CN101323780B - Low pervasion oilfield thermochemical cleanup additive and use thereof - Google Patents
Low pervasion oilfield thermochemical cleanup additive and use thereof Download PDFInfo
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- CN101323780B CN101323780B CN200810150553XA CN200810150553A CN101323780B CN 101323780 B CN101323780 B CN 101323780B CN 200810150553X A CN200810150553X A CN 200810150553XA CN 200810150553 A CN200810150553 A CN 200810150553A CN 101323780 B CN101323780 B CN 101323780B
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Abstract
The invention discloses a low permeability oil field thermochemical cleanup additive and applications thereof in acidification and fracturing technologies of low permeability oil field oil and water wells. The thermochemical cleanup additive consists of an agent A and an agent B. The agent A consists of certain parts by weight of phosphoric acid, sodium nitrite, dodecyl benzene sulfonic acid sodium, emulsifier, surfactant and water; the agent B consists of certain parts by weight of urea, ammonium chloride and water. The agent A and the agent B thermally react under certain conditions to produce a large amount of nitrogen, carbon dioxide and high-temperature-hot-water and a large amount of heat simultaneously, in addition, the nitrogen and the carbon dioxide with certain pressure can form a large amount of foam under the function of a highly efficient active foaming agent for residues to be drained out of the oil and water wells. The thermochemical cleanup agent does not burn or explode easily and is mainly applied to the cleanup technology of the acidification and fracturing techniques of the low permeability oil and water wells for solving the problems such as inadequate drainage strength, reducing pollutions of remaining operating fluid to reservoir stratums and effectively enhancing the acidification and fracturing effects.
Description
Technical field
The present invention relates to the thermochemistry cleanup additive and the application thereof of the acidifying of a kind of low permeability oil field oil and water well, fracturing technology use.
Background technology
Acidifying is by to stratum injection acid solution, dissolves the material of the reservoir that results in blockage in reservoir rock mineralogical composition and the operation process such as drilling well, completion, well workover and oil recovery, improves the penetrating quality of reservoir, thereby improves oil well production increasing and intensified injection of wells; Pressure break is to utilize ground high-pressure pump group, pump into high viscosity fracturing fluid in the well and produce the crack on the stratum with the discharge capacity that surpasses the formation absorption ability, add propping agent (as quartz sand etc.) filling and enter the crack, improve the flow conductivity on stratum, thereby improve oil well production increasing and intensified injection of wells.
Above-mentioned two technologies are subjected to paying much attention to and widespread use as the important well stimulation in oil field, but they all exist the operation raffinate of working later to return row's problem from the stratum.Generally early stage in oil-field development, employing in acid solution and fracturing liquid, add cleanup additive reduce acidifying or fracturing working fluid surface tension, change the wetting situation on stratum and help the row of returning of working fluid, and rely on the energy on stratum self that remaining working fluid is returned to discharge ground; But along with the dark people of oil-field development, reservoir pressure reduces gradually, and the raffinate that forms after oil and water well acidifying and the pressure break is difficult to only rely on the filling cleanup additive and discharges more voluntarily.Low permeability oil field particularly, working fluid residue are separated out back regular meeting and are stopped up the stratum in the fluid channel, cause the secondary pollution injury to the stratum, have influenced technological effect to a certain extent, and are difficult to remove in the secondary injury construction afterwards.
In order to solve the problem that the raffinate of working after Middle-Low Permeability Reservoirs acidifying, the pressure break returns row, the general in the past oil pump suction of adopting more, as the term suggests be exactly utilize the mechanical energy of oil well pump directly will work raffinate aspirates, ground is gone back in lifting, but there is the problem that the row of returning is untimely and corrode oil well pump, can not ensures the works better of pump and influence oil well production.
People had been developed the augmented injection liquid nitrogen again and liquid carbon dioxide helps technologies such as row in recent years, and liquid nitrogen and liquid carbon dioxide are injected the oil and water well of acidifying or pressure break, and the physical energy that utilizes gas expansion to produce gives rise to ground with raffinate in the pit shaft.Nitrogen is rare gas element in addition, and stability is strong, and compression factor is big, elastic energy is big, viscosity is low, penetrating power is strong, the flowability that helps keeping sand pressure, additional producing energy and improve crude oil, the effect that play the viscosity reduction displacement of reservoir oil, improves oil recovery factor; Carbonic acid gas be a kind of in You Heshui all very high gas of solubleness.When it is dissolved in the crude oil in a large number, can make crude oil volumetric expansion, viscosity degradation and reduction interfacial tension, crude oil is easier displaces for displacement of reservoir oil medium thereby make, and improves sweep efficiency and displacement efficiency; When it is dissolved in water, generate carbonic acid.Limestone in carbonic acid and the stratum and dolomite generate water miscible hydrocarbonate again, improve the rate of permeation on stratum, enlarge the swept volume of displacement of reservoir oil medium, help improving the recovery ratio of crude oil.
These two kinds of cleanup additives of nitrogen and carbonic acid gas respectively have the advantage of uniqueness in a word, but also all have the expense height, return problems such as row pressure power is low.Because the fluent meterial gasification needs to absorb a large amount of heat energy, reduced the temperature of surrounding environment in addition, more can not be satisfactory to the flowback effect of the higher hyposmosis oil well of viscosity of crude.
Summary of the invention
Technical problem to be solved by this invention is at above-mentioned deficiency of the prior art, and a kind of thermochemistry cleanup additive that is applicable to the acidifying of low permeability oil field oil and water well, fracturing technology is provided.Adopting this thermochemistry cleanup additive can be fully the row's of helping advantage of nitrogen and carbonic acid gas to be organically combined is integral, problems such as the two row's of returning dynamics is not enough, executive cost height have been solved simultaneously again, reduced of the pollution of remaining working fluid, effectively improved acidifying and fracturing effect reservoir.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of low pervasion oilfield thermochemical cleanup additive, it is characterized in that being made up of A agent and B agent, the raw material of described A agent is formed and weight percent is: phosphoric acid 0～5%, Sodium Nitrite 10～30%, Sodium dodecylbenzene sulfonate 0.1～1%, emulsifying agent 0.1～2%, tensio-active agent 0.001～0.1%, surplus is a water, described emulsifying agent is a polyoxyethylene octyl phenol ether, and described tensio-active agent is a fluorine surfactant.
The preparation method of described A agent is: add a certain amount of water in container earlier, add Sodium Nitrite, Sodium dodecylbenzene sulfonate, emulsifier polyoxyethylene octyl phenol ether, fluorine surfactant and the phosphoric acid of above-mentioned weight percent again, make the A agent after stirring.
The raw material of described B agent is formed and weight percent is: urea 5～20%, ammonium chloride 10～20%, water 60～85%.
The preparation method of described B agent is: the urea and the ammonium chloride of above-mentioned weight percent are placed in another container, add the water of above-mentioned weight percent, stir, treat to make the B agent after it dissolves fully.
Another object of the present invention provides the application of a kind of low pervasion oilfield thermochemical cleanup additive in acidifying of low permeability oil field oil and water well and fracturing technology.
The know-why of institute of the present invention foundation:
After the thermochemistry cleanup additive injects the stratum, under the certain condition of stratum, cause thermochemistry cleanup additive generation chemical reaction, generate a large amount of nitrogen and carbonic acid gas simultaneously and be accompanied by a large amount of heats, rely on the physical energy of the gentle volumetric expansion of these chemical reaction heat energy, replenish producing energy and discharge the work raffinate.
Its chemical equation is:
CO (NH
2)
2+ NH
4 ++ 3NO
2 -+ 2H
+3N
2↑+CO
2↑+5H
2O+Q (heat).
Phosphoric acid plays catalysis Sodium Nitrite and ammonium chloride, urea reaction in the A agent of the present invention.The content of phosphoric acid plays an important role to both thermal chemical reaction speed, if selected phosphoric acid consumption exceeds scope of the present invention, the reaction effect that all can not receive.The acid in the middle of the acidifying working fluid it is worthy of note, can not use phosphoric acid to make the initiation catalyzer in the acidification technique, because can should be reacted in catalysis.In addition the various chemical assistants except that Sodium Nitrite and phosphoric acid cooperate with each other the effect of the high-efficiency activated foaming that same-action reached be one-component can not possess.Each components contents scope also is the optimized results through obtaining after the test of many times in this prescription, only just can reach promising result in this ratio range.
The use that mixes of urea and ammonium chloride in the B agent of the present invention, be to have taken all factors into consideration thermal chemical reaction to produce the efficient of heat and the optimized results after reaction product nitrogen and the carbonic acid gas optimum volume ratio, therefore their percentage composition has keying action to the row's of helping effect, also is the test of many times results of screening.
The present invention compared with prior art has the following advantages: thermochemistry cleanup additive of the present invention is made up of A agent and B agent, and thermal chemical reaction takes place under certain condition for A agent and B agent, produces a large amount of nitrogen, carbonic acid gas and high-temperature-hot-water, a large amount of heats of simultaneous; In addition, nitrogen and carbonic acid gas with certain pressure can help the raffinate residue is returned the discharge oil and water well by a large amount of foams of formation under the effect of high-efficiency activated whipping agent, and this thermochemistry cleanup additive is nonflammable, non-explosive, and the row of returning is thorough, and is pollution-free to the stratum.
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment
Each raw material of following examples all by weight percentage.
Embodiment 1
The preparation of A agent: in container, add earlier 78.68% water, add 21% Sodium Nitrite, 0.15% Sodium dodecylbenzene sulfonate, 0.15% emulsifier polyoxyethylene octyl phenol ether, 0.02% fluorine surfactant again, make the A agent after stirring.
The preparation of B agent: urea with 12% and 12% ammonium chloride place in another container, add 76% water, stir, and treat to make the B agent after it dissolves fully.
Embodiment 2
The preparation of A agent: elder generation adds 78.08% water in container, add 21% Sodium Nitrite, 0.15% Sodium dodecylbenzene sulfonate, 0.15% emulsifier polyoxyethylene octyl phenol ether, 0.02% fluorine surfactant and 0.6% phosphoric acid again, make the A agent after stirring.
The preparation of B agent: urea with 5% and 10% ammonium chloride place in another container, add 85% water, stir, and treat to make the B agent after it dissolves fully.
Embodiment 3
The preparation of A agent: elder generation adds 89.6% water in container, add 10% Sodium Nitrite, 0.10% Sodium dodecylbenzene sulfonate, 0.10% emulsifier polyoxyethylene octyl phenol ether, 0.001% fluorine surfactant and 0.199% phosphoric acid again, make the A agent after stirring.
The preparation of B agent: urea with 20% and 20% ammonium chloride place in another container, add 60% water, stir, and treat to make the B agent after it dissolves fully.
Embodiment 4
The preparation of A agent: elder generation adds 61.9% water in container, add 30% Sodium Nitrite, 1% Sodium dodecylbenzene sulfonate, 2% emulsifier polyoxyethylene octyl phenol ether, 0.1% fluorine surfactant and 5% phosphoric acid again, make the A agent after stirring.
The preparation of B agent: urea with 15% and 15% ammonium chloride place in another container, add 70% water, stir, and treat to make the B agent after it dissolves fully.
Embodiment 5
The preparation of A agent: elder generation adds 81.95% water in container, add 15% Sodium Nitrite, 0.5% Sodium dodecylbenzene sulfonate, 0.5% emulsifier polyoxyethylene octyl phenol ether, 0.05% fluorine surfactant and 2% phosphoric acid again, make the A agent after stirring.
The preparation of B agent: urea with 16% and 16% ammonium chloride place in another container, add 68% water, stir, and treat to make the B agent after it dissolves fully.
Embodiment 6
The preparation of A agent: elder generation adds 70.33% water in container, add 26% Sodium Nitrite, 0.3% Sodium dodecylbenzene sulfonate, 0.3% emulsifier polyoxyethylene octyl phenol ether, 0.07% fluorine surfactant and 3% phosphoric acid again, make the A agent after stirring.
The preparation of B agent: urea with 10% and 10% ammonium chloride place in another container, add 80% water, stir, and treat to make the B agent after it dissolves fully.
One, the application of thermochemistry cleanup additive of the present invention in low permeability oil field oil and water well acidification technique, following technological operation program is carried out in suggestion: such as reservoir thickness is 32 meters, porosity 12%, 3 meters of treatment radius.Pharmaceutical quantities 130 sides are handled in total acidifying.
During operation, earlier with the hot abundant well-flushing of re-injection water.
1, clamp-on A agent 10 sides, described A agent is made up of the raw material of following weight percentage: Sodium Nitrite 21%, Sodium dodecylbenzene sulfonate 0.15%, polyoxyethylene octyl phenol ether 0.15%, fluorine surfactant 0.02% and water 78.68%;
2, clamp-on spacer pad 5 sides, described spacer pad is the aqueous solution that contains Repone K 1%;
3, clamp-on spearhead 20 sides: described spearhead is hydrochloric 5% and the aqueous solution of Repone K 1%;
4, clamp-on spacer pad 5 sides, described spacer pad is the aqueous solution that contains Repone K 1%;
5, clamp-on B agent 5 sides, described B agent is made up of the raw material of following weight percentage: urea 12%, ammonium chloride 12% and water 76%;
6, clamp-on spacer pad 5 sides, described spacer pad is the aqueous solution that contains Repone K 1%;
7, clamp-on main acid 60 sides: described main acid is the aqueous solution of hydrochloric acid 10%+ hydrofluoric acid 6%+ Fe stabilizer 2%+ acidification corrosion inhibitor 1%+ mutual solvent 1%+ Repone K 1%; Described mutual solvent is an ethylene glycol monobutyl ether;
8, clamp-on displacing liquid 20 sides: described displacing liquid is the aqueous solution of OP10 promoting agent 0.5%+ Repone K 1%;
9, closing well is 4～6 hours;
10, anti-flushing well acid discharge: it is that neutrality can stop anti-row that outlet returns that discharge opeing tests to expel liquid with the pH test paper;
11, trip out operating tool string, be lowered to flow string, opening well and making production.
The major advantage that thermochemistry cleanup additive of the present invention is applied to acidification technique is:
1) a large amount of heats that produced of thermochemistry cleanup additive generation chemical reaction and rare gas element can effective clean stratum organic depositions, improve follow-up acidifying efficient;
2) heat energy of chemical reaction generation can make colloid, bitum viscosity reduce, and the oil-water emulsion breakdown of emulsion also has very strong de-plugging effect;
3) nitrogen is rare gas element, and stability is strong, under high temperature and high pressure effect, can clean pit shaft effectively, removes the immediate vicinity of wellbore pollution and stops up, and improves its rate of permeation, effectively improves the flowability of crude oil; Carbonic acid gas can make that crude oil is easier displaces for displacement of reservoir oil medium, improves sweep efficiency and displacement efficiency, improves the rate of permeation on stratum simultaneously, enlarges the swept volume of displacement of reservoir oil medium, helps improving the recovery ratio of crude oil.
4) thermochemistry help row be that chemical reaction takes place in the stratum, rely on the physics mode of the gentle volumetric expansion of chemical reaction heat energy to discharge residual acid, the rare gas element and the whipping agent component that produce form a large amount of stable foams, reduce fluid column pressure and the frictional resistance of residual acid in the well letter, quicken residual acid and return row, reduce the pollution of residual acid, strengthened acidizing effect the stratum.
Two, the application of thermochemistry cleanup additive of the present invention in low permeability oil field fracture in oil and water wells technology is example with total chemicals treatment amount 195 sides, and following technological operation program is carried out in suggestion:
1, pressure testing;
2, (described spearhead can be used water-base gel fracturing fluid to pump into spearhead, mainly be made into by water 95.8%, gelatinizing agent polyacrylamide 2%, linking agent vulkacit H 2% and gel breaker Sodium Persulfate 0.2%): the construction pressurization, press off the stratum, pressure descends gradually, consumption 70 sides;
3, squeeze sand-carrying agent (described sand-carrying agent is meant and adds a certain amount of propping agent such as quartz sand etc. in above-mentioned water-base gel fracturing fluid): treat to begin to add sand 10 sides after pressure is reduced to operating pressure gradually, fluid volume 55 sides, average sand is than 18.2%;
4, clamp-on displacing liquid 20 sides (described displacing liquid is the aqueous solution of OP10 promoting agent 0.5%+ Repone K 1%);
5, clamp-on thermochemistry and help row A agent 20 sides, described A agent is made up of the raw material of following weight percentage: Sodium Nitrite 21%, phosphoric acid 0.6%, Sodium dodecylbenzene sulfonate 0.15%, polyoxyethylene octyl phenol ether 0.15%, fluorine surfactant 0.02% and water 78.08%;
6, clamp-on spacer pad 10 sides, described spacer pad is the aqueous solution that contains Repone K 1%;
7, clamp-on thermochemistry and help row B agent 10 sides, described B agent is made up of the raw material of following weight percentage: urea 12%, ammonium chloride 12% and water 76%;
8, closing well reaction 2～4h;
9, it is that neutrality can stop anti-row that drive a well open flow, discharge opeing, outlet return that discharge opeing tests to expel liquid with the pH test paper;
10, trip out operating tool string, be lowered to flow string, opening well and making production.
The major advantage that thermochemistry cleanup additive of the present invention is applied in pressure break (water base) technology is:
1) make aqueous gel break glue rapidly, fully;
2) corrosive shake increases flow conductivity;
3) a large amount of heat energy of Chan Shenging can play the effect of viscosity reduction, degraded to the polymer macromolecule in the fracturing liquid;
4) pollutent is partly returned drain into ground, reduce secondary pollution, improve measure effect.
Claims (2)
1. low pervasion oilfield thermochemical cleanup additive, it is characterized in that forming by A agent and B agent, the raw material of described A agent is formed and weight percent is: phosphoric acid 0～5%, Sodium Nitrite 10～30%, Sodium dodecylbenzene sulfonate 0.1～1%, emulsifying agent 0.1～2%, tensio-active agent 0.001～0.1%, surplus is a water, and described emulsifying agent is a polyoxyethylene octyl phenol ether, and described tensio-active agent is a fluorine surfactant;
The raw material of described B agent is formed and weight percent is: urea 5～20%, ammonium chloride 10～20%, water 60～85%.
2. the application of a kind of low pervasion oilfield thermochemical cleanup additive as claimed in claim 1 in acidifying of low permeability oil field oil and water well and fracturing technology.
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| CN101323780B true CN101323780B (en) | 2010-06-02 |
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| CN101323780A (en) | 2008-12-17 |
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