CN1252426A - Oil Well water plugging agent of surface-modifying asphalt - Google Patents
Oil Well water plugging agent of surface-modifying asphalt Download PDFInfo
- Publication number
- CN1252426A CN1252426A CN 99123221 CN99123221A CN1252426A CN 1252426 A CN1252426 A CN 1252426A CN 99123221 CN99123221 CN 99123221 CN 99123221 A CN99123221 A CN 99123221A CN 1252426 A CN1252426 A CN 1252426A
- Authority
- CN
- China
- Prior art keywords
- water
- pitch
- oil
- agent
- plugging agent
- 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.)
- Pending
Links
Abstract
The present invention relates to the application of organic high molecular compound in petroleum exploitation. By means of mechanical mixing with surfactant or surface sulfonating reaction, the hydrophobic asphalt is processed into water-soluble hydrophilic selective water-base water plugging agent. The product has an oil dissolving rate over 60%. It has a cost lower than available oil-soluble resin solution or emulsion, selectivity superior to available polymer gel, active condensed oil and similar water plugging agent. The surface sulfnoated asphalt has a sulfonating rate of 1-48%. The surface-modified asphalt is added directly to fresh water, sea water or salt water with the added amount of 4-40%.
Description
The present invention relates to a kind ofly, belong to the application of organic high molecular compound in oil development by pitch being carried out the water base plugging agent that surface modification processing is made.
After the production of hydrocarbons of a bite oil well through one period, tend to out water problems, promptly the liquid overwhelming majority of output is a water.This can make the pump efficiency of well on the beam reduce, and quickens the corrosion and the fouling of equipment such as pipeline, increases the burden of dehydrating of crude oil and sewage disposal, thereby seriously reduces the economic benefit of oil-field development.
The water of oil well output, its source comprise injection water, Bian Shui, Di Shui, levels water and interbedded water.The profile control of water injection well often can only alleviate and inject water from the oil well output, and can reduce the output that comprises the various water that inject water from oilwell water shutoff.
The method of oilwell water shutoff is selectively with nonselective.The selective blocking water law can a shutoff stratum the water outlet duct, the fuel-displaced duct of not shutoff is specially adapted to stop the output of injecting water, Bian Shui and end water substantially; Non-selective water blockoff then the water outlet duct on one section stratum and the shutoff simultaneously of fuel-displaced duct, only is applicable to the output that stops levels water and interbedded water.
Selective water shutoff agent is that water or oil content are water base plugging agent and oil-base water shutoff agent by its external phase.Oil-base water shutoff agent mainly contains polyurethane(s), active viscous crude, halogenated silanes and oil base cement etc., and there is bigger interfacial tension in the intersection of they and water, so they are not easy to enter the water outlet duct, but enters fuel-displaced duct easily.Therefore, oil-base water shutoff agent is the cost height not only, and water plugging effect is difficult to guarantee, also may stop up fuel-displaced duct sometimes.The water base plugging agent of existing selectivity comprises following four classes: a. water-soluble polymers with and the gel that forms with suitable linking agent, for example Zirconium gel water sealing agent introduced of Chinese patent CN1016650 (application number 86108877); B. water-based foam is met crude oil meeting froth breaking, and by the Jamin effect shutoff water outlet duct of bubble, but validity period is shorter; C. soap class, water-soluble silicate etc. such as sodium abietate can form precipitation with calcium, the magnesium ion in the local water and play plugging function; D. suspension or the milk sap of forming with oil-soluble resin and water (USP4352396,1982), or with the solution of polar organic solvent composition, for example alcoholic solution of rosin dimerization thing (USP2946383,1960).More than the water base plugging agent of first three class selectivity can not be dissolved by crude oil, also be difficult to de-plugging voluntarily even enter fuel-displaced duct on a small quantity; The water base plugging agent of above-mentioned the 4th class selectivity can preferentially enter the water outlet duct, and the part that enters fuel-displaced duct on a small quantity can be by de-plugging voluntarily after the crude oil dissolving, yet its cost is higher.
More than to the document of the commentary institute reference of prior art, except that providing three pieces of the patent No., main is " chemical agent for oil recovery " (press of University of Petroleum, 1997) of writing with reference to Zhao Fulin.
The basal component of pitch class material is bituminous matter and colloid, belong to the condensed ring unsaturated hydrocarbons is the organic polymer of main composition, in crude oil, can be dissolved into one molecule or be dispersed into fine particle, in water, then do not disperse, do not dissolve, therefore have the feasibility of optionally stopping up the water outlet duct and not stopping up fuel-displaced duct.But the pitch particle surface is hydrophobic, need carry out processing modifiedly to it, and it can be scattered in the water uniformly and stably by water-wet.Such technology has obtained Application and Development in other field, for example aspect building as the emulsified bitumen of cold-construction waterproofing paint, the Pitch Water Slurry that aspect the thermal technology, acts as a fuel, aspect drilling fluid as anti-collapse dose, the sulfonated gilsonite of plugging agent etc.Essence of the present invention is next for being applied to after bituminous composition in other field disperseing of using and water and preparation method thereof is suitably adjusted in addition aspect the oilwell water shutoff.
The objective of the invention is pitch is carried out the surface working modification of appropriateness, its hydrophobicity is being changed into the hydrophilic while, significantly do not reduce its solvability or fine dispersiveness in crude oil, be processed into cheaply, the water base plugging agent of high selectivity.The approach that realizes this purpose has mechanical mixing and sulfonating surface method.
Here said mechanical mixing is to quote the method for preparing Pitch Water Slurry or emulsified bitumen in the prior art, comprises dry mix and wet mixing method.Dry mix is that powdered pitch and water-free substantially tensio-active agent are directly mixed in proportion.Wet mixing method is earlier surfactant dissolves wiring solution-forming in water, this solution and pitch is mixed again, and is ground to the fineness of needs.Tensio-active agent and bituminous mass ratio are 2～26: 100.General anion surfactant, cats product, amphoterics and nonionogenic tenside all can adopt for this law, for example: alkylsulfonate, alkylbenzene sulfonate, sulfonated petro-leum, alkyl naphthalene sulfonate, soap or its component, alkyl alcohol sulfuric ester sodium salt, halogenation alkylamine, tetraalkyl ammonium halide, halogenated alkyl pyridine, polyxyethylated alkylphenol, polyoxyethylated alkyl alcohol, Span class tensio-active agent, Tween class tensio-active agent, alkyl amino acid inner salt or ammonium acid inner salt, or the like.
Here said sulfonating surface reaction method is the novel method of the preparation water dispersible asphalt that proposes of the present invention, comprises acid sulfonation method and alkaline sulfonation method.Acid sulfonation method promptly chlorsulfonic acid, sulphur trioxide or/and sulfuric acid mixes with the solid bitumen of powder morphology is full and uniform, reacted 5～50 minutes at 30～90 ℃, add sodium hydroxide then or/and potassium hydroxide solution, being neutralized to pH is 7～9.The alkalescence sulfonation method was pitch to be scattered in to contain sodium hydroxide or/and in the potassium hydroxide solution, add sulphite again or/and lay particular stress on sulphite earlier, 50～150 ℃ of reactions 10～90 minutes.Better, the control sulfonation degree is between 1～18% between 2～20 for sulphonating agent (all by sulphur trioxide) and bituminous mass ratio.
Sulfonating surface method of the present invention is compared with existing pitch sulfonation technology possesses three advantages: the oily molten rate of a. product has improved, and the molten rate of sulfonated gilsonite product oil of prior art generally is lower than 50%, and the molten rate of product oil of the present invention is more than 60%; B. working method of the present invention does not have influence substantially for the bituminous softening temperature, and the distortion granule content of product is higher, and when the softening temperature of raw material was lower than well temperature, the product particle easy deformation entered in the interior water outlet duct of well; C. save solvent oil, reduced production cost, reduced three-waste pollution.
By above-mentioned wet method mechanically mixing or formed liquid or the semi-fluid composition (suspension or milk sap) that contains many water of sulfonating surface reaction treatment pitch, can directly add water and be made into the use of water blockoff fluid, make powder-like product after also can and pulverizing and use through super-dry.Dosage is generally 4～40% by the butt conversion; Used water can be fresh water, salt solution or seawater.
Below further illustrate implementation procedure of the present invention with example, but be not to realize various conditions of the present invention in order to restriction.
Example 1
Being that 98～102 ℃ pitch is levigate with softening temperature takes by weighing 80 grams to all by 80 mesh sieves (aperture 0.177mm), is added on to contain 4.8 and restrain in the 100 ml water solution of Sodium dodecylbenzene sulfonatees, and stirring becomes semi-fluid composition, remembers and makes EG-1.Get 4.5 gram EG-1 and be added in 50 milliliters of diesel oil, be heated to 60 ℃, stirred 5 minutes, with No. 102 qualitative filter papers suction filtration in B, stay after the part drying on the filter paper quality and be 0.61 and restrain, account for 29% of butt composition, calculating oily molten rate thus is 71%.Other get 90 the gram EG-1 add in 800 ml distilled waters, stirred 5 minutes, form homodisperse suspension, with No. 102 qualitative filter papers suction filtration in B, stay that quality is 39.4 grams after the part drying on the filter paper, account for 93% of butt composition, promptly being out of shape granule content is 93%.
" protection reservoir technology " (the petroleum industry press of writing with reference to Zhang Shaohuai, Asia, Luoping etc.; 1993) the relevant experimental technique of Jie Shaoing; with (110 ℃ in the water base water blockoff fluid shutoff rock core that is added with EG-1 (dosage be 15%, in butt) and salt (30 grams per liter); 2MPa; 1 hour), with the rate of permeation of salt solution (concentration is 30 grams per liters) or kerosene mensuration rock core.Two sections each rock core are designated as side a and b respectively, and the A end is represented the stratum around the oil well, and the B end is represented the hole wall of the borehole wall or perforation; The rate of permeation of surveying the rate of permeation of water and oil all is from the A end injection liquid of exerting pressure, and from B termination holding liquid and measure its flow velocity, this moment, the B terminal pressure equated with atmospheric pressure; Add the pressure injection water blockoff fluid of 2MPa during shutoff from the B end, kept this pressure one hour, the pressure source of A end is closed, but does not communicate with atmosphere.
Get 18 gram EG-1 78～82 ℃ of bakings 6 hours, get 8.6 gram dry powder, this dry powder is added in the water, and stirring a little just becomes homodisperse suspension.
Example 2
Get the powdered asphalt raw material identical 50 grams with example 1, the limit is stirred this powdered asphalt limit and is sprayed sulfuric acid (chemically pure reagent) with little atomizer, sprayed 8 gram sulfuric acid in three minutes, continued stirring reaction 10 minutes, each particle of bituminous is all contacted with sulfuric acid, adding contains 28 milliliters of the aqueous solution of sodium hydroxide 4.2 grams and stirs then, and the said composition note is made EG-2.
Example 3
Get the powdered asphalt raw material identical 50 grams with example 1, with the 80 ml water solution thorough mixing that contain 2 gram sodium hydroxide, be heated to 95 ℃, slowly be sprinkled into powdery S-WAT (chemically pure reagent) while stirring, added 5 grams, continued stirring reaction again 15 minutes in 10 minutes, use the B suction filtration, 78～80 ℃ of oven dry, be ground into powdery, the said composition note is made EG-3.
Comparative Examples
Get powdered polypropylene acid amides (viscosity-average molecular weight 4.8 * 10
6, degree of hydrolysis 12%) and 3.5 grams are added in 350 ml distilled waters, fully after the dissolving, with salt acid for adjusting pH value to 5, add 20 milliliters of chromium nitrate solutions (concentration is 0.04 mol) while stirring, and the resulting composition note is made EG-4.
Measure EG-2, EG-3 and the distortion granule content of three kinds of samples of EG-4, oily molten rate and rock core sealing ratiod by the method identical with example 1, the method of pressing regulation among the oil and gas industry standard SY/Z Q014-89 " drilling fluid sulfonated gilsonite FT-1 " is measured the sulfonation degree of sulfonating surface asphalt sample, the results are shown in Table 1 and table 2.
The physical property of table 1 sample
| Sample | Distortion granule content/% | Softening temperature ℃ | The molten rate % of oil | Sulfonation degree % |
| ??EG-1 | ????93 | ????99 | ????71 | |
| ??EG-2 | ????90 | ????102 | ????66 | ????8 |
| ??EG-3 | ????91 | ????104 | ????67 | ????5 |
| ??EG-4 | ????0 |
In table 2, the 3rd, 14,22 and No. 32 rock core is shutoff under the condition of not injecting oil in rock core, and obviously three samples and the comparative sample by the present invention preparation has good water plugging effect equally; 11st, 14,26 and No. 37 rock cores are measured oily rate of permeation only contain irreducible water in rock core after and are just carried out shutoff injecting oil in rock core, refill oil then and reach more than ten times of volume of voids, record oily rate of permeation and be subjected to the injury of plugging agent of the present invention very little, and be subjected to the injury of comparative sample more remarkable.No. 8 rock cores carry out shutoff, so do not survey the preceding oily rate of permeation of shutoff inject oily irreducible water saturation, the oily injection oil that just do not stop of not reaching when flowing of rock core reaches stable state as yet; After this shutoff before injecting oil of No. 20 rock cores is once injected oil and is measured after the oily rate of permeation shutoff again for the second time, and the sealing ratiod of water is reached 87%, only is 3% to the sealing ratiod of oil.
The data declaration of table 2 novel plugging agent of the present invention has comparatively ideal selectivity.
The rock core sealing ratiod of table 2 sample 1.
1. EG-1, EG-2, EG-3 dosage in the water blockoff fluid is 150 grams per liters (butt); The contents on dry basis of EG-4 is 25 grams per liters
| Stone heart numbering | Sample | The water rate of permeation, μ m 2 | Oil saturation before the shutoff, % | The oil rate of permeation, μ m 2 | ||||
| Before the shutoff | After the shutoff | Sealing ratiod % | Before the shutoff | After the shutoff | Sealing ratiod % | |||
| ????3 | ??EX-1 | ??0.917 | ??0.085 | ????91 | ????0 | ????/ | ????/ | ????/ |
| ????8 | ??EX-1 | ??1.048 | ??0.120 | ????88.5 | ????40 | ????/ | ??0.736 | ????/ |
| ????11 | ??EX-1 | ??0.593 | ????/ | ????/ | ????0.72 | ??0.406 | ??0.394 | ????3 |
| ????14 | ??EX-2 | ??0.629 | ??0.044 | ????93 | ????0 | ????/ | ????/ | ????/ |
| ????16 | ??EX-2 | ??0.476 | ????/ | ????/ | ????74 | ??0.337 | ??0.324 | ????4 |
| ????20 | ??EX-2 | ??1.284 | ??0.162 | ????87 | ????0 | ??0.725 | ??0.703 | ????3 |
| ????22 | ??EX-3 | ??0.547 | ??0.021 | ????96 | ????0 | ????/ | ????/ | ????/ |
| ????26 | ??EX-3 | ??0.861 | ????/ | ????/ | ????70 | ??0.588 | ??0.547 | ????7 |
| ????32 | ??EX-4 | ??0.930 | ??0.874 | ????94 | ????0 | ????/ | ????/ | ????/ |
| ????37 | ??EX-4 | ??0.648 | ????/ | ????/ | ????73 | ??0.492 | ??0.367 | ????26 |
Claims (3)
1, a kind of water base plugging agent that is used for stopping up high moisture duct in the oil gas well and does not reduce oil gas duct output capacity is characterized in that with surface modification pitch being the main component of plugging action, is external phase with fresh water, seawater or salt solution; Surface modification pitch dosage calculates by butt and is generally 4～40%.
2, a kind of preparation surface modification bituminous method according to claim 1 is characterized in that carrying out the sulfonating surface reaction with particulate solid pitch and sulphonating agent, connects sulfonate radical on the part molecule on pitch particle surface, and sulfonation degree is between 1～18%; Used sulphonating agent is one among sulfuric acid, sulphur trioxide, these three kinds of materials of chlorsulfonic acid, two kind, or sulphite, lays particular stress on one among the sulphite, two kind.
3, the water base plugging agent of surface modification pitch according to claim 1, used surface modification pitch can be used as sulfonating surface method preparation as described in the claim 2, also can be with the composition in tensio-active agent and composite easy dispersion of pitch and the water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99123221 CN1252426A (en) | 1999-11-01 | 1999-11-01 | Oil Well water plugging agent of surface-modifying asphalt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99123221 CN1252426A (en) | 1999-11-01 | 1999-11-01 | Oil Well water plugging agent of surface-modifying asphalt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1252426A true CN1252426A (en) | 2000-05-10 |
Family
ID=5282836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99123221 Pending CN1252426A (en) | 1999-11-01 | 1999-11-01 | Oil Well water plugging agent of surface-modifying asphalt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1252426A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1327106C (en) * | 2005-08-23 | 2007-07-18 | 孙广森 | Chemical regulator for stratified waterflooding in water injection well and stratified water amount regulating construction method |
| CN101948680A (en) * | 2010-09-21 | 2011-01-19 | 大庆油田有限责任公司 | Bitumen particle profile control agent and preparation method thereof |
| CN102786919A (en) * | 2012-07-12 | 2012-11-21 | 中国石油天然气股份有限公司 | Emulsified asphalt profile control agent |
| US9127542B2 (en) | 2014-01-28 | 2015-09-08 | Lawrence O. Price | Subterranean well treatment process |
| CN105038747A (en) * | 2015-06-19 | 2015-11-11 | 大庆市天曼石油化工有限公司 | Chemical reactive modified asphalt profile modifying/water plugging agent and preparation method and application of profile modifying/water plugging agent |
-
1999
- 1999-11-01 CN CN 99123221 patent/CN1252426A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1327106C (en) * | 2005-08-23 | 2007-07-18 | 孙广森 | Chemical regulator for stratified waterflooding in water injection well and stratified water amount regulating construction method |
| CN101948680A (en) * | 2010-09-21 | 2011-01-19 | 大庆油田有限责任公司 | Bitumen particle profile control agent and preparation method thereof |
| CN101948680B (en) * | 2010-09-21 | 2013-06-19 | 大庆油田有限责任公司 | Preparation method of bitumen particle profile control agent |
| CN102786919A (en) * | 2012-07-12 | 2012-11-21 | 中国石油天然气股份有限公司 | Emulsified asphalt profile control agent |
| CN102786919B (en) * | 2012-07-12 | 2014-01-15 | 中国石油天然气股份有限公司 | Emulsified asphalt profile control agent |
| US9127542B2 (en) | 2014-01-28 | 2015-09-08 | Lawrence O. Price | Subterranean well treatment process |
| US9631134B2 (en) | 2014-01-28 | 2017-04-25 | Lawrence O. Price | Subterranean well treatment system |
| CN105038747A (en) * | 2015-06-19 | 2015-11-11 | 大庆市天曼石油化工有限公司 | Chemical reactive modified asphalt profile modifying/water plugging agent and preparation method and application of profile modifying/water plugging agent |
| CN105038747B (en) * | 2015-06-19 | 2017-09-22 | 大庆市天曼石油化工有限公司 | One kind chemical reaction modified pitch profile-controlling and plugging agent and preparation method thereof and purposes |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2009352654B2 (en) | Process for drying fine tailings or colloidal fluids | |
| CA2678818C (en) | Process for drying oil sand mature fine tailings | |
| US5110443A (en) | Converting heavy hydrocarbons into lighter hydrocarbons using ultrasonic reactor | |
| EP1648599B1 (en) | Apparatus and method for hydrating a gel for use in a subterranean well | |
| US5083613A (en) | Process for producing bitumen | |
| US20090011960A1 (en) | Drilling fluid composition comprising hydrophobically associating polymers and methods of use thereof | |
| US5283001A (en) | Process for preparing a water continuous emulsion from heavy crude fraction | |
| US20150111792A1 (en) | Spray dried emulsifier compositions, methods for their preparation, and their use in oil-based drilling fluid compositions | |
| WO1988000584A1 (en) | Organophilic polyphenolic acid adducts | |
| US3780806A (en) | Inverted mixed latex for water flooding | |
| CN1252426A (en) | Oil Well water plugging agent of surface-modifying asphalt | |
| CN101084166A (en) | Copolymer composition for particle aggregation | |
| US4964999A (en) | Process for forming stable emulsions of water soluble polysaccharides in hydrocarbon liquids | |
| EP0363300A1 (en) | Process for preparing an oil in an aqueous phase emulsion | |
| CN101240044A (en) | Method for preparing cross-linking polymer clew with bimodal distribution grain diameter | |
| EP0102827A2 (en) | A shear thickening composition with polyacrylic acid | |
| US4541965A (en) | Dispersants for aqueous slurries | |
| CN109749793B (en) | Method for preparing asphalt-based fuel oil | |
| CN1080854C (en) | Process for moving highly viscous petroleum products | |
| CA3092823A1 (en) | Binder and method of forming the binder for granulation, aggregation and structuring of mineral solids | |
| US2789097A (en) | Bituminous emulsions and process for making same | |
| CN109913190A (en) | A kind of preparation method for removing downhole polymer micelle cleaning agent | |
| DE2652045A1 (en) | Consolidation of loose oil-bearing formations - by injection of aq. dispersions of hardenable liquid resins | |
| WO2016159834A1 (en) | Liquid for extracting low-pressure gas and oil | |
| RU2365611C1 (en) | Composition of polysaccharide gel for damping and washing of wells and method of its preparing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C57 | Notification of unclear or unknown address | ||
| DD01 | Delivery of document by public notice |
Addressee: Ding Rui Document name: Deemed as a notice of withdrawal |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |