CN103086909A - Self-diverting agent for heterogeneous carbonate rock acidizing system - Google Patents
Self-diverting agent for heterogeneous carbonate rock acidizing system Download PDFInfo
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- CN103086909A CN103086909A CN2011103429246A CN201110342924A CN103086909A CN 103086909 A CN103086909 A CN 103086909A CN 2011103429246 A CN2011103429246 A CN 2011103429246A CN 201110342924 A CN201110342924 A CN 201110342924A CN 103086909 A CN103086909 A CN 103086909A
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Abstract
The invention relates to a self-diverting agent for a heterogeneous carbonate rock acidizing system. The self-diverting agent is characterized by: taking erucic acid as an initiator, adding 3-dimethylaminopropylamine to make them undergo a reaction under oil bath conditions and under the action of a water carrying agent dimethylbenzene and a catalyst KOH; subjecting the reacted mixed solution to pressure reduced vacuum pumping and cooling, thus obtaining erucamide tertiary amine; mixing the erucamide tertiary amine with a sodium chloroacetate solution and leaving them to react under water bath conditions; dissolving the reacted mixed solution in an acetone solution, conducting cooling to room temperature, and carrying out standing and pumping filtration so as to obtain erucamidopropyl betaine, i.e. the self-diverting agent for the heterogeneous carbonate rock acidizing system involved in the invention. Along with the progression of an acid-rock reaction, the acid solution system prepared in the invention can realize automatic viscosity change to generate high flow resistance, thus realizing effective distribution of the acid solution in a reservoir. The self-diverting agent has the characteristics of reducing acid solution filter loss, increasing the acid solution penetration distance, and ensuring effective self-diverting of the acid solution system.
Description
Technical field:
The present invention relates to a kind of for the heterogeneous carbonate acid system from diversion agent, belong to the Oilfield Chemicals design field.
Background technology:
For now, acidifying remains one of most widely used hydrocarbon-bearing pool reservoir stimulation modification measures.In the acidization of heterogeneous carbonate oil reservoir, according to the osmotic resistance minimum principle, at first the conventional acids such as gel acid, emulsified acid, cross-linked acid enter than most permeable zone, and be difficult to enter microfracture and the hole of low permeability layer, cause a large amount of leak-offs of acid solution and run out of very soon, EFFECTIVE RANGE reduces, and the acid stimulation effect is undesirable; On the other hand, the acidifying of most permeable zone easily causes too early product water, aerogenesis, increases injection pressure.Simultaneously, conventional acid show as viscosity larger, and its anti-shear performance is restricted owing to only showing superiority on viscosity, shows as system elasticity less, and system stability is relatively poor when acidifying turns to.
In order to obtain increasing production efficiently correctional effect, not only require acid solution that larger penetration depth is arranged, also require acid solution to have better flow state and suitable acid etching position at zone of interest, when acidifying turns to, stable system, the broken glue of residual acid thoroughly, do not pollute reservoir; Obviously, existing conventional acid technology can not satisfy the demand of actual production.
In order to satisfy above-mentioned requirements, need to develop a kind of can the reaction by sour rock and produce excitation mechanism, be formed on most permeable zone and produce full-bodied acid solution host, make follow-up acid solution can flow into low permeability reservoir, reduce the fluid loss rate of acid solution, improve the penetration depth of acid etching, and stable system when acid solution turns to, when running into oil gas, residual acid can automatically break glue, residual acid surfaces tension force is ultralow, be easy to be carried out reservoir by follow-up liquid, do not pollute reservoir, realize the volume increase modification measures of the heterogeneous carbonate of optimization.
Summary of the invention:
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of for the heterogeneous carbonate acid system from diversion agent, with the acid fluid system of its preparation along with the carrying out of sour rock reaction can realize automatically becoming sticky, produce higher resistance to flow, realize the effective distribution of acid solution in reservoir, have the filter loss that reduces acid solution, increase the penetration range of acid solution, guarantee that acid fluid system is from turning to the characteristics of effectively carrying out.
The present invention realizes above-mentioned purpose by following technical solution.
1, the preparation of erucicamide base tertiary amine:
As initiator, take the weight of erucic acid as benchmark, get a certain amount of erucic acid heating after it dissolves fully with erucic acid, add successively the 3-dimethylaminopropylamine of 40%--47% weight, the azeotropic agent dimethylbenzene of 20%--30% weight, rear logical N stirs
2, more dropwise add the catalyzer KOH of 0.5%--1.0% weight; React under the oil bath condition, temperature of reaction is 120 ℃～160 ℃, and the reaction times is 5～7 hours; With reacted mixed solution decompression vacuum pumping, the cooling erucicamide base tertiary amine that namely makes.Its reaction equation is as follows:
2, the preparation of erucicamide CAB:
Take the erucicamide base tertiary amine that makes as initiator, take the weight of erucicamide base tertiary amine as benchmark, take the sodium chloroacetate of 24%--27% weight, it is mixed with concentration is 20% sodium chloroacetate solution, be adjusted between 7～8 with the pH value of sodium bicarbonate with sodium chloroacetate solution, dropwise sodium chloroacetate solution joined in erucicamide base ertiary amine solution; React under water bath condition, temperature of reaction is 65 ℃～85 ℃, and the reaction times is 4～6 hours; Obtain thick product; By the volume ratio of 1: 2, above-mentioned thick product is dissolved in acetone soln, thick product is dissolved fully, be cooled to room temperature with water-bath, standing complete to crystal structure, suction filtration obtains coarse crystal; Coarse crystal is carried out acetone recrystallization 2～3 times, with the crystal drying that the obtains erucicamide CAB for making afterwards, be of the present invention a kind of for the heterogeneous carbonate acid system from diversion agent.Its reaction equation is as follows:
The present invention has following beneficial effect compared with prior art:
1, the acid fluid system with the present invention preparation very easily forms full-bodied spirrillum micella, is that under 5% condition, peak viscosity reaches 921mPas, breaks rapidly glue after residual acid mixes with the crude oil of different volumes ratio at dosage, and residual acid surfaces tension force reaches 1.8 * 10
-3MN/m.
2, acid fluid system and a certain proportion of crude oil with the present invention preparation mixes without the emulsification phenomenon, with after the local water compatibility of basic, normal, high salinity without the precipitated and separated phenomenon, solution is transparent.
3, the acid fluid system with the present invention's preparation has good high temperature resistance, anti-shear ability, and maximum temperature resistance reaches 105 ℃, and anti-shearing maximum reaches 1100s
-1
4, synthesis technique of the present invention is simple, and reaction conditions is gentle, and easy to use, cost is lower, can satisfy the requirement of heterogeneous carbonate self-diverting acid.
Embodiment:
The invention will be further described below in conjunction with specific embodiment:
1, the preparation of erucicamide base tertiary amine:
The erucic acid that adds 0.3mol in the there-necked flask of clean dried connects oil bath device, reflux, and slowly heating treats that erucic acid dissolves fully, adds successively 3-dimethylaminopropylamine 0.33mol, azeotropic agent dimethylbenzene 15g; Stir 30 seconds logical 3～5 minutes N afterwards
2, then utilize constant pressure funnel dropwise to add 2g catalyzer KOH, the conditioned reaction temperature is 140 ℃, and stirring reaction took out after 7 hours, and decompression vacuum pumping, remove impurity immediately, and is cooling, obtains erucicamide base tertiary amine.
2, the preparation of erucicamide CAB:
Take prepared erucicamide base tertiary amine 0.3mol; Take the sodium chloroacetate of 0.36mol, and it is mixed with concentration is 20% sodium chloroacetate solution, be adjusted between 7～8 with the pH value of sodium bicarbonate with sodium chloroacetate solution, utilize constant pressure funnel dropwise sodium chloroacetate solution to be joined in erucicamide base ertiary amine solution, the conditioned reaction temperature is 70 ℃, and stirring reaction was lowered the temperature after 6 hours, suction filtration obtains thick product.The thick product that makes is added in beaker, by the volume ratio of 1: 2, above-mentioned thick product is dissolved in acetone soln, thick product is dissolved fully, the acetone soln of thick product is cooled to room temperature with water-bath, standing complete to crystal structure, suction filtration, obtain coarse crystal, coarse crystal is carried out acetone recrystallization 2～3 times, the crystal that obtains was put under 60 ℃ of vacuum drying ovens dry 5 hours, the crystal that makes is the erucicamide CAB, be of the present invention a kind of for the heterogeneous carbonate acid system from diversion agent.
The present invention is used for the effect example of heterogeneous carbonate acid system:
Table 1: the viscoelastic property of bright acid and residual acid system
Table 2: acid fluid system turns to, temperature resistance, anti-shear performance
Broken colloidality energy after the residual acid of table 3 mixes with crude oil
As can be seen from Table 1, in bright acid system, storage modulus G ' is greater than out-of-phase modulus G ", namely represent the elasticity of bright acid system greater than viscosity, major embodiment goes out elasticity, is convenient to on-the-spot pump acid; In residual acid system, out-of-phase modulus G " greater than storage modulus G ', illustrate that when acid solution turns to, the system major embodiment is viscosity, can realize in time blocking macropore after sour rock reaction, complete from turning to function.
As can be seen from Table 2, along with the reduction of concentration of hydrochloric acid, system viscosity presents and first increases the trend that reduces afterwards, can change with concentration of hydrochloric acid realize auto-steering function.Acid fluid system can reach 105 ℃ by temperature resistance, can be at 1100s
-1Keep stable in scope.
As can be seen from Table 3, after the residual acid of different volumes ratio mixes with crude oil, system viscosity broken glue rapidly, reduced to below 9mPas rapidly by 65mPas, thus after acidifying finishes the row of returning smoothly.
Claims (3)
- One kind be used for the heterogeneous carbonate acid system from diversion agent, it is characterized in that:(1), the preparation of erucicamide base tertiary amine:As initiator, take the weight of erucic acid as benchmark, get a certain amount of erucic acid heating after it dissolves fully with erucic acid, add successively the 3-dimethylaminopropylamine of 40%--47% weight, the azeotropic agent dimethylbenzene of 20%--30% weight, rear logical N stirs 2, more dropwise add the catalyzer KOH of 0.5%--1.0% weight; React under the oil bath condition, temperature of reaction is 120 ℃～160 ℃, and the reaction times is 5～7 hours; With reacted mixed solution decompression vacuum pumping, the cooling erucicamide base tertiary amine that namely makes;(2), the preparation of erucicamide CAB:Take the erucicamide base tertiary amine that makes as initiator, take the weight of erucicamide base tertiary amine as benchmark, take the sodium chloroacetate of 24%--27% weight, it is mixed with concentration is 20% sodium chloroacetate solution, dropwise sodium chloroacetate solution is joined in erucicamide base ertiary amine solution; React under water bath condition, temperature of reaction is 65 ℃～85 ℃, and the reaction times is 4～6 hours; Obtain thick product; By the volume ratio of 1: 2, above-mentioned thick product is dissolved in acetone soln, thick product is dissolved fully, be cooled to room temperature with water-bath, standing complete to crystal structure, suction filtration obtains coarse crystal; Coarse crystal is carried out acetone recrystallization, with the crystal drying that the obtains erucicamide CAB for making afterwards, be of the present invention a kind of for the heterogeneous carbonate acid system from diversion agent.
- According to claim 1 a kind of for the heterogeneous carbonate acid system from diversion agent, it is characterized in that being adjusted between 7～8 with the pH value of sodium bicarbonate with sodium chloroacetate solution.
- According to claim 2 a kind of for the heterogeneous carbonate acid system from diversion agent, it is characterized in that coarse crystal is carried out acetone recrystallization 2～3 times, with the crystal drying that the obtains erucicamide CAB for making afterwards.
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| CN2011103429246A CN103086909A (en) | 2011-11-03 | 2011-11-03 | Self-diverting agent for heterogeneous carbonate rock acidizing system |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820098A (en) * | 2014-02-24 | 2014-05-28 | 中国石油大学(华东) | Non-damage self-diverting acid and preparation method and application |
| CN104479656A (en) * | 2014-11-04 | 2015-04-01 | 西南石油大学 | Variable-viscosity acid liquid used for acidifying processing |
| CN104910037A (en) * | 2015-06-02 | 2015-09-16 | 中国石油天然气股份有限公司 | Preparation method of amide surface-active acid thickener |
| CN106050213A (en) * | 2016-06-30 | 2016-10-26 | 中国海洋石油总公司 | Sandstone reservoir self-diverting acidizing method |
| CN106634938A (en) * | 2016-12-07 | 2017-05-10 | 中国石油天然气股份有限公司 | Compound type temperature-resisting viscoelastic self-diverting acid as well as preparation method and application thereof |
| CN107474818A (en) * | 2017-09-26 | 2017-12-15 | 中国石油化工股份有限公司 | A kind of high temperature resistant micro emulsion acid system and preparation method thereof |
| CN109294551A (en) * | 2018-10-18 | 2019-02-01 | 顺泰能源科技发展有限公司 | A kind of cleaning low damage agent of molecular cluster and its application |
| CN109762543A (en) * | 2019-02-20 | 2019-05-17 | 中国石油大学(华东) | A kind of heat-resistant salt-resistant is from Tackified emulsion work-in-progress control diversion agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820098A (en) * | 2014-02-24 | 2014-05-28 | 中国石油大学(华东) | Non-damage self-diverting acid and preparation method and application |
| CN103820098B (en) * | 2014-02-24 | 2016-01-20 | 中国石油大学(华东) | A kind of fanout free region self-diverting acid and preparation method thereof and application |
| CN104479656A (en) * | 2014-11-04 | 2015-04-01 | 西南石油大学 | Variable-viscosity acid liquid used for acidifying processing |
| CN104910037A (en) * | 2015-06-02 | 2015-09-16 | 中国石油天然气股份有限公司 | Preparation method of amide surface-active acid thickener |
| CN106050213A (en) * | 2016-06-30 | 2016-10-26 | 中国海洋石油总公司 | Sandstone reservoir self-diverting acidizing method |
| CN106050213B (en) * | 2016-06-30 | 2019-08-06 | 中国海洋石油总公司 | A kind of sandstone reservoir low damage distributary acid method |
| CN106634938A (en) * | 2016-12-07 | 2017-05-10 | 中国石油天然气股份有限公司 | Compound type temperature-resisting viscoelastic self-diverting acid as well as preparation method and application thereof |
| CN106634938B (en) * | 2016-12-07 | 2019-07-09 | 中国石油天然气股份有限公司 | A kind of compound temperature resistance viscoplasticity self-diverting acid and the preparation method and application thereof |
| CN107474818A (en) * | 2017-09-26 | 2017-12-15 | 中国石油化工股份有限公司 | A kind of high temperature resistant micro emulsion acid system and preparation method thereof |
| CN109294551A (en) * | 2018-10-18 | 2019-02-01 | 顺泰能源科技发展有限公司 | A kind of cleaning low damage agent of molecular cluster and its application |
| CN109762543A (en) * | 2019-02-20 | 2019-05-17 | 中国石油大学(华东) | A kind of heat-resistant salt-resistant is from Tackified emulsion work-in-progress control diversion agent and preparation method thereof |
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Application publication date: 20130508 |