CN1034376A - Acid thickening composition prepares the AMPS/Am multipolymer through radiation - Google Patents
Acid thickening composition prepares the AMPS/Am multipolymer through radiation Download PDFInfo
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Abstract
By water, the acid-thickened thing of the multipolymer of a kind of acid and a kind of 2-acrylamide-2-methyl propane sulfonic acid sodium that produces by radiation and acrylamide is formed is applicable to assorted gangue or the acid-treated water-soluble acid thickening composition in crack.This composition can directly be used and need not linking agent.They also are applicable to the acid treatment of mud.
Description
The application is that of the application № 610,221 that submitted May 14 in 1984 divides an application.
The invention relates to the promotion method that increases the recovery of oil amount.
Using the aqueous acidic composition to handle subterranean strata by acid treatment and/or break method is known with the method that increases hydrocarbon polymer output.To come the such aqueous acids method for compositions of thickening also be known by adding a kind of macromolecule tackifer water miscible or water dispersible.Also once various gels or linking agent and/or whipping agent were added in the water acid that contains polymkeric substance to make the slow setting acid gel that is suitable for injecting subterranean strata.Yet injecting condition is controlled in the service requirements of linking agent meticulously, even because small mistake will make this system can not gelation, or more cakes with moulded designs be with regard to gelation before material arrives injection device.
An object of the present invention is to provide improved acid thickening composition.
Second purpose of the present invention is to suppress the effect of acid to Wingdale, so that fresh acid can enter in the darker formation.
Another object of the present invention provides the improved method for preparing thickening acid.
A further object of the present invention provides improved acid treatment technology.
A further object of the invention provides the composition that is used for acid treatment and/or acid treatment and fracture, makes injecting method that bigger variation leeway be arranged.
According to the present invention, adopt and a kind ofly cause the 2-acrylamide-2-methyl propane sulfonic acid sodium (NaAMPS) generate and a kind of aqueous acid composition of water solubility copolymer thickening of acrylamide (Am) by radiation.For describing this invention, " thickening acid " this speech refers to the macromolecule tackifer that contains water-soluble or water dispersible and the aqueous acid that does not contain linking agent." gelation acid " this speech refers to the macromolecule tackifer that comprises water-soluble or water dispersible and contains the aqueous acids composition of a kind of linking agent or gelatinizing agents.The viscosity of aqueous acids depends on the molecular weight of macromolecule tackifer and the concentration in acid thereof.Viscosity also is the function of the thickening capabilities of used polymkeric substance own.Therefore here used polymer composition has good intrinsic thickening capabilities, can directly use and needn't add any linking agent or gelatinizing agents.
Here used " multipolymer " speech comprises from 2-acrylamide-2-methyl propane sulfonic acid sodium and the formed multipolymer bonding agent composition of acrylamide.These two kinds of monomers all can have been bought, and can prepare with the well-known technology of a kind of this technical field." AMPS " this speech is the trade mark of the prepared 2-acrylamide-2-methyl propane sulfonic acid of Lubrizol company.
Adopt known any energetic ion radiotechnology can prepare multipolymer of the present invention, but preferably a kind of as Phalanges etc. at United States Patent (USP) 4,137,969(1979 February 6) these multipolymers of preparation in the described salts solution, it is incorporated by reference here that it has disclosed the content of this respect.
In brief, this preferably method be such: a pH value is about 2 to 12 the aqueous solution and carries out radiation, the weight concentration of the monomer mixture of this aqueous solution is 10～40%, wherein 2-acrylamide-2-methyl propane sulfonic acid sodium accounts for 40～95 parts, acrylamide accounts for 5～60 parts (weight ratios), this solution also comprises a kind of salt, and its amount is at least the 3%(weight ratio).This salt is selected from vitriolate of tartar, Repone K, Potassium monofluoride, sal enixum, Tripotassium phosphate, Rhodiaphos DKP, potassium dihydrogen phosphate, sodium sulfate, sodium pyrosulfate, sodium-chlor, tertiary sodium phosphate, Di-Sodium Phosphate, monosodium phosphate, Lithium Sulphate, lithium hydrogen sulfate, lithium chloride, ammonium sulfate, monoammonium sulfate, ammonium chloride, triammonium phosphate, diammonium phosphate, monoammonium phosphate, Neutral ammonium fluoride, or the mixture of these salt.The energetic ion yield of radiation is 1,000 to 200,000 rad (rads) per hour, and total radiation dosage is 1,000 to 30,000 rad.If pH value of water solution is about 7 to 9 and aqueous solution salt when being a kind of ammonium salt, can obtain a kind of water miscible, be the aqueous solution of the high molecular weight copolymer of line style basically.
Resultant composition consists of: 40～95%2-acrylamide-2-methyl propane sulfonic acid sodium structural unit, 5～60% acrylamide structural units (weight ratio).Composition consists of 50～90% 2-acrylamide-2-methyl propane sulfonic acid sodium and 20～50% acrylamides preferably, best composition be above-mentioned two monomer structure unit be about respectively 70 and the 30(weight ratio).
Acid thickening composition of the present invention is suitable for rupturing acid treatment underground petroleum rock stratum most to increase the petroleum recovery amount.Yet, also they can be used for the acid treatment process of assorted gangue, promptly, acid is injected into the rock stratum, its injection speed is not enough in the rock stratum to produce crack or fracture, or thickened mud acid, and this mud acid is hydrochloric acid and much cape curtain ancient type of banner hoisted on a featherdecked mast rank an ancient spears of producing on the spot from HCl and ammonium bifluoride
Acid thickening composition of the present invention also can be used as the acid in filler/technic acid.This technical fee is very low, earlier with traditional hydraulic pressure method of breaking, carries out etch (being the propping agent of another kind of form) with acid on effect then.This technology is published in The Journal of Canadian Petroleum Technology(Canada petro-technology magazine by Hendrickson etc.) the 1st～5 page go up (January nineteen sixty-eight～March number), draw its content here as a reference.Also can propping agent and method of the present invention is shared with further raising oil production amount.Acid thickening composition of the present invention can penetrate full-bodied filler, and provides a kind of and have more conductive etch mode than crosslinked acid composition.When thermolysis filler fluid, it can dilute thickening acid, because thickening acid is uncrosslinked.And though acid thickening composition of the present invention can use under any temperature, their high-temperature stability makes them have another advantage, promptly is used for the rock stratum of high temperature and/or high divalent ion concentration.
By the dissolving of Na AMPS/Am multipolymer tackifier as defined above or be dispersed in the acid composition that can make this thickening in the aqueous acid solution.
The polymeric constituent of acid thickening composition of the present invention can stop by acid, shears, and the ionogen in the water is caused in heat or the rock stratum and in the tissue of rock stratum goes bad.Under the high shear rate of polymkeric substance in the acid thickening composition when the pumping acid composition is stable, for example, said composition reach 10 feet during 40,000 feet degree of depth in, by the pipeline of various size, be that the shearing of 10～60 barrels of per minutes is very stable for pump rate.Secondly, said composition is stable under the condition of rock temperature than higher (for example 170 (77 ℃) or higher) in a long time.This desirability that had both made at room temperature also very important stability improve composition of the present invention greatly, because can be before several days of use acid composition, these acid compositions of preparation under the condition of high hydrogen ion concentration (low pH value).Though any ratio 7 low pH values all are acidic conditionss, the present invention relates generally to the pH value to be about 3 or to be lower than 3 acid system, generally is to be not less than a determined value of 1.
Acid composition of the present invention also has good antifriction character.It has enough flowabilities, thereby can make fresh acid composition penetrate the rock stratum well, and flows to the fluid loss minimizing of rock stratum matrix (assorted gangue).Penetrate in case finish, said composition can keep in for some time and the contacting of rock stratum, at this section in the period, the acid in the composition can with the rock stratum in the drainage channel that makes new advances with developing of acid-soluble component reaction or enlarge the existing passage that passes through the rock stratum, promote fluidic output thus.Thereafter, said composition should be such: do not have permanent gel and produce, but the state of maintenance material itself, or becoming the fluid with enough flowabilities reclaims in a large number to open the crack that leads to recovery of oil that enlarges therefrom.Also can cause these cracks by injection pressure, perhaps these cracks exist, but in both cases, acid can enlarge them.Yet used acid composition really can keep enough viscosity, and unreacted stone flour or rock stratum are suspended in wherein, in fluid recycling process, these break flours and rock stratum can be removed.
The base stock of acid thickening composition is:
(1) water;
(2) acid; And
(3) macromolecule tackifer.
Water can be pure basically water, i.e. tap water, or seawater, or mimic seawater, or a kind of saliniferous solution are as place salt solution or primitive water.
Comprise and anyly can increase fluid (for example hydrocarbon polymer) flows into the velocity of flow in the well by the rock stratum acid effectively putting into practice when of the present invention used acid.Therefore, under suitable working conditions, the example of such acid can comprise mineral acid or mineral acid, example hydrochloric acid, nitric acid, thionamic acid and hydrofluoric acid.Can produce HF on the spot.In addition, C
1-C
4Organic acid, as formic acid, acetate, propionic acid, butyric acid, halogenated carboxylic acid, as Mono Chloro Acetic Acid and chloropropionic acid, and these sour mixtures, the such mineral acid of above-mentioned acid and HCl is shared, also suits.Better be to use non-oxidizable mineral acid.Best is hydrochloric acid.
Can be according to the kind of the kind of acid, processed rock stratum, above-mentioned consistency requires and the desired result who obtains changes acid in the particular procedure operation concentration or intensity.Say that generally the concentration of acid (or maxima solubility of acid) can be 0.4 to 60%(weight percent of acid thickening composition gross weight), mainly decide on the kind of acid.Usually the concentration range that adopts is 5 to 50%(weight percents).It is that benchmark calculates that the concentration of acid is preferably 15 to the 28%(gross weights by water and acid).This scope is representative especially for aqueous hydrochloric acid, though the maximum concentration of HCl is a 37%(weight in the hydrochloric acid).
Composition of the present invention can with tensio-active agent and usefulness, and available known foaming technique promptly adopts rare gas element, as nitrogen or carbonic acid gas to prepare a kind of 65 or high-grade foam material more.Remove the volume of gas in the foam material with the volume of total foam material, multiply by 100 grades that just can determine foam material then.These method of calculation by Norman still Venezuelan block ɡ, 324,669(1982 April 13) in open, incorporated by reference here.Put into practice the used acid of the present invention and also can comprise inhibiter, emulsifying agent, sequestrant, low friction compound, known conventional additive in fluid loss additives or the present technique.Composition of the present invention also can be with to be generally used for chemically acid proof oil wetted surface promoting agent shared so that acid resistance to be provided.
The amount for preparing the used Na AMPS/Am multipolymer of acid thickening composition of the present invention, according to used particular polymers, the purity of polymkeric substance and for the character requirement of final composition can change in a big way.But the amount of thickening acid should be the amount that will be enough to effective thickened aqueous acid solution needs after adding at least.Put into practice with regard to the purpose with regard to all, in this composition the amount of used polymkeric substance generally will from 0.01 to about 15%(weight) in the scope of (by the gross weight of said composition), be preferably 0.10 to about 3%(weight), be preferably 0.6 to 1.5%(weight).
The present invention bores the porous underground rock stratum penetrated to increase fluid with the acid treatment well, crude oil for example, the output of Sweet natural gas and the hydrocarbon polymer that obtains from the rock stratum etc.The acid treatment process comprises and a kind of acid imported under enough pressure in the well and this is clamp-oned the rock stratum, acid there with the rock stratum in acid-soluble component reaction.The present invention is that wherein sour effect is suppressed to direct a change of this technology, penetrates farther distance until the material of being injected in the rock stratum.Present technique is not limited in the rock stratum of peracid solubility, as Wingdale or rhombspar, also can be used for the rock stratum of other kind, as comprises the sandstone that resembles the acid-soluble component layers so the various carbonate.Often wish to increase the energy of the acid thickening composition of being injected by the pressure of known other rare gas element in nitrogen or this technology.
Example I
This example proves, if multipolymer is to prepare in the polymerization system that the gamma-rays radiation causes, then improved the 70/30(wt/wt of 2-acrylamide-2-methyl propane sulfonic acid sodium (NaAMPS) and acrylamide (Am)) effect of the inhibition acid of multipolymer.By contrast, if this 70/30(wt/wt) the NaAMPS/Am multipolymer is to prepare being caused in the polymerization system that method caused by chemistry, then the effect of the inhibition acid of this multipolymer will be hanged down.
Three kinds of copolymer sample and a kind of copolymer sample that cause preparation by chemical method that cause preparation by radiation in sour inhibition test, have been adopted.Wherein a kind of radiation copolymerization matter sample (Reten
547E) demonstrate the roughly the same viscosity of sample (SPX 5025) that causes with chemistry, and other two kinds of radiation copolymerization matter sample (Reten
547C) and Reten
Viscosity 547D), a kind of viscosity than chemistry initiation sample (SPX 5025) is low, and another kind of than its height.Based on the viscosimetric analysis result, sample Reten
The molecular weight of 547E and SPX 5025 is considered to proximate.The table I combines acid and suppresses result of experiment.
The table I
The 70/30(wt/wt of NaAMPS and Am)
The acid of multipolymer suppresses
*Effect Wingdale weight
The loss of copolymer sample experiment viscosity
*(gram/minute)
Reten
547C
a1 medium 0.16
Reten
547E
b2 are similar to SPX5025 0.20
Reten
547D
c3 low 0.22
SPX 5025
d4 are similar to Reten
547E 0.31
*The Wingdale sample (5/8 cubic inch) that will obtain from the Smackouer rock stratum of the Hopkins in continent, Texas contacts 10 minutes with a solution of being made up of 1 part of copolymer solution and 28 parts of hydrochloric acid (weight ratio) under 200 temperature.Limestone block contains the multipolymer (experiment 1 that radiation causes at each, 2,3) weight loss proves that than low this fact of weight loss in the solution of the multipolymer that contains the chemical method initiation (experiment 4) multipolymer that radiation causes has more effective sour restraining effect in the solution.
A, b, cThese multipolymers are to prepare in the polymerization system that is caused by the gamma-rays radiation.
dThis multipolymer prepares by the chemical method initiated polymerization.
Referring to the experimental result in the table I, obviously, the multipolymer that radiation causes (experiment 1,2, the 3) multipolymer that (the Wingdale weight loss values is lower) causes than chemical method aspect the acid inhibition (experiment 4: the Wingdale weight loss values is than higher) is more effective.Noticeable another fact is, the similar multipolymer of viscosity, and (experiment 2 and 4) suppresses to have shown very big difference on the effect in acid to suppose that their molecular weight is also similar.This difference indicates significantly: the multipolymer that the multipolymer that radiation causes causes than chemical method has bigger acid and suppresses effect.If time sufficiently long, the acid of thickening the most at last and the acid of not thickening consume the Wingdale of as much.
The surprising advantageous effects of the material that causes for radiation, a kind of possible explanation is: this material has better thread-like molecule configuration.This is just opposite with theory hypothesis, because from the angle of theory, the molecule of radiation initiation gained should have more side chain rather than line style configuration.The radiating material also is by proton institute terminated.
The example II
One 7,830 feet of New Mexico Roosevelt, hole static temperature at the bottom of the 155FBHST() Fusselman well is to finish in the matrix mode with 14,000 gallons of 15-28%HCl at first.Initial output is: 113 BOPD(bucket oil/skies), and 55 BWPD(bucket water/skies), and 57 MMCFGPD(cubic feet gas/skies), this output drops to 3 BOPD with annual 60% speed.
By sifting out waterpower sand seam this well is handled again, the oil yield before and after handling does not change.
After four months, again this well is handled, used 500 gallon 15% destruction acid, and break, contain the DSGA polymkeric substance as thickening material in this HCl solution with 15,000 gallons 20%HCl.12,000 gallons of fillers and 6,000 gallons of irrigations have also been used.DSGA is the trade mark of 70/30 NaAMPS/Am multipolymer of radiation method production.The acid of three batches of filler gelations alternately is pumped in the well with the speed of 13BPM and the nitrogen speed with 400scf/bb1.
After with the DSGA polymer treatment, initial output is 23BOPD, 2BWPD and 31MCFGPD.In preceding 30 days, output average out to 35BOPD, 5BWPD and 57MCFGPD.Preceding 6 months output average out to 31BOPD, 6BWPD and 33MCFGPD.
The example III
The 282F of North Dakota State Mckenzie, 110 feet distance is run through in 12,570 feet rock stratum, inland lake.Get a well with 5000 gallons of 15%HCl during beginning, the output in first month is 590BOPD and 30BWPD.In the production of the first two years, output drops to 77BOPD year by year, 21BWPD and 130MCFGPD.
(concentration is that 130 pounds/1000 gallons 28%HCl and 13,000 gallons of fillers and flush fluid are handled this well to contain the DSGA polymkeric substance with 20,000 gallons.Use the ball sealing water conservancy diversion.This well yield is 440BOPD, 35BWPD and 830MCFGPD after just having handled.The stable rate that first month exploits with pump is 516BOPD, 71BWPD and 860MCFGPD.
The example IV
The 160F well in the Charles of Montana State Roosevelt " C " rock stratum runs through the 6262-76 foot.Average permeability is 0.41md, and mean porosities is 14%.This well be at first with 1,500 gallon of 15%HCl exploitation, use ball sealing with the speed of 2BPM.Initial output is 142BOPD and 28BWPD.After 5 months, output has dropped to 72BOPD and 11BWPD.
With 2000 gallon 15% HCl, be that 7,000 gallons (500 gallons/foot) contain DSGA polymkeric substance (100 pounds/1000 gallons) and break 14 feet zone as 28% acid of gelatinizing agents once more then.This processing comprises two batches of filler material, and the acid of gelation and irrigation, rate of pumping are 7BPM.The volume of filler and irrigation is 6,000 gallons.In first rinse step, the combination of using ball sealing and phenylformic acid thin slice is as water conservancy diversion.All fluids comprise 500scf/bb1 nitrogen.
The initial potential of this well is 261BOPD and 45BWPD.The output average out to 208BOPD and the 29BWPD of earlier month.
The example V
The 132F of the Andrews of Texas, the Wolfcamp rock stratum band of 8094-8144 foot was produced 10 years, when output is reduced to 2BOPD, 52MCFGPD, and during not water outlet, be stopped use.This well is to build up with 16,000 gallon 15% acid at first.Initial output is average 33BOPD.
Abandoning the Wolfcamp area after 14 years, reenter this area.The mean yield of lease is 5BOPD.The phase of giving is by using DSGA polymkeric substance (90 pounds/1000 gallons) may reach the output of 15BOPD in thickening acid crack treatment.With 10,500 gallons of 28%DSPA and 9,000 gallons of fillers and the flush fluid speed with 12BPM, and with 1, after the 000scf/bb1 nitrogen treatment, the initial output of this well is 39BOPD.
Though described the present invention in detail in order to describe face, should not think that the present invention only limits to this.Be that various changes and modifications can be arranged within the spirit and scope of the present invention.
Claims (18)
1, in the presence of the acid thickening composition that does not contain linking agent, the injecting material of at least a good composition is infiltrated through subterranean strata, handle a kind of method of this rock stratum, this acid thickening composition comprises:
(1) water
(2) a kind of acid; With
(3) causing the multipolymer that the monomer mixture of 2-acrylamide-2-methyl propane sulfonic acid sodium and acrylamide makes by the energetic ion radiation, is benchmark in the gross weight of said composition, and the content range of this multipolymer is 0.01 to 15% (weight).
2, according to the method for claim 1, under enough pressure, be injected into the rock stratum that said composition is mentioned to break.
3, according to the method for claim 1, the temperature of the rock stratum of being mentioned is minimum to be 170 °F.
4, according to the method for claim 1, the concentration of the acid of being mentioned is 15 to 28%(weight).
5, according to the method for claim 1, after injection liquid crushes the rip current body, the composition of being mentioned is injected to carry out acid etch.
6, according to the method for claim 1, under mud acid treatment condition, carry out the acid treatment of being mentioned.
7, according to the method for claim 1, an acid of being mentioned and a propping agent are shared.
8,, use a kind of rare gas element to increase the energy of the composition of being injected according to the method for claim 1.
9, according to the composition of claim 1, the composition of being mentioned is by the water of being mentioned substantially, and sour and said multipolymer is formed.
10, according to the method for claim 1, the multipolymer of being mentioned comprises 50-90%(weight) said 2-acrylamide-2-methyl propane sulfonic acid sodium and about 30%(weight) said acrylamide.
11, according to the method for claim 1, the multipolymer of being mentioned comprises about 70%(weight) said 2-acrylamide-2-methyl propane sulfonic acid sodium and about 30%(weight) said acrylamide.
12, according to the method for claim 1, the acid of being mentioned is (1) HF that produces on the spot and the composition of HCl or (2) a kind of organic acid and HCl.
13, according to the method for claim 1, be benchmark with the gross weight of the composition mentioned, the amount of the multipolymer of being mentioned is 0.1 to 3%(weight), and be benchmark with the acid mentioned and the gross weight of water, the concentration of the acid of being mentioned is 15 to 28%(weight).
14, the acid of mentioning according to the process of claim 1 wherein is hydrochloric acid.
15, the acid thickening composition of mentioning according to the process of claim 1 wherein also comprises a whipping agent.
16, according to the method for claim 15, wherein the whipping agent of being mentioned is nitrogen or carbonic acid gas and a kind of tensio-active agent.
17, according to the process of claim 1 wherein that the cold of shelves nurse fervent in the name of a river in Anhui Province gnaws ∈ numbness, 000 to 200,000 rad (rads), total radiation dosage is for being 1000 to 30,000 rads.
18, the radiation of mentioning according to the process of claim 1 wherein is to carry out in the pH value is about 2 to 12 the aqueous solution, and this solution contains 10-40%(weight) monomer mixture mentioned, this solution also comprises 3%(weight at least) a kind of salt, this salt is selected from vitriolate of tartar, Repone K, Potassium monofluoride, sal enixum, Tripotassium phosphate, Rhodiaphos DKP, potassium dihydrogen phosphate, sodium sulfate, sodium pyrosulfate, sodium-chlor, tertiary sodium phosphate, Di-Sodium Phosphate, monosodium phosphate, Lithium Sulphate, lithium hydrogen sulfate, lithium chloride, ammonium sulfate, monoammonium sulfate, ammonium chloride, triammonium phosphate, diammonium phosphate, monoammonium phosphate, Neutral ammonium fluoride, or their mixture, if when water-soluble salt is ammonium salt, pH value of water solution is about 7 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87106785 CN1034376A (en) | 1987-09-09 | 1987-10-05 | Acid thickening composition prepares the AMPS/Am multipolymer through radiation |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP87113190A EP0306546A1 (en) | 1987-09-09 | 1987-09-09 | Irradiation produced AMPS/Am copolymers in thickened acid compositions |
| CN 87106785 CN1034376A (en) | 1987-09-09 | 1987-10-05 | Acid thickening composition prepares the AMPS/Am multipolymer through radiation |
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| Publication Number | Publication Date |
|---|---|
| CN1034376A true CN1034376A (en) | 1989-08-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87106785 Pending CN1034376A (en) | 1987-09-09 | 1987-10-05 | Acid thickening composition prepares the AMPS/Am multipolymer through radiation |
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| CN (1) | CN1034376A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775551A (en) * | 2011-05-13 | 2012-11-14 | 中国石油化工股份有限公司 | Random copolymer, its preparation method and application |
| CN114810020A (en) * | 2021-01-19 | 2022-07-29 | 中国石油化工股份有限公司 | Fracturing method for uniformly extending multiple clusters of cracks and application |
-
1987
- 1987-10-05 CN CN 87106785 patent/CN1034376A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775551A (en) * | 2011-05-13 | 2012-11-14 | 中国石油化工股份有限公司 | Random copolymer, its preparation method and application |
| CN102775551B (en) * | 2011-05-13 | 2014-04-02 | 中国石油化工股份有限公司 | Random copolymer, preparation method and application thereof |
| CN114810020A (en) * | 2021-01-19 | 2022-07-29 | 中国石油化工股份有限公司 | Fracturing method for uniformly extending multiple clusters of cracks and application |
| CN114810020B (en) * | 2021-01-19 | 2024-06-11 | 中国石油化工股份有限公司 | Fracturing method for uniformly extending multi-cluster cracks and application |
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