CN104098738B - A kind of low-molecular-weight clay stabilizer preparation method - Google Patents
A kind of low-molecular-weight clay stabilizer preparation method Download PDFInfo
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Abstract
The invention belongs to technical field of oil production engineering, one low-molecular weight polymer clay stabilizer preparation method of the present invention is provided, this clay stabilizer is as raw material with the ammonium salt containing carbon carbon and 2 acrylamidos 2 methyl propane sulfonic acid (AMPS), under conditions of initiator exists, polymerization is prepared from aqueous, and polymer number-average molecular weight is less than 50,000.This polymer stabilizer introduces sulfonic acid group, adds water solublity and the heat-resisting property of polymer.It can form multipoint adsorption with multiple clay particles in water simultaneously, after absorption, forms one layer of absorption protecting film on the surface of clay particle, prevents expansion and the migration of clay particle；This stabilizer has the performance of high temperature resistance, and heat-resisting property reaches more than 120 DEG C.
Description
Technical field
The invention belongs to technical field of oil production engineering, relate to a kind of low-molecular-weight clay stabilizer preparation method.
Background technology
Clay mineral is widely present in oil reservoir, and the oil reservoir in the whole world 97% contains clay mineral the most to some extent.Generally when oil reservoir argillaceous 5%～20%, then it is assumed that it is the oil reservoir that clay content is higher.If improper measures on stream, will result in swelling clay mineral, disperse and migrate, thus block the throat of formation pore structure, reduce the permeability on stratum, produce formation damage.In order to protect the permeability of hydrocarbon formations, it is necessary to use the clay mineral in chemical treatments good ground.The inorganic agent that can prevent swelling clay mineral is referred to as anti-soil adhesion extender (expansion-resisting agent).The inorganic agent that can prevent small bits of clay from migrating is referred to as anti-soil adhesion fine migration agent (anti-migration agent), both belongs to clay stabilizer.
Clay stabilizer substantially can be divided into three phases according to different structures and the development in this respect of the difference of chemical drugs that used: in the 1. later stage fifties to the sixties, mainly stablizes clay with inorganic salts；2. clay is stablized with inorganic many nuclear polymers and cationic surfactant the seventies；3. research and the experiment stablizing clay with cationic organic polymer has mainly been carried out after the eighties.
Inorganic salt is non-permanent clay stabilizing chemical, and in oil recovery process, the sodium ion in formation water will replace these ions again, and the effect stablizing clay when its concentration is reduced to a certain degree will disappear.This kind of clay stabilizer can not produce multipoint adsorption, therefore to preventing clay movement DeGrain, is used primarily in the operations such as drilling well, pressure break, acidifying.
Application inorganic cationic polymer clay stabilizers such as hydroxy Al, iron carbonyl, zirconyl hydroxy again after inorganic salt, the mechanism of its stable clay is that the metal ion of more than trivalent and trivalent is (such as A13+、Cr3+、Zr3+、Zr4+、Ti4+Deng) dissociate polynuclear hydroxy bridge complex ion under certain condition, this complex ion has the highest positive electricity price and structure is similar to clay, and energy adsorbed close, on surface of clay, reduces the elecrtonegativity of surface of clay, migrate with efficiently controlling clay swell and microgranule, large-area reservoir can be processed.The effect duration that inorganic cationic polymer stablizes clay is longer than inorganic salt, but acid resistance is poor, it is impossible to for the sandstone formation that carbonate content is high.Best inorganic cationic polymer is hydroxy Al and zirconyl hydroxy.
Cationic surfactant, owing to can dissociate the cation of surface activity in water, can adsorb on the surface of clay particle, neutralizes the negative charge of surface of clay, so can be as expansion-resisting agent.But generation precipitation is easily reacted when cationic surfactant makees anti-clayswelling agent with other anion chemical agent.It addition, the shortcoming of its maximum is the wettability making reservoir becomes oil-wet, the relative permeability of water is caused to decline.
Organic cationic polymer is the polymer of nitrogenous, sulfur and phosphorus.More be polyquaternary amine salts substances; it dissociates in water and produces the macromolecule cation of high positive electricity price, can form multipoint adsorption, after absorption with multiple clay particles simultaneously; form one layer of absorption protecting film on the surface of clay particle, prevent expansion and the migration of clay particle.But such material the most generally also exists non-refractory, the shortcoming that anti-swollen performance is inadequate.
Summary of the invention
The present invention provides a kind of low-molecular weight polymer clay stabilizer preparation method.
The purpose of the present invention is achieved through the following technical solutions: this clay stabilizer is as raw material with the ammonium salt containing carbon-carbon double bond and 2-acrylamide-2-methylpro panesulfonic acid (AMPS), under conditions of initiator exists, polymerization is prepared from the most in aqueous, and polymer number-average molecular weight is less than 50,000.
The described ammonium salt containing carbon-carbon double bond is: the mixture of the one or two kinds of in solution property, dimethyl diallyl ammonium chloride, diethyl diallyl ammonium chloride, trimethylallylammonium chloride, triethyl-allyl ammonia chloride, acrylyl oxy-ethyl-trimethyl salmiac, methyl-propen acyloxyethyl trimethyl ammonium chloride, triallyl ammonio methacrylate, triallyl ethyl ammonium chloride.
Described polymeric reaction temperature is-6 DEG C ~ 95 DEG C.
The described response time is 0.2h ~ 10h.
Described initiator is sodium sulfite, potassium sulfite and Ammonium persulfate., potassium peroxydisulfate or any two kinds of redox systems being made into of hydrogen peroxide, and the dosage of initiator is ammonium salt and the 0.01% ~ 2.0% of 2-acrylamide-2-methylpro panesulfonic acid gross mass.
The ratio of the amount of described ammonium salt and 2-acrylamide-2-methylpro panesulfonic acid (AMPS) material is 1:(1 ~ 5).
Detailed description of the invention
The technique present invention being described below in conjunction with embodiment.
Embodiment 1
A certain amount of 90% acetic acid solution is added in 0.5L there-necked flask, a certain amount of 2-acrylamide-2-methylpro panesulfonic acid is added under stirring, continue stirring, control certain heating rate and material is heated to 90 DEG C, stop heating, lower the temperature with chilled brine, material is made gradually to be cooled to 8 DEG C ~ 10 DEG C, maintain 1h, filter and separate filtrate and 2-acrylamide-2-methylpro panesulfonic acid crystal, standby in the following test of 2-acrylamide-2-methylpro panesulfonic acid crystal.
Embodiment 2
Equipped with motor stirrer, the there-necked flask of reflux condensing tube and thermometer adds 200.0g distilled water, cooled down by freezing liquid, in control there-necked flask, temperature is at about 0 DEG C, 10.0g dimethyl diallyl ammonium chloride and 40.0g2-acrylamide-2-methylpro panesulfonic acid crystal it is sequentially added under stirring, stirring is to being completely dissolved, add pH value regulator, regulation reacting liquid pH value is neutral, add 1.0g sodium sulfite-potassium peroxydisulfate initiator, it is passed through nitrogen 30min, heating up and controlling reaction temperature is 60 DEG C, 3h is reacted under stirring, reaction terminates i.e. to obtain clay stabilizer product after vacuum drying is pulverized again, it is numbered 1#。
Embodiment 3
Equipped with motor stirrer, the there-necked flask of reflux condensing tube and thermometer adds 200.0g distilled water, cooled down by freezing liquid, in control there-necked flask, temperature is at about 0 DEG C, 8.0g diethyl diallyl ammonium chloride and 40.0g2-acrylamide-2-methylpro panesulfonic acid crystal it is sequentially added under stirring, stirring is to being completely dissolved, add pH value regulator, regulation reacting liquid pH value is neutral, add 0.5g sodium sulfite-ammonium persulfate initiator, it is passed through nitrogen 30min, heating up and controlling reaction temperature is 35 DEG C, 6h is reacted under stirring, reaction terminates i.e. to obtain clay stabilizer product after vacuum drying is pulverized again, it is numbered 2#。
Embodiment 4
Equipped with motor stirrer, the there-necked flask of reflux condensing tube and thermometer adds 200.0g distilled water, cooled down by freezing liquid, in control there-necked flask, temperature is at about 0 DEG C, 15.0g acrylyl oxy-ethyl-trimethyl salmiac and 45.0g2-acrylamide-2-methylpro panesulfonic acid crystal it is sequentially added under stirring, stirring is to being completely dissolved, add pH value regulator, regulation reacting liquid pH value is neutral, add 0.3g sodium sulfite-potassium peroxydisulfate initiator, it is passed through nitrogen 30min, heating up and controlling reaction temperature is 65 DEG C, 5h is reacted under stirring, reaction terminates i.e. to obtain clay stabilizer product after vacuum drying is pulverized again, it is numbered 3#。
Embodiment 5
Equipped with motor stirrer, the there-necked flask of reflux condensing tube and thermometer adds 200.0g distilled water, cooled down by freezing liquid, in control there-necked flask, temperature is at about 0 DEG C, 4.0g diethyl diallyl ammonium chloride it is sequentially added under stirring, 10.0g acrylyl oxy-ethyl-trimethyl salmiac and 40.0g2-acrylamide-2-methylpro panesulfonic acid crystal, stirring is to being completely dissolved, add pH value regulator, regulation reacting liquid pH value is neutral, add 0.8g sodium sulfite-potassium peroxydisulfate initiator, it is passed through nitrogen 30min, heating up and controlling reaction temperature is 50 DEG C, 3.5h is reacted under stirring, reaction terminates i.e. to obtain clay stabilizer product after vacuum drying is pulverized again, it is numbered 4#。
Embodiment 6
Equipped with motor stirrer, the there-necked flask of reflux condensing tube and thermometer adds 200.0g distilled water, cooled down by freezing liquid, in control there-necked flask, temperature is at about 0 DEG C, 10.0g trimethylallylammonium chloride and 40.0g2-acrylamide-2-methylpro panesulfonic acid crystal it is sequentially added under stirring, stirring is to being completely dissolved, add pH value regulator, regulation reacting liquid pH value is neutral, add 0.8g sodium sulfite-potassium peroxydisulfate initiator, it is passed through nitrogen 30min, heating up and controlling reaction temperature is 55 DEG C, 2.5h is reacted under stirring, reaction terminates i.e. to obtain clay stabilizer product after vacuum drying is pulverized again, it is numbered 5#。
Embodiment 7
Equipped with motor stirrer, the there-necked flask of reflux condensing tube and thermometer adds 200.0g distilled water, cooled down by freezing liquid, in control there-necked flask, temperature is at about 0 DEG C, 10.0g trimethylallylammonium chloride it is sequentially added under stirring, 1.0g triallyl ammonio methacrylate and 40.0g2-acrylamide-2-methylpro panesulfonic acid crystal, stirring is to being completely dissolved, add pH value regulator, regulation reacting liquid pH value is neutral, add 0.7g sodium sulfite-potassium peroxydisulfate initiator, it is passed through nitrogen 30min, heating up and controlling reaction temperature is 40 DEG C, 3.5h is reacted under stirring, reaction terminates i.e. to obtain clay stabilizer product after vacuum drying is pulverized again, it is numbered 6#。
Embodiment 8
The most accurately weigh above-mentioned 1 ~ No. 6 clay stabilizer sample of 10.0 g, be accurate to 0.1 g, be dissolved in 990.0
In g distilled water, it is accurate to 0.1 g, stirs 30
Min, forms homogeneous solution, puts on 1 respectively#~6#, stand-by.
Embodiment 9
The anti-dilative of product is have rated according to " SY/T5971-94 water filling clay stabilizer method of evaluating performance ".
This experiment clay stabilization agent solution used is by being joined solution in embodiment 8, result of the test is shown in Table 1.
Table 1 product anti-dilative is tested
From anti-dilative data it can be seen that the clay stabilizer agent that the present invention develops all has the good ability preventing bentonite hydration swelling.
Embodiment 10
Reference standard " SY-T 5613-2000 mud shale physicochemical property test method " evaluates the sample suppression scattered ability of Shale Hydration.Rock sample used is Deyang, Sichuan landwaste, with 3% dioxygen washing 10min, is then dried.Taking the clay stabilization agent solution that 350mL embodiment is prepared respectively, adding 4-8 mesh landwaste 50g, cleaning with clear water after heat rolling 16h at a temperature of 120 DEG C, cross 40 mesh sieves, at a temperature of 105 DEG C, dry 4h, calculating primary recovery of weighing, the results are shown in Table 2.
Table 2 landwaste rolls recovery test
From table 2, the clay stabilizer product of preparation still has the stronger scattered ability of suppression Shale Hydration after 120 DEG C of heat rollings.
Embodiment 11
Evaluate SY/T6335-1997 according to China National Petroleum industry standard and carry out the experiment of sample linear dilatancy.Instrument is NP-3 shale expansion tester.
Weigh 8.00g at 105 DEG C of scholars 3 DEG C, dry two grades of bentonite (a diameter of 0.15-0.044mm) of 4h, at pressure made on the machine tabletting (pressure 10MPa, time 5min).Tabletting is put in shale expansion instrument, adds the certain density stabiliser solution (joined solution in embodiment 8) prepared, measure the expansion rate of mud shale tabletting after test solution soaks.The expansion rate of mud shale tabletting is the least, illustrates that the ability of the suppression hydration and expansion of clay of product is the strongest；Otherwise it is the poorest.Experimental result is as shown in table 3.
Table 3 linear expansion rate is tested
From table 3, the clay stabilizer product of preparation can suppress the hydration swelling of clay effectively.
Claims (4)
1. the preparation method of a low-molecular-weight clay stabilizer, it is characterized in that this clay stabilizer is with the ammonium salt containing carbon-carbon double bond and 2-acrylamide-2-methylpro panesulfonic acid as raw material, under conditions of initiator exists, polymerization is prepared from aqueous, and polymer number-average molecular weight is less than 50,000；The ammonium salt added and the ratio of the amount of 2-acrylamide-2-methylpro panesulfonic acid material are 1:(1 ~ 5)；Described initiator is sodium sulfite, potassium sulfite and Ammonium persulfate., potassium peroxydisulfate or any two kinds of redox systems being made into of hydrogen peroxide, and the dosage of initiator is ammonium salt and the 0.01% ~ 2.0% of 2-acrylamide-2-methylpro panesulfonic acid gross mass.
A kind of low-molecular-weight clay stabilizer preparation method the most according to claim 1, is characterized in that the described ammonium salt containing carbon-carbon double bond is: the mixture of the one or two kinds of in solution property, dimethyl diallyl ammonium chloride, diethyl diallyl ammonium chloride, trimethylallylammonium chloride, triethyl-allyl ammonia chloride, acrylyl oxy-ethyl-trimethyl salmiac, methyl-propen acyloxyethyl trimethyl ammonium chloride, triallyl ammonio methacrylate, triallyl ethyl ammonium chloride.
A kind of low-molecular-weight clay stabilizer preparation method the most according to claim 1, is characterized in that described reaction temperature is-6 DEG C ~ 95 DEG C.
A kind of low-molecular-weight clay stabilizer preparation method the most according to claim 1, is characterized in that the described response time is 0.2h ~ 10h.
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| CN104312575A (en) * | 2014-10-31 | 2015-01-28 | 重庆科技学院 | Efficient clay inhibitor for shale gas fracturing and preparation method of efficient clay inhibitor |
| CN106753316B (en) * | 2017-02-07 | 2019-10-01 | 西安石油大学 | A kind of multi-functional clay stabilizer |
| CN111087981B (en) * | 2018-12-25 | 2022-07-26 | 北京石大博诚科技有限公司 | Inhibitor for drilling fluid and preparation method thereof |
| CN109837073B (en) * | 2019-03-21 | 2021-01-19 | 西安石油大学 | Shale plugging inhibitor for drilling shale gas horizontal well and preparation method thereof |
| CN110358510B (en) * | 2019-07-16 | 2021-08-17 | 荆州市众天化工有限公司 | Strong-sensitive anti-swelling inhibitor for continental facies shale and preparation method thereof |
| CN111607375B (en) * | 2020-06-16 | 2022-09-23 | 胜利油田凯渡石油技术开发有限公司 | Anti-swelling shrinkage and expansion-shrinkage agent for low-permeability sensitive oil reservoir and preparation method thereof |
| CN113355060A (en) * | 2021-05-28 | 2021-09-07 | 浙江大川新材料股份有限公司 | Novel clay stabilizer and preparation method thereof |
| CN114805682B (en) * | 2022-05-23 | 2023-05-09 | 东营众悦石油科技有限公司 | Amphoteric clay stabilizer and preparation method thereof |
| CN117645684A (en) * | 2023-12-06 | 2024-03-05 | 山东滨州昱诚化工科技有限公司 | Anti-swelling clay stabilizer and synthesis method thereof |
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| CN102220112A (en) * | 2011-05-18 | 2011-10-19 | 北京兴有丰科科技发展有限公司 | Inorganic-organic salt-resisting and high temperature-resisting polymer fluid loss additive for drilling fluid |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |