CN1308413C - Oil well acidizing fluid containing organic phosphinic acid - Google Patents
Oil well acidizing fluid containing organic phosphinic acid Download PDFInfo
- Publication number
- CN1308413C CN1308413C CNB2004100527251A CN200410052725A CN1308413C CN 1308413 C CN1308413 C CN 1308413C CN B2004100527251 A CNB2004100527251 A CN B2004100527251A CN 200410052725 A CN200410052725 A CN 200410052725A CN 1308413 C CN1308413 C CN 1308413C
- Authority
- CN
- China
- Prior art keywords
- acid
- oil well
- fluid
- oil
- acidizing fluid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention relates to an oil well acidizing fluid which contains organic phosphinic acid. The oil well acidizing fluid mainly solves the problem that the previous technology does not relate to acidizing effect data, or the problems of high corrosion rate of acid fluid for clay soil, low corrosion rate of the acid fluid for quartz, short operating range of the acid fluid, shallow acidizing depth and the like existing in the prior art. The oil well acidizing fluid has the technical scheme that the oil well acidizing fluid adopts acidizing fluid which uses amino trimethylene phosphonic as a main ingredient so that the problems are better solved. The oil well acidizing fluid can be used in the industrial exploitation of raw oil.
Description
Technical field
The present invention relates to a kind of oil well acidation liquid that contains organic phospho acid, the particularly acidizing fluid of using about acid treatment of oil formation in the Oil extraction that contains organic phospho acid.
Background technology
Crude oil generally all is imbedded in underground very dark oil reservoir the inside, and these oil reservoir great majority all are made up of sedimentogeneous rock.Sedimentogeneous rock mainly contains two kinds and has form, i.e. sandstone and limestone.Crude oil in the sandstone oil reservoir mainly is to be stored in the hole or slit of rock; Crude oil in the limestone oil reservoir mainly is stored in the crack or solution cavity of rock.With regard to world wide, the sandstone oil reservoir be crude oil mainly contain form, China mainly contains based on sandstone, the oil reservoir that people are usually said mainly also is meant sandstone (sandstone) oil reservoir.
Sandstone is by rock particles (main component sio
2), cementing matter and hole three parts form.The hole of rock is not only the container of oil storage, also is the passage of fluid flow simultaneously, and the hole major part in the rock is interconnected, but disconnected stagnant pore is also arranged.The hole of rock is many more, big more, and the connectivity between them is just good more, and the flow condition of oil, gas, water or other fluid is just good more.Have this character just because of reservoir rock, crude oil could flow to the shaft bottom at a distance from oil reservoir.
With regard to the porosity or the rate of permeation of reservoir rock, in the difference oil recovery phase in different oil district or same oil district, its numerical value differs greatly.The oil reservoir of high porosity or high permeability can fuel-displaced in large quantities or water filling, and low permeability layer is then less fuel-displaced or not fuel-displaced, and water filling is few or annotate and do not intake, and this recovery ratio of just giving the stable high yield in oil field and improving crude oil brings huge difficulty.
Oil production through more than 100 years, most of in the world at present oil fields have all entered the exploitation middle and later periods, after oil reservoir has experienced primary oil recovery and secondary oil recovery, because the decline of blowhole rate and obstruction still have the petroleum-in-place above 60% to remain in the blowhole of oil reservoir.Because oil belongs to Nonrenewable resources, so how to satisfy under the prerequisite of economic benefit, fully the recover petroleum resource becomes problem eternal in the oilfield development process.In order to recover or improve the rate of permeation of oil reservoir, the oil field generally adopts acid solution that oil reservoir is handled with the raising oil recovery factor both at home and abroad, thereby the acidifying technology has become at present oil well production increasing both at home and abroad, one of important measures of intensified injection of wells, yet, adopt conventional acidizing fluid, but exist acid solution clay dissolution rate height, low to the quartz dissolution rate, be confined to de-plugging, acid solution operating distance is short, and shortcomings such as acidifying depth as shallow can not reach effective transformation effect; Conventional acid is to the excessive corrosion of clay cement, and the destructible ma causes near wellbore formation to cave in, and initiation is shaked out, impact effect; The conventional acid corrosion is stronger, and is more serious to corrosion such as oil, string of casing.Need work out a kind of novel acid solution and solve above production problem.
The gel acid that a kind of acidifying strata is used is disclosed among the Chinese patent literature CN1061033A.This gel acid is only applicable to carbonate strata acidification of oil gas well or fracture acidizing, and concrete component comprises hydrochloric acid, is the hcl acidifying inhibiter of main component with aldehyde ketone amine condenses, tensio-active agent, water-soluble acidproof positively charged ion and water.Do not relate to sandstone formation acidifying problem in the document.
A kind of acidifying corrosion inhibitor for oil well and preparation method thereof is disclosed among the Chinese patent literature CN1163301A.It is to be raw material by naphthenic acid imidazoline diamide Soxylat A 25-7, through the hydrochloric acid quaterisation, obtains a kind of water-soluble fabulous naphthenic acid imidazoline diamide Soxylat A 25-7 quaternary ammonium salt cationic acidification corrosion inhibitor after the dilution.Unexposed acidizing effect data in the document.
Summary of the invention
Technical problem to be solved by this invention is not relate to the acidizing effect data in the conventional art or exist acid solution to clay dissolution rate height in existing use technology, low to the quartz dissolution rate, make acid solution operating distance short, problems such as acidifying depth as shallow provide a kind of new oil well acidation liquid that contains organic phospho acid.This acidizing fluid has the clay dissolution rate low, and to quartz dissolution rate height, the acidification time is long, the characteristics that the acidifying radius is big.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of oil well acidation liquid that contains organic phospho acid comprises following component by weight percentage:
A) 84～93% water;
B) 2～6% Amino Trimethylene Phosphonic Acid;
C) 1～10% HF.
In the technique scheme, the consumption preferable range of HF is 1～6% by weight percentage.
Being prepared as follows of the Amino Trimethylene Phosphonic Acid of using among the present invention:
With formaldehyde, bicarbonate of ammonia, three kinds of raw material one-step synthesis of phosphorus trichloride, its reaction equation is as follows:
Synthetic summary:
Thermometer is being housed, reflux condensate device, whipping appts, carbonic acid gas, the hydrogen chloride tail gas absorption unit is in the four-hole boiling flask of phosphorus trichloride Dropping feeder.At room temperature earlier bicarbonate of ammonia and formaldehyde are added in the bottle, stir, there is this moment a large amount of carbon dioxides to produce, begin to drip phosphorus trichloride subsequently, produce a large amount of HCl gases, exothermic phenomenon occurs, control reaction temperature is being carried out below 40 ℃, dripping the phosphorus trichloride speed control was advisable at about 4～6 hours, phosphorus trichloride dropwises and follow-up continuing is warming up to 50～60 ℃, and constant temperature 1 hour continues to be warming up to 70～80 ℃ again, constant temperature 1 hour, be warmed up to 110 ℃ at last, constant temperature 0.5 hour its objective is in order to react thorough, emit a large amount of HCl gases, and reclaim.
The present invention contains the preparation method of the oil well acidation liquid of organic phospho acid: the acidizing fluid component need only be got final product by institute's expense wiring solution-forming.
Among the present invention since the oil well acidation liquid that contains organic phospho acid to the corrosion ability of quartz greater than corrosion ability to clay, really played the matrix acidifying effect, and organic phospho acid is a polyprotonic acid, can fractional ionization go out hydrogen ion, the energy long duration of action enlarges the effect that the acidifying radius reaches deep acidizing in the stratum, has performances such as slow, low injury, antiscale, its corrosion rate to clay can be less than 25%, to rock (SiO
2) the corrosion rate can reach more than 30%, for oil well production increasing, intensified injection of wells, raising water flooding later stage surplus oil tap the latent power and difficultly adopt reserves, the low permeability layer producing capacity provides strong technical support, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Respectively Amino Trimethylene Phosphonic Acid is made into weight percent concentration and is 7%, 10% and 15% and 30% acidizing fluid, the temperature of acidification reaction system is 80 ℃, and the reaction times is 4 hours, respectively to SiO
2Rock sample (2877 meters of well depth) carries out the test of corrosion rate, and its test-results is as follows:
| Organic phospho acid | Rock sample weight (gram) | Acidizing fluid concentration % (weight) | Acidizing fluid add-on (milliliter) | Rock sample corrosion rate |
| Amino Trimethylene Phosphonic Acid | 5 | 7 | 30 | 12.86 |
| Amino Trimethylene Phosphonic Acid | 5 | 10 | 30 | 34.36 |
| Amino Trimethylene Phosphonic Acid | 5 | 15 | 30 | 35.67 |
| Amino Trimethylene Phosphonic Acid | 5 | 30 | 30 | 51.4 |
[comparative example 1]
Mud acid is changed in acid among the embodiment 1, and its weight is composed as follows: 15%HCl+3%HF, and all the other conditions are constant, and its rock sample corrosion rate is 45.16%.
[embodiment 2]
Organic phospho acid is made into weight concentration is: the oil well acidation liquid of 6% Amino Trimethylene Phosphonic Acid+4.5%HF, test by condition and the step of embodiment 1, and its result is as follows: to quartzy (SiO
2) rock sample corrosion rate is 32.70%, is 15.11% to the clay dissolution rate.
[embodiment 3]
Organic phospho acid is made into weight concentration is: 6% Amino Trimethylene Phosphonic Acid+* acidizing fluid of %HF, test by condition and the step of embodiment 1, its result is as follows:
[embodiment 4]
Organic phospho acid is made into weight concentration is: the acidizing fluid of 4% Amino Trimethylene Phosphonic Acid+5%HF, test by condition and the step of embodiment 1, and its result is as follows: quartzy corrosion rate is 33.07%, and the corrosion rate of clay is 24.93%.
[embodiment 5]
Organic phospho acid is made into weight concentration is: the acidizing fluid of 2% Amino Trimethylene Phosphonic Acid+5%HF, carry out erodible test by condition and the step of embodiment 1, and its result is as follows: quartzy corrosion rate is 31.94%, and the corrosion rate of clay is 21.36%.
[embodiment 6]
Organic phospho acid is made into weight concentration is: the acidizing fluid that 5% Amino Trimethylene Phosphonic Acid+3.0%HCl+1.0%HF forms, carry out erodible test by condition and the step of embodiment 1, and just changing temperature is 60 ℃, its test-results is as follows:
| Souring temperature (℃) | Rock sample weight (gram) | Acidizing fluid add-on (milliliter) | Acidificatoin time (hour) | Corrosion rate (%) |
| 60 | 5.0 | 30 | 0.5 | 29.8 |
| 60 | 5.0 | 30 | 2.0 | 29.8 |
| 60 | 5.0 | 30 | 4.0 | 29.8 |
| 60 | 5.0 | 30 | 6.0 | 29.9 |
| 60 | 5.0 | 30 | 9.0 | 33.0 |
| 60 | 5.0 | 30 | 12.0 | 34.7 |
[comparative example 2]
Change the acid among the embodiment 6 into mud acid, its weight is composed as follows: 15%HCl+3%HF, and all the other conditions are constant, and its test-results is as follows:
| Souring temperature (℃) | Rock sample weight (gram) | Acidizing fluid add-on (milliliter) | Acidificatoin time (hour) | Corrosion rate (%) |
| 60 | 5.0 | 30 | 0.5 | 42 |
| 60 | 5.0 | 30 | 2.0 | 42 |
| 60 | 5.0 | 30 | 4.0 | 42 |
| 60 | 5.0 | 30 | 6.0 | 42 |
| 60 | 5.0 | 30 | 9.0 | 42 |
| 60 | 5.0 | 30 | 12.0 | 42 |
[embodiment 7]
Certain oilfield reservoir lithology is better, poor properties, ma quartz content height (content is 53～72%), conventional acidizing fluid is relatively poor at this area's effect, adopt the acidizing fluid corrosion ability stronger among the embodiment 6 to this stratum quartz, carry out the matrix transformation, obtained augmented injection effect preferably after the acidifying, average individual well daily water-injection rate is by 10.3 meters
3/ sky rises to 73.1 meters
3/ day, 62.8 meters of individual well augmented injections
3/ day, water injection intensity is by 0.507 meter
3/ day MPa rises to 5.060 meters
3/ day MPa, 215 days average effective phases, 38.3 meters of the former average daily output liquid of every mouthful of oil well of its correspondence
3, 3.2 tons of average day produce oils, average day production fluid is 46.8 meters after the acidifying
3, 5.2 tons of average day produce oils.
Claims (2)
1, a kind of oil well acidation liquid that contains organic phospho acid comprises following component by weight percentage:
A) 84～93% water;
B) 2～6% Amino Trimethylene Phosphonic Acid;
C) 1～10% HF.
2, according to the described oil well acidation liquid that contains organic phospho acid of claim 1, it is characterized in that the consumption of HF is 1～6% by weight percentage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100527251A CN1308413C (en) | 2004-07-12 | 2004-07-12 | Oil well acidizing fluid containing organic phosphinic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100527251A CN1308413C (en) | 2004-07-12 | 2004-07-12 | Oil well acidizing fluid containing organic phosphinic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1721496A CN1721496A (en) | 2006-01-18 |
| CN1308413C true CN1308413C (en) | 2007-04-04 |
Family
ID=35912111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100527251A Active CN1308413C (en) | 2004-07-12 | 2004-07-12 | Oil well acidizing fluid containing organic phosphinic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1308413C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104293325A (en) * | 2014-09-09 | 2015-01-21 | 中国石油集团渤海钻探工程有限公司 | Viscosity reducer for drilling fluid and preparation method thereof |
| CN105837749B (en) * | 2016-04-07 | 2018-01-05 | 西南石油大学 | A kind of retardant and a kind of retarded acid working solution |
| CN108219767B (en) * | 2016-12-14 | 2021-06-15 | 中国石油化工股份有限公司 | Offshore oilfield acidification yield increasing system and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1218846A (en) * | 1997-11-28 | 1999-06-09 | 中国石油化工总公司 | Composite corrosion-inhibiting antisludging agent for strong corrosive water |
| CN1487048A (en) * | 2003-07-22 | 2004-04-07 | 大庆油田有限责任公司 | Solid wax-resisting scale inhibitor for well |
-
2004
- 2004-07-12 CN CNB2004100527251A patent/CN1308413C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1218846A (en) * | 1997-11-28 | 1999-06-09 | 中国石油化工总公司 | Composite corrosion-inhibiting antisludging agent for strong corrosive water |
| CN1487048A (en) * | 2003-07-22 | 2004-04-07 | 大庆油田有限责任公司 | Solid wax-resisting scale inhibitor for well |
Non-Patent Citations (1)
| Title |
|---|
| 油田化学品开发应用现状及展望 续完 刘继德等，精细与专用化学品 1999 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1721496A (en) | 2006-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2885004A (en) | Treatment of wells | |
| CN101787864B (en) | Method for plugging water from oil reservoir fractured water logging oil well developed by injecting water into low-permeable reservoir stratum | |
| CN101747886B (en) | Fracturing fluid stock solution, full-filling preposition-free sand adding fracturing method and fracturing fluid cross-linking solution thereof | |
| CN107216866B (en) | A kind of method of Carbonate Reservoir seam dictyosome product acidfracturing treatment | |
| CN105089603A (en) | Reservoir modifying method through forming crack network by temporary plugging turning in cracks | |
| CN105089596A (en) | Hydraulic fracturing treatment method of an unconventional reservoir oil and gas well | |
| CN103502386A (en) | Thickened viscoelastic fluids and uses thereof | |
| CN109958426A (en) | A kind of fracturing process improving deep layer shale gas crack complexity | |
| CN108822819A (en) | A kind of super low percolation oilfield oil-water well combined removing plug by acid liquid | |
| CN105940080A (en) | Stimulation method and system for enhancing oil production | |
| CN1919963A (en) | Brine cement slurry adapted for salt hole air reserved storeroom | |
| CN105154056B (en) | A kind of anhydrous pressure break liquid and preparation method thereofs of LPG suitable for unconventional reservoir and application | |
| CN1081288C (en) | Steam chemical incoming-outcoming method for extracting superthick oil | |
| CN102382243B (en) | Amphiphilic polymer and application | |
| CN1308413C (en) | Oil well acidizing fluid containing organic phosphinic acid | |
| CN111100622A (en) | Clean fracturing fluid for deep coal-bed gas well and preparation method and application thereof | |
| CN102120930A (en) | Oil reservoir modification acid liquor and oil production method by using same | |
| CN108690599A (en) | A kind of corrosion acidifying solution and preparation method thereof for clay mineral | |
| CN103967466B (en) | PGZ closes down in oil field well restore exploitation and production-increasing technique | |
| CN1303183C (en) | Acidizing fluid for oil well | |
| CN100352884C (en) | Oil well acidification composition | |
| CN1329476C (en) | Acidification composition for oil well | |
| Felber | Selected US department of energy’s EOR technology applications | |
| CN1285701C (en) | Oil well acidizing fluid containing organic phosphono and sulfonic acid | |
| Wang et al. | Study of new ultra-temperature polymer fracturing fluid material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |