is formed along metal surface, so as to play inhibition protection
The effect of oil production equipment.
2nd, sodium gluconate：A kind of multi-hydroxy carboxy acid's type scale remover, in solvay-type cleaning agent, to calcium, iron, magnesium, barium,
Strontium plasma has fabulous coordination ability, and the corresponding carbonate of these ions, silicates and Sulfates are had very
Good complexing cleaning ability, while also having good corrosion mitigating effect, and assumes cooperative effect, matches somebody with somebody in carboxylate complexing de-plugging agent
Fang Zhong, can strengthen complexing effect.
3rd, polyethylene glycol：Polyethylene glycol is the general name of the ethylene glycol high polymer that mean molecule quantity is 200～6000, due to which
The difference of molecular weight, property are also variant, and through our experimental studies, the molecular weight of final selected polyethylene glycol is 1500～2000
When, then it is remarkably improved the hydrophily and wetability of de-plugging agent.
4th, triethanolamine：When oil field stratum cleans de-plugging, there is good solubilizing effect, the two of stratum can be absorbed well
Carbonoxide and hydrogen sulfide gas.There is very strong cleansing power to pitch shape colloid in oil field stratum.Can be made using triethanolamine
De-plugging agent rapidly enters the deep of polymer to form flushing channel, makes de-plugging agent that asphalitine is gradually expanded, softens, last shape
Into the aqueous solution that colloid is soluble in water.
5th, lactic acid second fat：It is important aromatic series intermediate and Organic Chemicals, as medical, agriculture intermediate,
And can be used as solvent, cleaning agent, lubricant etc..It has preferable temperature expression range, can be compatible with water and organic system, Yi Sheng
Thing is degraded, and can replace most of halogen He poisonous solvents.Lactic acid second fat is the food additives recommended to the utmost by U.S. FDA
With medical material etc..
6th, sodium sulfate of polyethenoxy ether of fatty alcohol and amino acid sodium：We are drawn through up to a hundred research：Anionic surface
Activating agent sodium sulfate of polyethenoxy ether of fatty alcohol is used in mixed way with zwitterionic surfactant amino acid sodium, due to anion table
The negative electrical charge of face activating agent and the interphase interaction of zwitterionic surfactant center positive charge, so that form complex compound.And
The emulsibility of this complex compound, wetability, dispersiveness, permeability, make the composite performance not available for single component.Hydrophilic and close
Oiliness is better than original anion surfactant and amphion surface-active.1.0 are adopted in the present invention:1.2 mole
Sodium sulfate of polyethenoxy ether of fatty alcohol mix with amino acid sodium, its dissociation constant and relative adsorption force data result show, this
Two kinds of surfactants can quantitatively form complex compound, and in relatively low concentration, its surface tension is very low, and surface-active is very big,
There is good cooperative effect.
7th, active attapulgite：Active attapulgite is a kind of silicate crystal mineral containing Shuifu County's magnesium, and it can be effectively
Carrier as surfactant.Attapulgite as carrier, is using at organic coupling agent after overactivation and modification
Reason attapulgite, coupling agent with chemical bonds, make sodium sulfate of polyethenoxy ether of fatty alcohol and amino acid sodium surfactant and
Vanadium pentoxide catalyst adsorbs on many micropore surfaces of concave convex rod, is mutually tied with active attapulgite surface in modes such as coverings
Close, reach surface and improve the purpose of the process based prediction model at interface, and molten in adsorbable agent of active attapulgite
Agent, to make this product of solid powdery.
8th, vanadic anhydride：Vanadic anhydride in this agent as catalyst, in oil field stratum and oil well petroleum pipeline
The deposition dirt of divalence sulfonate is reacted with the polybasic carboxylic acid amine salt in this de-plugging agent, in the effect of the catalyst of vanadic anhydride
Under, generate metal carboxylate micromolecular compound soluble in water.
9th, lipase：Lipase is a kind of biocatalyst, is made up of the protein that biologically active cell is produced, in order to
Prevent lipase from isolating, the big carrier of specific surface area to be selected selects active attapulgite to keep its stability, experimental study
Carrier effect as this enzyme is best.Polymer material dirt in the presence of biology enzyme easily occurs biodegradable, becomes oligomer
And monomer, water-soluble oligomer is decomposed into, is reduced viscosity, is made polymer material dirt degradable.
10th, sorbitan carboxylic esterses：It is a kind of good emulsifying agent, in molecule, contains hydrophilic and lipophilic group simultaneously
Surfactant, stable, emulsification can be played when oil field stratum cleans de-plugging in noodle oriented attachment, solving
Blocking agent liquid dispersion is to stratum micropore and capillary deep.In the present invention, sorbitan carboxylic esterses are used as surfactant
Application effect be many, its major function has emulsification, lubrication, adjusts the effect such as viscosity, also has antibiotic property concurrently, improves oil
Surface tension between layer and de-plugging agent, is allowed to form uniform decomposer or emulsion, and calcium and magnesium metal ion is had clearly
The effect of washing and biodegradability.
11st, p-hydroxy benzenyl sulfonate sodium：Because containing hydroxy functional group, be a kind of good complexing agent, to iron, copper, calcium, magnesium from
Son has very strong complexing and corrosion inhibition；And have good dissolution to the divalence sulfonic acid salt crust in ternary displacement system,
Enhance cleansing power.
12nd, t-butyl hydroperoxide：T-butyl hydroperoxide be to oil field stratum in the polymer material deliquescent oxygen of dirt
Agent, is the introducing agent as oxide group in this de-plugging agent, can drive polymer material to ternary in oil field stratum and aoxidize
And chain rupture, reaction generation micromolecular compound soluble in water.
13rd, double ethylene glycol laurates：It is used as defoamer, due to cleaning during de-plugging, the kinds of surface activating agent meeting of interpolation
Produce foam, cause entrainment, and affect plugging removal effect, therefore add this product can when de-plugging is cleaned, effectively eliminate by
In the foam that surfactant causes.
We using modern science and technology principle, are adopted to health, ecological environment from from the viewpoint of environmental friendliness
Harmless new raw material, new reaction, new process and new method, realize the objective that patented product of the present invention is developed with Ecological harmony.This
Patent of invention is exactly with Green Chemistry Theory and technology, from nontoxic development of raw materials green synthesis process, creates ring
The production process of border friendly, patented product of the present invention in oil field stratum de-plugging, to operator and the nontoxic nothing of oilfield environment
Evil.Association mechanism of the present invention is as follows with the main technical requirements for developing the present invention：
1st, oilfield chemistry neutral de-plugging agent mechanism
During oil extraction, due to stratum water of the oil extraction using separate sources and the mixing of ground injection water,
Stratum hydromining go out during cooling, the heating in oil water separation process will produce incrustation scale.In order to improve oil recovery factor and
Water or aqueous alkali is injected to stratum, can also produce scale formation.In oil field modal dirt be calcium carbonate scale, calcium silicates dirt,
Calcium sulfate scale, strontium sulfate scale and barium sulfate scale etc., generally will be high for content in some metallic corrosion products and some oil field water, easy
The salt that the solubility of precipitation is high is also included within dirt.Fouling occurs mainly in the formation rock surface that current pass through, pipeline and sets
Standby surface, causes the corrosion of the blocking of stratum, pipeline, pipeline and equipment, affects normal Petroleum Production, or even causes oil reservoir
Possible permanent damage.The generation for taking measures to prevent dirt is needed for this, removes the dirt that is tied in line equipment in time.
Fouling is similar with the precipitation process of wax, and the generation of dirt is through dirty nucleus formation, the growth of dirty nucleus and dirt
Deposition three phases.Dirt is grown on some active sites of the surface of solids, forms the particle of dirt.In due to oil-reservoir water, injection water
There are multiple positive and negative ions, dirt is often made up of multiple inorganic matters.Dirt is the molten of multiple inorganic matters with the balance of water phase
Solution, ionization equilibrium, its equilibrium condition and equilibrium composition are by constitute the solubility product of each dirty composition, ionic product, ionization equilibrium
Relational expression, ionic strength and various ion activity Relationship of Coefficients formulas etc. are determined.Aqueous ion and solid under certain conditions
There is chemical reaction in surface mass, such as corrosion, aqueous ion are to the dissolving of rock composition or aqueous ion in rock
The deposition on stone surface etc., therefore dirty precipitation is also relevant with the equilibrium constant of these chemical reactions.
The present invention is considered from pore structure angle, according to complex scheme, is improved with expandable pores venturi and recover reservoir infiltration
For the purpose of property.This neutral de-plugging agent system is to aoxidize, chain rupture and complexing dissolving dirt, react shallower generation pastel, can keep away
Exempt to produce particle because of precipitation, for medium-high permeable reservoir, the maintenance of pore structure is relatively good, brings for this fanout free region de-plugging
Negative effect comparatively small, for low permeability reservoir, de-plugging safety coefficient is high, and success rate is also high.If using acidifying
De-plugging, once acidifying failure, those sediments insoluble in acid are with the pore constriction on particulate form flowing blocking stratum so that storage
Layer carries out the difficulty of storey increase design again and substantially increases.The neutral de-plugging agent that the present invention is provided is with de-plugging dredging pore constriction, extensive
For the purpose of multiple reservoir permeability, acid-soluble to the carbonate in reservoir, silicates and metal oxide etc. non-shale is blocked
Material is dissolved as pastel.The neutral de-plugging agent de-plugging provided using the present invention, does not injure reservoir skeleton, and complexing dissolving is potential
Sediment is also relatively easy to control, therefore, to reservoir fanout free region.
Neutral complexing de-plugging is a kind of method of use chemosmosis, solubilising, oxidation, chain rupture and conversion, occurs dirty type
Chemical reaction is converted into water soluble salt, therefore has good dissolubility to dirt in neutral conditions, has very strong between the structure of dirt
Penetration power, can enter dirt crystal grain between, dirt is completely dissolved, the carbonate scale and sulfate scale of calcium, magnesium, barium and strontium is made
Dissolve in water, generate solubility calcium, magnesium, barium and strontium salt class；With the active group of neutral de-plugging agent, sulfate scale can be converted
For water miscible compound；Polybasic carboxylic acid amine in the divalence sulfonic acid salt crust and this agent that deposit in oil reservoir, oil well petroleum pipeline
Salt etc. reacts, and in the presence of vanadium pentoxide catalyst, generates the Sulfonates hydrotrope of small molecule.Pitch dirt in its stratum
With-the OH in other polymer scales and this agent（Alcoholic extract hydroxyl group and phenolic hydroxyl group）, the group such as-ONa there is cooperative effect, reaction chain rupture life
Into molecular weight polymers soluble in water, to reach the purpose for thoroughly removing high polymer material dirt and pitch dirt.In oil field stratum
Polymer material dirt by removing of random depolymerization, side base and low-molecular material etc., can cause poly- in the presence of this de-plugging agent
The chain-breaking reaction that the molecular weight of acrylamide polymer material dirt reduces, makes polymer degradable.
2nd, the technical requirements of oil field stratum neutral de-plugging agent are selected
Oil field neutral de-plugging agent, is formed by multiple complexing agents, bleeding agent, wetting agent and kinds of surface activating agent compounding,
, when the prescription of neutral de-plugging agent of the present invention is studied, each selected component is neutral or meta-alkalescence material, each for we
Kind of component all without producing corrosion to metal material, and various ingredients used its compatibilities, intersolubility, anti-corrosive properties, wetting
Property and stability all fine, in de-plugging agent do not contain H+、Cl-、S2-、SO4 2-Etc. the ion for being also easy to produce corrosive medium.Material used
All it is nontoxic, tasteless, corrosion-free or meta-alkalescence material, and is easy to degrade in the earth formation, free from environmental pollution.The de-plugging agent pair
Carbonate, silicate, phosphate and phosphatic calcium, magnesium ion have good oxidation, chain rupture, coordination, complexing, infiltration and molten
Solution is acted on, and chemical cleaning speed is fast, also has good scavenging action to silicate scale and sulfate scale, is complexed de-plugging in oil field
Cheng Zhong, due to not containing H in this agent+And Cl-, corrosion is not produced to producing well equipment and oil recovery bar and well, without dead angle, in the earth formation
Precipitation is not produced, and the secondary stifled well for not causing cleaning materials to precipitate can be in normal temperature under the conditions of 100 DEG C, and the descaling and blockage relieving time is 24
Hour or so, it is often more important that corrosion-free safe chemistry de-plugging is really achieved, than traditional pickling de-plugging, biological plugging releasing and solvent
De-plugging safety and reliability.
3rd, the security reliability of neutral de-plugging agent
Without inorganic acid, organic acid, highly basic and cleaning corrosion inhibiter, pH is 6～7 to neutral de-plugging agent of the present invention, is by multiple
The compoundings such as pharmaceutical intermediate, neutral complexing agent, oxidant, surfactant, defoamer are formed, in oil field stratum De-plugging speed
Hurry up, to asphalitine dirt, sulfosalt surfactant is dirty, polyacrylamide material is dirty, various calcium and magnesium salt crust have very strong dissolving to make
With during cleaning de-plugging, being really achieved corrosion-free Chemical cleaning de-plugging, than traditional chemical cleaning inorganic acid, organic
Acid, highly basic safety and reliability, completely eliminate because emulsifying uneven or misoperation with corrosion inhibiter failure, corrosion inhibiter during acidifying strata
Deng corrosion of the burst factor to oil production equipment, the acidifying solution for replacing hydrochloric acid and hydrofluoric acid is entirely capable of during oil field stratum de-plugging
Stifled process.
Details are as follows for neutral de-plugging agent major technique effect of the present invention：
1st, one-step method can complete the de-plugging of oil field stratum
The present invention mainly by polyepoxy sodium succinate, sodium gluconate, p-hydroxy benzenyl sulfonate sodium, ethyl lactate, lipase,
The kinds of surface activating agent such as sorbitan carboxylic esterses, vanadic anhydride and sodium sulfate of polyethenoxy ether of fatty alcohol and amino acid sodium
Composition, the pH of de-plugging agent are 6～7, without inorganic acid and organic acid, also without hydrogen ion, chlorion and sulfate radical etc. be harmful to from
Son, rate of corrosion are less than 0.1g/ (m2H), corrosion-free safe de-plugging is reached.Using this neutral de-plugging agent in oil field stratum de-plugging
Cheng Zhong, can be in normal temperature under the conditions of 100 DEG C, and one-step method completes the chemical cleaning de-plugging to all kinds of incrustation scales, without the need for neutralisation treatment and
Passivation Treatment, saves the chemical plugging removal time, improves de-plugging efficiency.
2nd, polymer material dirt and asphalitine dirt that stratum ternary composite driving produce are removed
Divalence petroleum sulfonate to being produced by surfactant in ternary compound oil drive system oil recovery process of the invention
The compound scale that the precipitations such as precipitation dirt, polyacrylamide polymers material dirt and Ferric oxide scale are generated, in 24 hours, free from corrosion clear
Wash the chemically neutral descaling and blockage relieving that oil field stratum is completed under working condition.This de-plugging agent can quickly dissolve oil field stratum studies on asphaltene
The tamper of dirt, makes the bleeding agent of interpolation rapidly enter the inside of organic polymer material dirt, makes de-plugging agent and organic polymer material
Dirty rapid contact, makes asphalitine dirt and polymer material dirt expansion, converts, eventually form the small molecule solution for being easily soluble in water.
3rd, protection stratum support and capillary can safe de-pluggings
Neutral de-plugging agent of the present invention, with de-plugging dredge pore constriction, recover reservoir permeability for the purpose of, to carbonate scale,
Silicate scale, sulfate scale, the de-plugging of the polymer material dirt of sulfonate surfactant dirt, with good complexing, ooze
Permeability and dissolubility, can penetrate the deep of oil field stratum, and de-plugging area is big, reaction residue into pasty state, do not produce residue and
The phenomenons such as secondary precipitate particulate, make reservoir exempt from acid infringement, have to capillary reaming to act on, protect stratum support.
Prior art acidifying hydrochloric acid and the reaction of hydrofluoric acid and formation rock ore deposit acutely, consume fast, solution cavity is big and de-plugging effectively away from
From short, de-plugging area is little and not thorough, it is difficult to reach the purpose of deep acidification, affects acidizing effect.
Neutral de-plugging agent of the present invention can reach the purpose of removing clog in deep reservoir, and neutral de-plugging liquid movement 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, be reservoir fluid extraction formed good
Good passage, reduces additional capillary pressure, improves the relative permeability of crude oil, and improves tar productivity.
4th, de-plugging waste liquid is degradable, without the row's of returning floor treatment
As all components of neutral de-plugging agent of the present invention are all by degradable complexing agent, emulsifying agent, dispersant and oxygen
The dirt reaction that is cleaned in agent composition, with oil field stratum, generates degradable small molecule salt, can reach oilbearing stratum pair
The quality of water quality and environmental requirement.With this de-plugging agent to oil field stratum chemical plugging removal after, oil field stratum cleaning de-plugging waste liquid not
With the earthward row of returning, liquid waste processing operation and expense after cleaning de-plugging is reduced, the pollution to environment is reduced.
Specific embodiment
The molecular weight of the polyethylene glycol that embodiment is used is 1500～2000.
Embodiment 1, weighs raw material：Polyepoxy sodium succinate 35kg, sodium gluconate 20kg, polyethylene glycol 2kg, three ethanol
Amine 2kg, ethyl lactate 9kg, sodium sulfate of polyethenoxy ether of fatty alcohol 9kg, amino acid sodium 11kg, active attapulgite 14kg, five
V 2 O 0.2kg, lipase 5kg, sorbitan carboxylic esterses 6kg, p-hydroxy benzenyl sulfonate sodium 15kg, t-butyl hydroperoxide
4kg and double ethylene glycol laurate 0.2kg.Above-mentioned raw materials are prepared into oil extraction in oil field stratum neutral de-plugging agent group in the steps below
Compound：
1st, by polyepoxy sodium succinate 35kg, sodium gluconate 20kg, polyethylene glycol 2kg, triethanolamine 2kg, lactic acid second
Ester 9kg and active attapulgite 5kg, are crushed with grinder, stir 40 minutes to uniform, system with mixer after crossing 20 mesh sieves
Obtain the first powder.
2nd, by sodium sulfate of polyethenoxy ether of fatty alcohol 9kg, amino acid sodium 11kg and active attapulgite 7kg, mixed with taper
Close mixer and 1 hour is stirred to uniform, make sodium sulfate of polyethenoxy ether of fatty alcohol with amino acid sodium by active attapulgite carrier
Fully adsorb, after then crushing 20 mesh sieves, the second powder was obtained.
3rd, by vanadic anhydride 0.2kg, lipase 5kg and active attapulgite 2kg, 40 are stirred with cone blender
Minute, to uniform, cross 40 mesh sieves and the 3rd powder is obtained.
4th, by sorbitan carboxylic esterses 6kg, p-hydroxy benzenyl sulfonate sodium 15kg, t-butyl hydroperoxide 4kg and double second two
Alcohol laurate 0.2kg, stirs 40 minutes to uniform with tapered mixing and blending machine, crosses 20 mesh sieves and the 4th powder is obtained.
5th, obtained first powder, the second powder, the 3rd powder and the 4th powder mixing and stirring are made oil field
Producing formation neutral de-plugging agent.
Embodiment 2, weighs raw material：Polyepoxy sodium succinate 33kg, sodium gluconate 18kg, polyethylene glycol 3kg, three ethanol
Amine 3kg, ethyl lactate 10kg, sodium sulfate of polyethenoxy ether of fatty alcohol 7kg, amino acid sodium 8.5kg, active attapulgite 10kg,
Vanadic anhydride 0.15kg, lipase 6kg, sorbitan carboxylic esterses 8kg, p-hydroxy benzenyl sulfonate sodium 16kg, hydrogen peroxide uncle
Butyl 6kg and double ethylene glycol laurate 0.16kg.Above-mentioned raw materials are prepared into the neutral solution in oil extraction in oil field stratum in the steps below
Plugging agents in combination thing：
1st, by polyepoxy sodium succinate 33kg, sodium gluconate 18kg, polyethylene glycol 3kg, triethanolamine 3kg, lactic acid second
Ester 10kg and active attapulgite 4kg, are crushed with grinder；Remaining is with embodiment 1.
2nd, by sodium sulfate of polyethenoxy ether of fatty alcohol 7kg, amino acid sodium 8.5kg and active attapulgite 5kg, mixed with taper
Closing mixer and 1 hour being stirred to uniform, remaining is with embodiment 1.
3rd, by vanadic anhydride 0.15kg, lipase 6kg and active attapulgite 1kg, stirred with cone blender,
Remaining is with embodiment 1.
4th, by sorbitan carboxylic esterses 8kg, p-hydroxy benzenyl sulfonate sodium 16kg, t-butyl hydroperoxide 6kg and double second two
Alcohol laurate 0.16kg, is stirred with tapered mixing and blending machine, and remaining is with embodiment 1.
5th, with embodiment 1.
Embodiment 3, weighs raw material：Polyepoxy sodium succinate 30kg, sodium gluconate 23kg, polyethylene glycol 2.5kg, three second
Hydramine 2.5kg, ethyl lactate 12kg, sodium sulfate of polyethenoxy ether of fatty alcohol 10kg, amino acid sodium 12kg, active attapulgite
13kg, vanadic anhydride 0.1kg, lipase 7kg, sorbitan carboxylic esterses 5kg, p-hydroxy benzenyl sulfonate sodium 18kg, peroxidating
Hydrogen tert-butyl group 3kg and double ethylene glycol laurate 0.1kg.Above-mentioned raw materials are prepared into oil extraction in oil field stratum in the steps below neutral
De-plugging agent composition：
1st, by polyepoxy sodium succinate 30kg, sodium gluconate 23kg, polyethylene glycol 2.5kg, triethanolamine 2.5kg, breast
Acetoacetic ester 12kg and active attapulgite 5.5kg, are crushed with grinder；Remaining is with embodiment 1.
2nd, by sodium sulfate of polyethenoxy ether of fatty alcohol 10kg, amino acid sodium 12kg and active attapulgite 5.5kg, taper is used
Mixing and blending machine stirs 1 hour to uniform, and remaining is with embodiment 1.
3rd, by vanadic anhydride 0.1kg, lipase 7kg and active attapulgite 2kg, stirred with cone blender,
Remaining is with embodiment 1.
4th, by sorbitan carboxylic esterses 5kg, p-hydroxy benzenyl sulfonate sodium 18kg, t-butyl hydroperoxide 3kg and double second two
Alcohol laurate 0.1kg, is stirred with tapered mixing and blending machine, and remaining is with embodiment 1.
5th, with embodiment 1.
Embodiment 4, weighs raw material：Polyepoxy sodium succinate 36kg, sodium gluconate 24kg, polyethylene glycol 3kg, three ethanol
Amine 4kg, ethyl lactate 11kg, sodium sulfate of polyethenoxy ether of fatty alcohol 8kg, amino acid sodium 9.6kg, active attapulgite 15kg,
Vanadic anhydride 0.2kg, lipase 7kg, sorbitan carboxylic esterses 7kg, p-hydroxy benzenyl sulfonate sodium 17kg, the tertiary fourth of hydrogen peroxide
Base 7kg and double ethylene glycol laurate 0.3kg.Above-mentioned raw materials are prepared into oil extraction in oil field stratum neutral de-plugging agent in the steps below
Composition：
1st, above-mentioned polyepoxy sodium succinate, sodium gluconate, polyethylene glycol, triethanolamine, ethyl lactate and 6kg are lived
Property attapulgite, is crushed with grinder；Remaining is with embodiment 1.
2nd, by above-mentioned sodium sulfate of polyethenoxy ether of fatty alcohol, amino acid sodium and 7kg active attapulgites, mixed with taper
Mixer stirs 1 hour to uniform, and remaining is with embodiment 1.
3rd, by above-mentioned vanadic anhydride, lipase and 2kg active attapulgites, stirred with cone blender, its
Remaining same embodiment 1.
4th, by above-mentioned sorbitan carboxylic esterses, p-hydroxy benzenyl sulfonate sodium, t-butyl hydroperoxide and double ethylene glycol moons
Cinnamic acid ester, is stirred with tapered mixing and blending machine, and remaining is with embodiment 1.
5th, with embodiment 1.
Embodiment 5, weighs raw material：Polyepoxy sodium succinate 32kg, sodium gluconate 25kg, polyethylene glycol 3kg, three ethanol
Amine 3kg, ethyl lactate 10kg, sodium sulfate of polyethenoxy ether of fatty alcohol 8.5kg, amino acid sodium 10.2kg, active attapulgite
15kg, vanadic anhydride 0.15kg, lipase 6.5kg, sorbitan carboxylic esterses 7kg, p-hydroxy benzenyl sulfonate sodium 16kg, peroxide
Change hydrogen tert-butyl group 5kg and double ethylene glycol laurate 0.25kg.Above-mentioned raw materials are prepared into oil extraction in oil field stratum in the steps below
Neutral de-plugging agent composition：
1st, above-mentioned polyepoxy sodium succinate, sodium gluconate, polyethylene glycol, triethanolamine, ethyl lactate and 6kg are lived
Property attapulgite, is crushed with grinder；Remaining is with embodiment 1.
2nd, by above-mentioned sodium sulfate of polyethenoxy ether of fatty alcohol, amino acid sodium and 7kg active attapulgites, mixed with taper
Mixer stirs 1 hour to uniform, and remaining is with embodiment 1.
3rd, by above-mentioned vanadic anhydride, lipase and 2kg active attapulgites, stirred with cone blender, its
Remaining same embodiment 1.
4th, by above-mentioned sorbitan carboxylic esterses, p-hydroxy benzenyl sulfonate sodium, t-butyl hydroperoxide and double ethylene glycol moons
Cinnamic acid ester, is stirred with tapered mixing and blending machine, and remaining is with embodiment 1.
5th, with embodiment 1.
Claims (3)
1. a kind of oil extraction in oil field stratum neutral de-plugging agent composition, it is characterised in that：It is made up of the raw material of following portions by weight：Poly-
30～36 parts of epoxy sodium succinate, 18～25 parts of sodium gluconate, 2～3 parts of polyethylene glycol, 2～4 parts of triethanolamine, lactic acid second
9～12 parts of ester, 7～10 parts of sodium sulfate of polyethenoxy ether of fatty alcohol, 8～12 parts of amino acid sodium, 10～15 parts of active attapulgite,
0.1～0.2 part of vanadic anhydride, 5～7 parts of lipase, 5～8 parts of sorbitan carboxylic esterses, p-hydroxy benzenyl sulfonate sodium 15～18
Part, 0.1～0.3 part of 3～7 parts of t-butyl hydroperoxide and double ethylene glycol laurates.
2. a kind of oil extraction in oil field stratum neutral de-plugging agent composition as claimed in claim 1, it is characterised in that：Polyethylene glycol
Molecular weight is 1500～2000.
3. the preparation method of the oil extraction in oil field stratum neutral de-plugging agent composition described in a kind of claim 1 or 2, it is characterised in that
Comprise the steps：
A, by 30～36 parts of polyepoxy sodium succinate, 18～25 parts of sodium gluconate, 2～3 parts of polyethylene glycol, triethanolamine 2～4
4～6 parts of part, 9～12 parts of ethyl lactate and active attapulgite, are crushed with grinder, are stirred after crossing 20 mesh sieves, are made
Obtain the first powder；
B, by 5～7 parts of 7～10 parts of sodium sulfate of polyethenoxy ether of fatty alcohol, 8～12 parts of amino acid sodium and active attapulgite, use
Cone blender stirs 1 hour to uniform, makes sodium sulfate of polyethenoxy ether of fatty alcohol with amino acid sodium by active attapulgite
Native carrier fully adsorbs, and the second powder was obtained after then crushing 20 mesh sieves；
C, by 1～2 part of 0.1～0.2 part of vanadic anhydride, 5～7 parts of lipase and active attapulgite, mixed with taper
Machine stirs 40 minutes to uniform, crosses 40 mesh sieves and the 3rd powder is obtained；
D, by 5～8 parts of sorbitan carboxylic esterses, 15～18 parts of p-hydroxy benzenyl sulfonate sodium, 3～7 parts of t-butyl hydroperoxide with
0.1～0.3 part of double ethylene glycol laurates, stir 40 minutes to uniform with tapered mixing and blending machine, cross 20 mesh sieves and be obtained the 4th
Powder；
E, obtained first powder, the second powder, the 3rd powder and the 4th powder mixing and stirring are made oil extraction in oil field
Stratum neutral de-plugging agent.
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