CN106147743A - A kind of petroleum-gas fiedl acid stimulation injection agent and preparation method thereof - Google Patents
A kind of petroleum-gas fiedl acid stimulation injection agent and preparation method thereof Download PDFInfo
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- CN106147743A CN106147743A CN201510196745.4A CN201510196745A CN106147743A CN 106147743 A CN106147743 A CN 106147743A CN 201510196745 A CN201510196745 A CN 201510196745A CN 106147743 A CN106147743 A CN 106147743A
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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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- 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
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
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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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
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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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/32—Anticorrosion additives
Abstract
The invention provides a kind of petroleum-gas fiedl acid stimulation injection agent, be made up of following material: in terms of the weight of material each in every liter of solution, surfactant 3.00g～6.00g, Compound-acid pickling inhibitor 1.20g～2.40g, Fe3+、Al3+Stabilizer 3.20g～6.40g, compound chloro organic carboxylic ester 208.55g～417.10g, remaining is aqueous solvent.The present invention is a kind of potential acid system, can be used in the sandstone formation of formation temperature >=60 DEG C and the acid stimulation of carbonate formation and increase water injection technology measure, solve conventional acidulation and there is the problems such as " construction equipment and tube corrosion ", " site operation personnel exists acid injury risk ", " acid-rock reaction speed is fast, and acidifying EFFECTIVE RANGE is short ", " it is the most thorough that row is returned in residual acid "；Will not react with rock injecting during stratum, it is to avoid in conventional acidulation, acid rock contact i.e. reacts and do not arrives the shortcoming of earth formation deep.
Description
Technical field
The invention belongs to oil gas field acid stimulation technical field, be specifically related to a kind of petroleum-gas fiedl acid stimulation injection agent and preparation method thereof.
Background technology
Acidifying is oil, oil/gas well stimulation, the effective ways of water injection well stimulation, it is to inject one or more acid solutions or acid mixed solution to stratum by well, utilize acid and the chemical reaction of part mineral in stratum, interconnected pore or natural/hydraulic fracture wall rock in corrosion reservoir and be dissolved in drilling well, completion, leak into during well workover and oil producing operation or the external tamper such as mud that leak-off enters in formation pore or crack (include leaking into thing or leak-off liquid and formation fluid and rock and react the precipitation tamper of generation), to expand or dredging stratum filtration passage, improve or improve the permeance property of reservoir, increase stratum flow conductivity, so that well production increment, water injection well stimulation.
Mode according to acidizing treatment and purpose, its technical process can be divided into pickling, matrix acidifying (also referred to as hole acidifying) and fracture acidizing (including matrix acidizing) three major types.When non-specified otherwise, acidizing treatment is exactly stratum matrix acidifying operation, matrix acidifying is under the conditions of less than formation rock fracture pressure, acid solution is injected interstitial space (intergranular, hole or crack), utilize the tamper of acid solution corrosion near wellbore zone with renwing stratum permeability or with the fine particle in acid solution solution porosity, cement etc. with expandable pores space, a kind of well stimulation of improving in-place permeability.Matrix acidifying is little because of operation pressure, free from flaw produces, acid solution is fast with tamper in hole or fine particle (especially carbonate mineral) response speed, make EFFECTIVE RANGE little, sandstone formation is generally within 1.5 meters, high temperature (>=120 DEG C) carbonate formation EFFECTIVE RANGE is less, but with the extensible EFFECTIVE RANGE of increase of infusion discharge capacity and displacement fluid liquid measure.
Matrix acidifying includes that conventional substrate is acidified (abbreviation conventional acidulation) and unconventional matrix acidifying (being called for short unconventional acidifying).Conventional acidulation refers to, on ground, one or more mixed acid are configured to acidic aqueous liquid liquid, after acid solution pumps into stratum, at once with the matrix acidifying of stratum acidolysis material chemically reactive.Conventional acidulation exists problems such as " acid-rock reaction speed are fast, and EFFECTIVE RANGE is little ", " construction equipment and tube corrosion " and " site operation personnel exists acid injury risk ".
Unconventional acidifying refers to one or more materials be hybridly prepared on ground neutrality (pH=7.0) pressed powder or is dissolved in water be configured to neutrality (pH=7.0) aqueous solvent, after pumping into subsurface formations, under formation temperature conditions, reaction generates acidic materials or hydrolysis generates acidic materials, newly-generated acidic materials again with the matrix acidifying of the acidolysis material chemically reactive in stratum, under formation temperature conditions, reaction generates acidic materials or hydrolysis generates the material of acidic materials and is referred to as " potential acid " material.
Since the nineties in 20th century, Oil Exploration in China exploitation research institute, Jilin Oil Field etc. successively develop phosphoric acid/Fluohydric acid. (A-924) system, CCl4The spontaneous acid working solution such as system, LZR system, is applied to mining site and achieves effect, be that China is to the contribution in Acidizing Technology development history.
Phosphoric acid/Fluohydric acid. (A-924) system, CCl4System, LZR system are that Acidizing Technology content is enriched and innovates by China oil field scientific worker, produce oil field and are made that positive contribution.But they also exist very important problem in the application, with regard to CCl4For system, this system is a kind of potential acid system (the most spontaneous acid system), it is desirable to have FeCl3In the presence of catalyst, it is being not less than under conditions of 120 DEG C the acid (CCl that could hydrolyze required for producing4+2H2O
=4HCl+CO2).CCl4System needs hot environment, and the stratum (50 DEG C～120 DEG C) low to temperature is inapplicable.It addition, the catalyst ferric chloride added in stratum hydrolysis, can be with FeCO3、Fe(OH)3、Fe2S3, the sedimentary form such as FeS occur, oil and gas flow passage is together constituted secondary blocking injury.
Summary of the invention
It is an object of the invention to overcome conventional acidulation the problems referred to above and the requirement to high temperature of the existing potential acid system, the problem that the most sedimentary formation constitutes secondary blocking injury to oil and gas flow passage.
To this end, the invention provides a kind of petroleum-gas fiedl acid stimulation injection agent, it is made up of following material: in terms of the weight of material each in every liter of solution, surfactant 3.00g～6.00g, Compound-acid pickling inhibitor 1.20g～2.40g, Fe3+、Al3+Stabilizer 3.20g～6.40g, compound chloro organic carboxylic ester 208.55g～417.10g, remaining is aqueous solvent.
Described surfactant model is CL-6 or CL-8.
Described Compound-acid pickling inhibitor is the compound of halogenated phosphates and hexynol, and combined weight ratio is 1: 1.
Described Fe3+、Al3+Stabilizer is arabo-ascorbic acid triethanolamine.
Described compound chloro organic carboxylic ester is the compound of methylchloroformate and ethyl chloroformate, and combined weight is than for methylchloroformate: ethyl chloroformate=1.00: 1.15.
Present invention also offers the preparation method of a kind of petroleum-gas fiedl acid stimulation injection agent, comprise the following steps:
Step 1) presses 1: 1 combined weight ratio, is joined by halogenated phosphates in hexynol and is uniformly mixing to obtain Compound-acid pickling inhibitor；Powder arabo-ascorbic acid is joined in pulpous state triethanolamine, is uniformly mixed, until measuring reactant mixture pH value is 7.0 i.e. to obtain arabo-ascorbic acid triethanolamine Fe3+、Al3+Stabilizer；By methylchloroformate: ethyl chloroformate=1.00: 1.15, methylchloroformate is joined in ethyl chloroformate and be uniformly mixing to obtain compound chloro organic carboxylic ester；
Step 2) first in preparation container, add a certain amount of water, 3.00g～6.00g surfactant is added to the water and mixes uniformly, under agitation, sequentially add Compound-acid pickling inhibitor 1.20g～2.40g, the Fe in step 1)3+、Al3+Stabilizer 3.20g～6.40g, conjunction chloro organic carboxylic ester 208.55g～417.10g, then to preparation container in add water to 1L locate, after stirring mensuration pH value in the range of 7.0 ± 0.2, obtain the injection agent finished product of 1L.
The invention has the beneficial effects as follows: the present invention is a kind of potential acid system, can be used in sandstone formation and the acid stimulation of carbonate formation (formation temperature >=60 DEG C) and increase water injection technology measure, solve conventional acidulation and there is the problems such as " construction equipment and tube corrosion ", " site operation personnel exists acid injury risk ", " acid-rock reaction speed is fast, and acidifying EFFECTIVE RANGE is short ", " it is the most thorough that row is returned in residual acid "；Will not react with rock injecting during stratum, it is to avoid in conventional acidulation, acid rock contact i.e. reacts and do not arrives the shortcoming of earth formation deep.
Detailed description of the invention
Embodiment 1:
A kind of preparation method of petroleum-gas fiedl acid stimulation injection agent:
Step 1) presses 1: 1 combined weight ratio, by halogenated phosphates ((C5H5N-C16H33)+Cl-) join hexynol (C3H7CH (OH) CCH, Dongbei Pharmaceutical General Factory produce) in be uniformly mixing to obtain Compound-acid pickling inhibitor；Powder arabo-ascorbic acid is joined pulpous state triethanolamine (N (CH2CH2OH)3In), it is uniformly mixed, until measuring reactant mixture pH value is 7.0 i.e. to obtain arabo-ascorbic acid triethanolamine Fe3+、Al3+Stabilizer；By methylchloroformate: ethyl chloroformate=1.00: 1.15, by methylchloroformate (ClCOOCH3) join ethyl chloroformate (ClCOOC2H5Compound chloro organic carboxylic ester it is uniformly mixing to obtain in)；
Step 2) in 1000 liters of enamel reaction stills, first add water to 700 liters of places, 3000g surfactant CL-6 is added to the water and mixes uniform, under agitation, sequentially add Compound-acid pickling inhibitor 1200g, the Fe in step 1)3+、Al3+Stabilizer 3200g, compound chloro organic carboxylic ester 208.55kg, then in preparation container, add water locate to 1000 liters, after stirring, mensuration pH value is in the range of 7.0 ± 0.2, obtains the injection agent finished product of 1000 liters.
Surfactant CL-6 in the present embodiment is formed by nonionic surfactant and zwitterionic surfactant are compounding, and by the development and production of Shandong chemical research institute, water is Fructus Persicae 56 wellblock water, is called for short Fructus Persicae 56 water, and its water chemistry composition is shown in Table 1:
Table 1. Fructus Persicae 56 water hydratable forms
Principle: injection agent of the present invention is " potential acid " aqueous solvent, owing to this injection agent is neutral (pH=7.0) aqueous solution, dosing and injection process do not exist the problem such as " construction equipment and tube corrosion " and " site operation personnel exists acid injury risk ", the most there is not the problem of " acid-rock reaction is carried out at once; EFFECTIVE RANGE is short " behind stratum of injecting, after being only injected into stratum, under formation temperature effect, in the range of the regular hour, hydrolysis generates hydrochloric acid (ClCOOCH3+H2O→HCl+CO2+CH3OH, ClCOOC2H5+H2O→HCl+CO2+C2H5OH) after, just react with formation rock, will not react with formation rock during injecting stratum, thus earth formation deep can be injected into pointedly, by conventional acidulation process less than place carry out acidification, reach old well earth formation deep de-plugging and new well earth formation deep transformation purpose, say, that this agent can be squeezed the most pointedly with greater need for earth formation deep.
This injection agent is injecting during stratum and will not react with rock, it is to avoid in conventional acidulation, acid rock contact i.e. reacts and do not arrives the shortcoming of earth formation deep." carbon dioxide " that hydrolysis discharges not only can change acid rock (carbonate formation) chemical reaction equilibrium (2HCl+CaCO3→CaCl2+CO2+H2O,2HCl+MgCO3→MgCl2+CO2+H2O) so that acid rock (carbonate formation) reacting balance carries out extending acidifying distance；Also it is a kind of energizer simultaneously, is conducive to the residual acid in acidifying later stage to return row.It addition, methanol and ethanol in hydrolyzate are mutual solvents, for gas-bearing formation, there is the function preventing water from locking, for oil reservoir, have the effect reducing oil water interfacial tension, simultaneously, residual acid in the later stage return row release pressure time be vaporizated into gaseous state, drive residual acid to return row, order about residual acid return row the most thorough.
1, the molten mistake of formation rock/calcium carbonate reagent is tested:
Under 60 DEG C of constant temperatures, the molten mistake test effect after the hydrolysis completely of this injection agent of 1L see table 2,
Molten mistake test effect after the hydrolysis completely of table 2. 1L injection agent
From the point of view of experimental result: under 60 DEG C of constant temperatures, molten mistake long 8 layers of sandstone 2.36g～4.12g, molten five layers of carbonate rock 89.41g～179.12g of flatus layer horse, molten mistake calcium carbonate reagent 101.20 g～202.30g after the hydrolysis completely of this aqueous solvent of 1L.
2. Sandstone Cores displacement experiment:
Choose Xi28-31Jing length 8 formation core, according to SY/T5336-1996 standard, rock core is processed, measure the ratio of formation water permeability before and after being acidified: under 60 DEG C of constant temperature, after long 8 formation water saturated cores, then measure core permeability K with long 8 formation water forward displacementsd, more reversely inject potential sour water solvent (concentration is least concentration/min or upper concentration/max) 2.0 PV to rock core, placed under 60 DEG C of constant temperature for 6 times, finally measure core permeability K with long 8 formation water forward displacementsd /, calculate Kd //KdRatio.Long 8 formation water water chemistry compositions are shown in Table 3, and coreflooding experiment effect is shown in Table 4.
The long 8 formation water water chemistry compositions of table 3.
The long 8 formation water displacement rock core test effects (test temperature 60 DEG C) of table 4.
From the point of view of experimental result: under 60 DEG C of constant temperatures, long 8 stratum sandstone core permeabilities before and after the test aqueous solvent acidifying of displacement length 8 formation water, permeability is brought up to 0.243mD～3.280mD by 0.182mD～2.070mD, and permeability improves 33%～58%.
Embodiment 2:
A kind of preparation method of petroleum-gas fiedl acid stimulation injection agent:
Step 1) is with embodiment 1；
Step 2) in 1000 liters of enamel reaction stills, first add Fructus Persicae 56 water to 700 liters of places, 3600g surfactant CL-6 is added to the water and mixes uniform, under agitation, sequentially add Compound-acid pickling inhibitor 1440g, the Fe in step 1)3+、Al3+Stabilizer 3840g, compound chloro organic carboxylic ester 250.26kg, then in preparation container, add Fructus Persicae 56 water locate to 1000 liters, after stirring, mensuration pH value is in the range of 7.0 ± 0.2, obtains the injection agent finished product of 1000 liters.
Embodiment 3:
A kind of preparation method of petroleum-gas fiedl acid stimulation injection agent:
Step 1) is with embodiment 1；
Step 2) in 1000 liters of enamel reaction stills, first add Fructus Persicae 56 water to 600 liters of places, 4200g surfactant CL-6 is added to the water and mixes uniform, under agitation, sequentially add Compound-acid pickling inhibitor 1680g, the Fe in step 1)3+、Al3+Stabilizer 4480g, compound chloro organic carboxylic ester 291.97kg, then in preparation container, add Fructus Persicae 56 water locate to 1000 liters, after stirring, mensuration pH value is in the range of 7.0 ± 0.2, obtains the injection agent finished product of 1000 liters.
Embodiment 4:
A kind of preparation method of petroleum-gas fiedl acid stimulation injection agent:
Step 1) is with embodiment 1；
Step 2) in 1000 liters of enamel reaction stills, first add Fructus Persicae 56 water to 600 liters of places, 4800g surfactant CL-8 is added to the water and mixes uniform, under agitation, sequentially add Compound-acid pickling inhibitor 1920g, the Fe in step 1)3+、Al3+Stabilizer 5120g, compound chloro organic carboxylic ester 333.68kg, then in preparation container, add Fructus Persicae 56 water locate to 1000 liters, after stirring, mensuration pH value is in the range of 7.0 ± 0.2, obtains the injection agent finished product of 1000 liters.
Surfactant CL-8 in the present embodiment is formed, by the development and production of Shandong chemical research institute by nonionic surfactant and zwitterionic surfactant are compounding.
Embodiment 5:
A kind of preparation method of petroleum-gas fiedl acid stimulation injection agent:
Step 1) is with embodiment 1；
Step 2) in 1000 liters of enamel reaction stills, first add Fructus Persicae 56 water to 500 liters of places, 5400g surfactant CL-8 is added to the water and mixes uniform, under agitation, sequentially add Compound-acid pickling inhibitor 2160g, the Fe in step 1)3+、Al3+Stabilizer 5760g, compound chloro organic carboxylic ester 375.39kg, then in preparation container, add Fructus Persicae 56 water locate to 1000 liters, after stirring, mensuration pH value is in the range of 7.0 ± 0.2, obtains the injection agent finished product of 1000 liters.
Embodiment 6:
A kind of preparation method of petroleum-gas fiedl acid stimulation injection agent:
Step 1) is by with embodiment 1；
Step 2) in 1000 liters of enamel reaction stills, first add Fructus Persicae 56 water to 500 liters of places, 6000g surfactant CL-8 is added to the water and mixes uniform, under agitation, sequentially add Compound-acid pickling inhibitor 2400g, the Fe in step 1)3+、Al3+Stabilizer 6400g, compound chloro organic carboxylic ester 417.10kg, then in preparation container, add Fructus Persicae 56 water locate to 1000 liters, after stirring, mensuration pH value is in the range of 7.0 ± 0.2, obtains the injection agent finished product of 1000 liters.
In sum, the present invention is a kind of potential acid system, can be used in acid stimulation and the increase water injection technology measure of sandstone formation (formation temperature >=60 DEG C), it is more suitable for high temperature (>=120 DEG C) carbonate formation, solve conventional acidulation and there is the problems such as " construction equipment and tube corrosion ", " site operation personnel exists acid injury risk ", " acid-rock reaction speed is fast, and acidifying EFFECTIVE RANGE is short ", " it is the most thorough that row is returned in residual acid "；Will not react with rock injecting during stratum, it is to avoid in conventional acidulation, acid rock contact i.e. reacts and do not arrives the shortcoming of earth formation deep.
The properties of product method of testing that the present embodiment describes the most in detail belongs to the known of the industry or common testing methods, describes the most one by one.
Exemplified as above is only the illustration to the present invention, is not intended that the restriction to protection scope of the present invention, within the every and same or analogous design of the present invention belongs to protection scope of the present invention.
Claims (6)
1. a petroleum-gas fiedl acid stimulation injection agent, it is characterised in that be made up of following material: in terms of the weight of material each in every liter of solution, surfactant 3.00g～6.00g, Compound-acid pickling inhibitor 1.20g～2.40g, Fe3+、Al3+Stabilizer 3.20g～6.40g, compound chloro organic carboxylic ester 208.55g～417.10g, remaining is aqueous solvent.
A kind of petroleum-gas fiedl acid stimulation injection agent the most according to claim 1, it is characterised in that: described surfactant model is CL-6 or CL-8.
A kind of petroleum-gas fiedl acid stimulation injection agent the most according to claim 1, it is characterised in that: described Compound-acid pickling inhibitor is the compound of halogenated phosphates and hexynol, and combined weight ratio is 1: 1.
A kind of petroleum-gas fiedl acid stimulation injection agent the most according to claim 1, it is characterised in that: described Fe3+、Al3+Stabilizer is arabo-ascorbic acid triethanolamine.
A kind of petroleum-gas fiedl acid stimulation injection agent the most according to claim 1, it is characterised in that: described compound chloro organic carboxylic ester is the compound of methylchloroformate and ethyl chloroformate, and combined weight ratio is for methylchloroformate: ethyl chloroformate=1.00∶1.15。
6. according to the preparation method of a kind of petroleum-gas fiedl acid stimulation injection agent described in any one of Claims 1 to 5, it is characterised in that comprise the following steps:
Step 1) presses 1: 1 combined weight ratio, is joined by halogenated phosphates in hexynol and is uniformly mixing to obtain Compound-acid pickling inhibitor；Powder arabo-ascorbic acid is joined in pulpous state triethanolamine, is uniformly mixed, until measuring reactant mixture pH value is 7.0 i.e. to obtain arabo-ascorbic acid triethanolamine Fe3+、Al3+Stabilizer；By methylchloroformate: ethyl chloroformate=1.00: 1.15, methylchloroformate is joined in ethyl chloroformate and be uniformly mixing to obtain compound chloro organic carboxylic ester；
Step 2) first in preparation container, add a certain amount of water, 3.00g～6.00g surfactant is added to the water and mixes uniformly, under agitation, sequentially add Compound-acid pickling inhibitor 1.20g～2.40g, the Fe in step 1)3+、Al3+Stabilizer 3.20g～6.40g, compound chloro organic carboxylic ester 208.55g～417.10g, then in preparation container, add water locate to 1L, after stirring, mensuration pH value is in the range of 7.0 ± 0.2, obtains the injection agent finished product of 1L.
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| CN111057534A (en) * | 2019-11-18 | 2020-04-24 | 中国石油天然气股份有限公司 | Emulsion acidification yield-increasing and injection-increasing agent and preparation and use methods thereof |
| CN111849453A (en) * | 2019-04-30 | 2020-10-30 | 深圳市百勤石油技术有限公司 | Polychlorinated ketol self-acid generator and use method thereof |
| CN112342010A (en) * | 2020-09-23 | 2021-02-09 | 南阳市华庆中能能源技术开发有限公司 | Polychlorinated ether alcohol self-acid generator and use method thereof |
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| CN111849453A (en) * | 2019-04-30 | 2020-10-30 | 深圳市百勤石油技术有限公司 | Polychlorinated ketol self-acid generator and use method thereof |
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