CN108611084A - Complexing agent for Reservoir Acidization and preparation method thereof, application - Google Patents
Complexing agent for Reservoir Acidization and preparation method thereof, application Download PDFInfo
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- CN108611084A CN108611084A CN201611133607.2A CN201611133607A CN108611084A CN 108611084 A CN108611084 A CN 108611084A CN 201611133607 A CN201611133607 A CN 201611133607A CN 108611084 A CN108611084 A CN 108611084A
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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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
Abstract
The invention discloses a kind of complexing agent for Reservoir Acidization and preparation method thereof, applications, belong to technical field of petrochemical industry.It is in terms of 100% by the gross mass of the complexing agent, which includes the following components'mass percentage：Organic acid and/or acylate, 10%~30%；Gluceptate, 20%~30%；Alkyl imidazoline class compound, 10%~25%；Surfactant, 5%~10%；Water, surplus.The complexing agent retardative property is good, complexing of metal ion ability is strong, corrosion rate is low, can effectively reduce acid-rock reaction rate, realize the deep penetration of acid solution；Calcium, iron, magnesium plasma effectively in complexing reservoir inhibit the generation of precipitation；And effectively reduce corrosion of the acid solution to down-hole string；To realize the Efficient Development of reservoir, increase oil and gas production.
Description
Technical field
The present invention relates to technical field of petrochemical industry, more particularly to a kind of complexing agents and its preparation side for Reservoir Acidization
Method, application.
Background technology
Sandstone oil reservoir has the characteristics that low porosity and low permeability, anisotropism are strong, for such oil reservoir, generally use Acidizing Technology pair
It is developed.Currently, being acidified common acid fluid system mainly has hydrochloric acid, mud acid (compounding to obtain by hydrochloric acid and hydrofluoric acid) etc.,
There are numerous prominent questions in the reaction process with sandstone reservoir for existing acid fluid system.For example, mud acid and sandstone reservoir
Acid-rock reaction excessive velocities, and due to the excessive corrosion mineral of acid solution, Container Rock Sanding, plugging hole is caused to shout channel；While with
The progress of acid-rock reaction, the pH value of acid solution constantly increases, and acid solution and clay mineral etc. easily generate aluminosilicate, metal hydroxide
The precipitations such as object, fluosilicate.
Addition may be used into acid solution have slow, scale suppression effect complexing agent to slow down acid solution and rock stratum reacts fast
Rate simultaneously prevents fouling.For example, application No. is US61/424,271, entitled " include suitable for handle carbonate containing stratum
The patent application of the fluid of complexing agent ", application No. is the 200880124468.4, entitled " acid waters containing complexing agent
The patent application of solution and application thereof " and application No. is 200910219440.5, it is entitled that " heavy metal species are complexed
The complexing agent that can be used for acidification of oil field process is reported in the patent application of the preparation method of agent ".
In the implementation of the present invention, the inventors discovered that having at least the following problems in the prior art：Existing network
When mixture is applied to the acidification of sandstone oil reservoir, there are retardative properties, and poor, complexing of metal ion energy force difference and corrosion rate height etc. are asked
Topic.
Invention content
In order to solve the above technical problems, the embodiment of the present invention provides that a kind of retardative property is good, complexing of metal ion energy
Power is strong, and the low complexing agent suitable for acidizing sandstone oil reservoir of corrosion rate realizes reservoir to realize the deep penetration of acid solution
Efficient Development increases oil and gas production.
Specifically, including technical solution below：
In a first aspect, the embodiment of the present invention provides a kind of complexing agent for Reservoir Acidization, with total matter of the complexing agent
Amount is 100% meter, and the complexing agent includes the following components'mass percentage：
Organic acid and/or acylate, 10%~30%；
Gluceptate, 20%~30%；
Alkyl imidazoline class compound, 10%~25%；
Surfactant, 5%~10%；
Water, surplus.
Optionally, the organic acid be selected from least one of formic acid and acetic acid, the acylate be selected from organic salt with
And at least one of organic phosphate.
Optionally, the organic salt is selected from ammonium acetate, and the organic phosphate is selected from ethylenediamine tetraacetic methene sodium phosphate.
Optionally, the gluceptate in glucoheptonic acid ammonium, sodium glucoheptonate and glucoheptonic acid potassium at least
It is a kind of.
Optionally, the alkyl imidazoline class compound is selected from 1- (2- aminoethyls) -2- alkyl imidazolines, 1- (2- methyl -
Thiocarbamide ethyl) at least one of -2- alkyl imidazolines and 1- (2- phenyl-thioureas ethyl) -2- alkyl imidazolines.
Optionally, 1- (2- the aminoethyls) -2- alkyl imidazolines are selected from 1- (2- aminoethyls) -2- ethyl imidazol(e) quinolines；Institute
It states 1- (2- methyl-thioureas ethyl) -2- alkyl imidazolines and is selected from 1- (2- methyl-thioureas ethyl) -2- pentadecyl imidazolines；Institute
It states 1- (2- phenyl-thioureas ethyl) -2- alkyl imidazolines and is selected from 1- (2- phenyl-thioureas ethyl) -2- pentadecyl imidazolines.
Optionally, the surfactant is selected from perfluoroalkyl ethers lauryl alcohol amine anion surfactant and perfluor alkane
At least one of base ether quaternary cationics.
Optionally, the perfluoroalkyl ethers lauryl alcohol amine anion surfactant is selected from perfluoro-ethyl ether lauryl alcohol amine.
Second aspect, the embodiment of the present invention provide a kind of preparation method of above-mentioned complexing agent, which includes：
At a temperature of 50 DEG C~60 DEG C, and under stirring conditions, by organic acid and/or acylate, alkyl imidazoline class compound,
Water, gluceptate and surfactant are added in container, continue stirring to system is transparent, after clarification up to the complexing
Agent.
The third aspect, the embodiment of the present invention provide a kind of application of above-mentioned complexing agent in Reservoir Acidization.
Further, above application is specially：It is used after the complexing agent is mixed with hydrochloric acid, water according to preset ratio
In the acid solution of Reservoir Acidization.
The advantageous effect of technical solution provided in an embodiment of the present invention：
The embodiment of the present invention is optimized by component to complexing agent and proportioning, has obtained a kind of retardative property
The New Chelating Agents good, complexing of metal ion ability is strong, corrosion rate is low.For same sandstone reservoir, the present invention is added and implements
The slow rate of the more conventional mud acid of acid fluid system of the complexing agent of example is up to 40% or more, to which acid-rock reaction speed be greatly lowered
Rate is conducive to the deep penetration of acid solution.There is stronger complexing power to calcium, iron, magnesium ion, effectively inhibit secondary, precipitate three times
Generation.Corrosion of the acid solution to down-hole string can be effectively reduced simultaneously, realizes the Efficient Development of reservoir, increases oil and gas production.
The acidification of the complexing agent provided in an embodiment of the present invention sandstone reservoir strong especially suitable for low porosity and low permeability, anisotropism
Construction, additionally it is possible to be used for 150 DEG C or more of temperature reservoirs.
Specific implementation mode
To keep technical scheme of the present invention and advantage clearer, embodiment of the present invention is made below further detailed
Description.Unless otherwise defined, all technical terms used in the embodiment of the present invention all have usually manages with those skilled in the art
The identical meaning of solution.
In a first aspect, the embodiment of the present invention provides a kind of complexing agent for Reservoir Acidization, with the gross mass of the complexing agent
For 100% meter, complexing agent includes the following components'mass percentage：
Organic acid and/or acylate, 10%~30%；
Gluceptate, 20%~30%；
Alkyl imidazoline class compound, 10%~25%；
Surfactant, 5%~10%；
Water, surplus.
It is novel that an embodiment of the present invention provides a kind of retardative properties is good, complexing of metal ion ability is strong, corrosion rate is low
Complexing agent effectively reduces acid-rock reaction rate, realizes the depth of acid solution by the mutual cooperation between each component, synergistic effect
It penetrates；The generation that calcium, iron, magnesium plasma effectively in complexing reservoir inhibit secondary, precipitate three times；And acid solution is effectively reduced to well
The corrosion of lower tubular column；To realize the Efficient Development of reservoir, increase oil and gas production.
Specifically, in complexing agent provided in an embodiment of the present invention, organic acid, the acidity of acylate are weaker, in acid
Ionization substep during karst erosion carries out, and the speed of release hydrogen ions is slower, to slow down acid-rock reaction rate.
In the embodiment of the present invention, organic acid can be at least one of low-carbons carboxylic acids such as formic acid, acetic acid, and acylate can
To be selected from least one of organic salt, organic phosphate etc..Wherein, organic salt is specifically as follows ammonium acetate, organic phosphate tool
Body can be ethylenediamine tetraacetic methene sodium phosphate.
In a kind of specific embodiment, using formic acid, acetic acid, ammonium acetate and organic phosphate according to mass ratio 4:2:
2:The mixture of 2 ratio compounding.
Gluceptate has multiple hydroxyls and multiple carboxyls in molecular structure, can form multiple match with metal ion
Position body, plays complexing, and complexing power goes out far above common ethylenediamine tetra-acetic acid (EDTA), diethylene triamine pentacetic acid (DTPA)
(DTPA), the complexing power of the aminocarboxylics acids such as Hedta (HEDTA).
It will be appreciated by persons skilled in the art that in commercially available gluceptate, gluceptate is in addition to small molecule
Outside form exists, also exist with multimeric forms, poly gluceptate has better complexing power.
Gluceptate can be selected from the soluble gluceptate such as glucoheptonic acid ammonium, sodium glucoheptonate, glucoheptonic acid potassium
At least one of, in a kind of specific embodiment, gluceptate is glucoheptonic acid ammonium, sodium glucoheptonate and glucoheptose
Sour potassium is according to mass ratio 4:3:The mixture of 3 ratio compounding.
Alkyl imidazoline class compound can be adsorbed on metal surface, and certain oxidizing substances in acid solution are complexed,
To realize preferable rust inhibition, and then reduce extent of corrosion of the acid solution to down-hole string.
Alkyl imidazoline class compound can be selected from 1- (2- aminoethyls) -2- alkyl imidazolines, 1- (2- methyl-thiourea second
Base) at least one of -2- alkyl imidazolines and 1- (2- phenyl-thioureas ethyl) -2- alkyl imidazolines.Wherein, 1- (2- ammonia
Ethyl) -2- alkyl imidazolines are specifically as follows 1- (2- aminoethyls) -2- ethyl imidazol(e) quinolines, 1- (2- methyl-thioureas ethyl) -2-
Alkyl imidazoline is specifically as follows 1- (2- methyl-thioureas ethyl) -2- pentadecyl imidazolines, 1- (2- phenyl-thioureas ethyl) -
2- alkyl imidazolines are specifically as follows 1- (2- phenyl-thioureas ethyl) -2- pentadecyl imidazolines.
Surfactant can reduce the interfacial tension of grease, increase the wet degree of water of rock, while can also realize residual acid
The preferably row of returning.
In the embodiment of the present invention, surfactant can be selected from perfluoroalkyl ethers lauryl alcohol amine anion surfactant with
And at least one of perfluoroalkyl ethers quaternary cationics.Wherein, perfluoroalkyl ethers lauryl alcohol amine anion
It is multiple that surfactant is specifically as follows perfluoro-methyl ether lauryl alcohol amine, perfluoro-ethyl ether lauryl alcohol amine or a variety of perfluoroalkyl ethers
The mixture matched.
In complexing agent provided in an embodiment of the present invention, dosage arbitrary value, act in the range of restriction of each component
For example, the mass percent of organic acid and/or acylate can be 10%, 12%, 14%, 15%, 16%, 18%,
20%, 22%, 24%, 25%, 26%, 28%, 30% etc.；The mass percent of gluceptate can be 20%, 22%,
24%, 25%, 26%, 28%, 30% etc.；The mass percent of alkyl imidazoline class compound can be 10%, 12%,
14%, 15%, 16%, 18%, 20%, 22%, 24%, 25% etc.；The mass percent of surfactant can be 5%,
6%, 7%, 8%, 9%, 10% etc..
Second aspect, the embodiment of the present invention provide a kind of preparation method of above-mentioned complexing agent, which includes：
At a temperature of 50 DEG C~60 DEG C, and under stirring conditions, by organic acid and/or acylate, alkyl imidazoline class compound,
Water, gluceptate and surfactant are added in container, continue stirring to system is transparent, after clarification up to complexing agent.
It should be noted that in above-mentioned preparation method, the charging sequence of water and gluceptate in no particular order, and has
Machine acid and/or acylate, alkyl imidazoline class compound should sequentially add before water and gluceptate, surfactant
It is eventually adding.And surfactant should be slowly added to, it is made to come into full contact with and be uniformly mixed with solution under the action of stirring.
When system is transparent, clarification, after no precipitation, can continue to stand a period of time, such as used again after 1 hour.
The third aspect, the embodiment of the present invention provide a kind of application of above-mentioned complexing agent in Reservoir Acidization.By above-mentioned network
Mixture injects reservoir after being mixed with acid solution (such as hydrochloric acid, mud acid etc.) with acidizing treatment.
In a kind of specific embodiment, by above-mentioned complexing agent, hydrochloric acid and water according to mass ratio 1:1:8 ratio is mixed
It closes, injects reservoir.
The technical solution of the embodiment of the present invention is described in further detail below by specific data.
Experimental method used in following embodiment is conventional method unless otherwise specified.
Material used in following embodiment, reagent etc., be not specified production firm and specification person be can be by purchased in market
The conventional products of acquisition.
In following embodiment, the group of each component becomes in complexing agent：
A：The combination (hereinafter referred to as organic acid) of organic acid and acylate is：40% formic acid, 20% acetic acid, 20% acetic acid
Ammonium, 20% ethylenediamine tetraacetic methene sodium phosphate, the above percentage are mass percent, are to be incited somebody to action in terms of 100% by the gross mass of organic acid
Formic acid, acetic acid, ammonium acetate and ethylenediamine tetraacetic methene sodium phosphate are mixed with other components as a whole after mixing.
B：Gluceptate：40% glucoheptonic acid ammonium, 30% sodium glucoheptonate, 30% glucoheptonic acid potassium, the above percentage
It is in terms of 100%, by glucoheptonic acid ammonium, sodium glucoheptonate and glucoheptose by the gross mass of gluceptate for mass percent
Sour potassium is mixed with other components as a whole after mixing.
C：Alkyl imidazoline class compound：1- (2- aminoethyls) -2- ethyl imidazol(e) quinolines.
D：Surfactant：Perfluoro-ethyl ether lauryl alcohol amine.
Unless otherwise instructed, the mass percent of the hydrochloric acid described in following embodiment is pure hydrochloric acid, i.e. hydrogen chloride
Mass percent.
Embodiment 1
The present embodiment provides three kinds for Reservoir Acidization complexing agents and corresponding preparation method, and to its retardative property into
Row test.
The formula of the complexing agent of the present embodiment is as shown in table 1.
The formula for the complexing agent that 1 embodiment 1 of table provides
Each percentage is mass percent in table 1, and by the gross mass of complexing agent I in terms of 100%.
The preparation method of the complexing agent of the present embodiment is as follows：
At a temperature of 50 DEG C, and under stirring conditions, according to the proportioning of each component in table 1, successively by organic acid, alkane
Base imidazolines, water, gluceptate and surfactant are added in container, continue stirring to system it is transparent,
Clarification, and up to complexing agent after standing 1 hour.
By hydrochloric acid, the complexing agent of the present embodiment and water example 10 in mass ratio：10：80 ratio is compounded to obtain complex acid
System, using the core of two blocks of the AE of H Oil Fields and XL as sample, (total rock of the core sample of AE and XL blocks analyzes knot
Fruit is as shown in table 2), the sour karst erosion experiment of 2h is carried out under 90 DEG C of water bath conditions.Complex acid under different organic acids component
Slow rate test result such as table 3.
The total rock of the core sample of 2 AE and XL blocks of table is analyzed
Corrosion situation of the complexing acid system of 3 different organic acids content of table to sandstone mineral
In table 3, for slow rate on the basis of the corrosion rate of regular mud acid, i.e. the corrosion inhibition rate of regular mud acid is 0.
As can be seen from Table 3, the complexing acid system under different organic acids content is big to the slow rate of the above block
In 40%, there is stronger slow property；Acid system is complexed to the corrosion rate of block between 20%~32%, there is certain corrosion
Ability (the corrosion rate of regular mud acid is 35% or so).
Embodiment 2
The present embodiment provides three kinds of complexing agents for Reservoir Acidization and corresponding preparation methods, and to it to metal ion
Complex performance tested.
The formula of the complexing agent of the present embodiment is as shown in table 4.
The formula for the complexing agent that 4 embodiment 2 of table provides
Each percentage is mass percent in table 4, and by the gross mass of complexing agent I in terms of 100%.
The preparation method of the complexing agent of the present embodiment is as follows：
At a temperature of 55 DEG C, and under stirring conditions, according to the proportioning of each component in table 4, successively by organic acid, alkane
Base imidazolines, water, gluceptate and surfactant are added in container, continue stirring to system it is transparent,
Clarification, and up to complexing agent after standing 1 hour.
Measure the metal of blank group (not plus complexing agent) and experimental group (complexing agent is added) respectively using indicator titration method
The complexing power of the New Chelating Agents to calcium ion, iron ion and magnesium ion of the present embodiment is obtained by calculation in ion complexation value.
Influence of the different glucoheptonic acid salt contents to complexing of metal ion ability, is shown in Table 5.
Influence of the complexing agent of the different glucoheptonic acid salt contents of table 5 to complexing of metal ion ability
As can be seen from Table 5, poly- glucoheptonic acid salt content is preferably 25%~30%, complexing provided in this embodiment
Agent is 272mg/g, 167mg/g, 455mg/g respectively to the highest complexing value of calcium, magnesium, iron three classes ion.
Embodiment 3
The present embodiment provides four kinds for Reservoir Acidization complexing agents and corresponding preparation method, and to its corrosive nature into
Row measures.
The formula of the complexing agent of the present embodiment is as shown in table 6.
The formula for the complexing agent that 6 embodiment 3 of table provides
The preparation method of the complexing agent of the present embodiment is as follows：
At a temperature of 60 DEG C, and under stirring conditions, according to the proportioning of each component in table 6, successively by organic acid, alkane
Base imidazolines, water, gluceptate and surfactant are added in container, continue stirring to system it is transparent,
Clarification, and up to complexing agent after standing 1 hour.
By hydrochloric acid, the complexing agent of the present embodiment and water example 10 in mass ratio：10：80 ratio is compounded to obtain complex acid
System carries out static corrosion test at 90 DEG C, and N80 steel discs are put into above-mentioned complexing acid system and impregnate 4h.Different alkyl miaows
Influence of the oxazoline compound content to steel disc rate of corrosion is shown in Table 7.
Influence of the complexing acid system of the different alkyl imidazoline kind compound contents of table 7 to corrosion rate
As can be seen from Table 7, the complexing acid system of different alkyl imidazoline kind compound contents, is being not added with other
100g/m is respectively less than to the corrosion rate of steel disc in the case of corrosion inhibiter2·h.With the increase of alkyl imidazoline content, complexing
Acid is gradually reduced the corrosion rate of steel disc, and the content of alkyl imidazoline class compound is preferably 20%~25%.
The conventional acid fluid system for being not added with corrosion inhibiter is measured the corrosion rate of N80 steel discs simultaneously, test condition：
90 DEG C, corrode 4h.It the results are shown in Table 8.
The acid fluid system that table 8 is not added with corrosion inhibiter measures the corrosion rate of steel disc
In table 8, the formula of mud acid：10%HCl+2%HF+87% water；
Concentration of hydrochloric acid is 10%；
MH acid：10%HCl+3%SA601+4%SA701+83% water.
As can be seen from Table 8, the corrosion rate of the acid fluid system of the complexing agent of the present embodiment is added to far below normal
Acid solution such as hydrochloric acid, mud acid, MH acid are advised to the corrosion rate of steel disc.
The above is merely for convenience of it will be understood by those skilled in the art that technical scheme of the present invention, not limiting
The present invention.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in this
Within the protection domain of invention.
Claims (10)
1. a kind of complexing agent for Reservoir Acidization, which is characterized in that by the gross mass of the complexing agent be 100% in terms of, it is described
Complexing agent includes the following components'mass percentage：
Organic acid and/or acylate, 10%~30%；
Gluceptate, 20%~30%；
Alkyl imidazoline class compound, 10%~25%；
Surfactant, 5%~10%；
Water, surplus.
2. complexing agent according to claim 1, which is characterized in that the organic acid in formic acid and acetic acid at least one
Kind, the acylate is selected from least one of organic salt and organic phosphate.
3. complexing agent according to claim 1, which is characterized in that the gluceptate is selected from glucoheptonic acid ammonium, Portugal heptan
At least one of sodium saccharate and glucoheptonic acid potassium.
4. complexing agent according to claim 1, which is characterized in that the alkyl imidazoline class compound is selected from 1- (2- ammonia
Ethyl) -2- alkyl imidazolines, 1- (2- methyl-thioureas ethyl) -2- alkyl imidazolines and 1- (2- phenyl-thioureas ethyl) -2-
At least one of alkyl imidazoline.
5. complexing agent according to claim 4, which is characterized in that 1- (2- the aminoethyls) -2- alkyl imidazolines are selected from
1- (2- aminoethyls) -2- ethyl imidazol(e) quinolines；
1- (2- methyl-thioureas the ethyl) -2- alkyl imidazolines are selected from 1- (2- methyl-thioureas ethyl) -2- pentadecyl miaows
Oxazoline；
1- (2- phenyl-thioureas the ethyl) -2- alkyl imidazolines are selected from 1- (2- phenyl-thioureas ethyl) -2- pentadecyl miaows
Oxazoline.
6. complexing agent according to claim 1, which is characterized in that the surfactant is selected from perfluoroalkyl ethers lauryl alcohol
At least one of amine anion surfactant and perfluoroalkyl ethers quaternary cationics.
7. complexing agent according to claim 6, which is characterized in that the perfluoroalkyl ethers lauryl alcohol amine anionic surface is lived
Property agent be selected from perfluoro-ethyl ether lauryl alcohol amine.
8. a kind of preparation method of claim 1~7 any one of them complexing agent, which is characterized in that including：50 DEG C~60
At a temperature of DEG C, and under stirring conditions, by organic acid and/or acylate, alkyl imidazoline class compound, water, Portugal heptan
Sugar lime and surfactant are added in container, continue stirring to system is transparent, after clarification up to the complexing agent.
9. a kind of application of claim 1~7 any one of them complexing agent in Reservoir Acidization.
10. application according to claim 9, which is characterized in that mix the complexing agent and hydrochloric acid, water according to preset ratio
The acid solution for Reservoir Acidization is obtained after conjunction.
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Application publication date: 20181002 |