CN112251213B - Composite chemical stimulant in geothermal system - Google Patents
Composite chemical stimulant in geothermal system Download PDFInfo
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- CN112251213B CN112251213B CN202011103701.XA CN202011103701A CN112251213B CN 112251213 B CN112251213 B CN 112251213B CN 202011103701 A CN202011103701 A CN 202011103701A CN 112251213 B CN112251213 B CN 112251213B
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- defoaming agent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/725—Compositions containing polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention relates to the technical field of high-temperature geothermal resource exploitation, in particular to a composite chemical stimulant in a geothermal system, which comprises earth acid of 15% HCl + 1% HF, a particle stabilizer and a strong acid system defoaming agent, wherein the strong acid system defoaming agent comprises a polyether defoaming agent, a polyether ester defoaming agent and/or a silicon-free defoaming agent. The invention adopts a proper formula of the earth acid, so that the potassium feldspar, the albite and the quartz in the rock core are subjected to corrosion. The particle stabilizer is added, so that the phenomenon that rock particles fall off and block a flow channel is avoided, the excellent chemical stimulation effect of the low-concentration soil acid is kept, the permeability of the chemical stimulator in a thermal reservoir rock mass can be obviously improved, meanwhile, under the action of the defoaming agent, a large amount of foams of a product generated after the reaction of HCl and carbonate are eliminated in real time, the connectivity of artificial cracks of the rock mass is enhanced, and the permeability of the chemical stimulator in the thermal reservoir rock mass is improved.
Description
Technical Field
The invention relates to the technical field of high-temperature geothermal resource exploitation, in particular to a composite chemical stimulant in a geothermal system.
Background
Under the background of global warming, governments of various countries pay great attention to energy conservation and emission reduction. Geothermal energy is a renewable clean new energy source, and the energy source is very abundant, has great development and utilization potential, and has become an effective substitute of the traditional fossil energy source. Research shows that the Enhanced Geothermal system (EGS Enhanced Geothermal Systems) is hardly influenced by the external environment and hardly causes pollution and damage to the human environment. The enhanced geothermal system is an artificial geothermal system which economically extracts a considerable amount of geothermal energy from underground deep low-permeability dry and hot rock bodies through an artificial fracturing technology. In EGS engineering, the poor hydraulic connection between a production well/an injection well and an artificial geothermal reservoir fracture network is often encountered, and the capacity requirement of the EGS cannot be met. In order to expand fracture networks and increase the permeability of thermal reservoirs, research reports use EGS chemical stimulation, that is, chemical stimulation liquid is injected into the fractures of the thermal reservoirs near wells at injection pressure lower than the fracture pressure of the formations, and rock minerals are dissolved by means of chemical erosion to increase the permeability of the formations.
At present, a common chemical stimulant is earth acid formed by mixing hydrochloric acid and hydrofluoric acid, and a conventional earth acid (acid content is calculated by mass fraction) of 12% HCl + 3% HF is commonly used in the field of petroleum and gas for reservoir production increase, but previous researches show that high-concentration earth acid is severely corroded for rock mineral and is very easy to form secondary precipitation in a reservoir, so that researchers select low-concentration earth acid of 10% HCl + 0.5% HF for research, but the low-concentration earth acid is not beneficial to improvement of permeability. Therefore, on one hand, secondary sedimentation of a reservoir caused by severe corrosion of rock mineral by the chemical stimulant is avoided, and on the other hand, the formula of the chemical stimulant is optimized when the permeability of the chemical stimulant in the rock is improved.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a composite chemical stimulant in a geothermal system, and a proper earth acid formula is found, namely the earth acid of 15% HCl + 1% HF, so that potassium feldspar, albite and quartz in a rock core are corroded. The particle stabilizer is added, so that the phenomenon that rock particles fall off and block a flow channel in the chemical stimulation process is avoided, the excellent chemical stimulation effect of low-concentration soil acid is kept, the permeability of the thermal reservoir rock is remarkably improved, and meanwhile, the defoaming agent eliminates a large amount of foams of a product generated after the reaction of HCl and carbonate in real time, so that the permeability of the thermal reservoir rock is further improved.
The technical scheme for solving the technical problems is as follows:
the composite chemical stimulant in the geothermal system comprises earth acid of 15% HCl + 1% HF, a particle stabilizer and a strong acid system defoaming agent, wherein the strong acid system defoaming agent comprises a polyether defoaming agent, a polyether ester defoaming agent and/or a silicon-free defoaming agent, and the addition amount of the particle stabilizer is 1.5-2% of the mass of the earth acid; the addition amount of the strong acid system defoaming agent is 15-20% of the mass of the soil acid.
Furthermore, the particle stabilizer is a clay stabilizer prepared by the reaction of epichlorohydrin and polyquaternium.
Further, the preparation method of the particle stabilizer comprises the steps of dissolving epoxy chloropropane and short-chain multi-charge cationic polyquaternary ammonium salt in a solvent according to a molar ratio of 1-2: 1, placing the solution in a reaction kettle, adding an initiator, heating to 30-100 ℃, and reacting for 2-5 hours to obtain the particle stabilizer.
Furthermore, the addition amount of the solvent is 10-20 times of the total amount of the epichlorohydrin and the short-chain multi-charge cationic polyquaternium, and the addition amount of the initiator is 1-2% of the total mass of the mixed solution.
Further, the short-chain multi-charge cationic polyquaternium is white powder or particles with the molecular weight of 2-10 ten thousand, and the cationic degree is 10-20%.
Further, the polyether defoamer contains no less than 96% by mass of polyoxypropylene ethylene glycol glyceryl ether.
Further, the polyether ester defoaming agent contains not less than 20% by mass of organosilicon modified polyether ester compounds.
The invention has the beneficial effects that:
the invention provides a composite chemical stimulant, which adopts a proper earth acid formula, namely 15% HCl + 1% HF, so that potassium feldspar, albite and quartz in a rock core are subjected to corrosion. The particle stabilizer is added, so that the phenomenon that rock particles fall off and block a flow channel is avoided, the excellent chemical stimulation effect of the low-concentration soil acid is kept, the permeability of the thermal reservoir rock is remarkably improved, and meanwhile, the defoaming agent eliminates a large amount of foams of a product generated after the reaction of HCl and carbonate in real time, so that the permeability of the thermal reservoir rock is further improved.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments.
Example 1:
the composite chemical stimulant in the geothermal system comprises 15% HCl + 1% HF earth acid, a particle stabilizer and a strong acid system defoamer, wherein the addition amount of the particle stabilizer is 1.5% of the mass of the earth acid; the addition amount of the strong acid system defoaming agent is 15% of the mass of the earth acid, and the strong acid system defoaming agent comprises polyether defoaming agent, polyether ester defoaming agent and silicon-free defoaming agent in a mass ratio of 3:2: 1. The polyether defoamer contains 98 mass percent of polyoxypropylene ethylene glycol glyceryl ether. The polyether ester defoaming agent contains 35% of organic silicon modified polyether ester compound by mass. The particle stabilizer is a clay stabilizer prepared by reacting epichlorohydrin with polyquaternium. The preparation method of the particle stabilizer comprises the steps of dissolving epoxy chloropropane and short-chain multi-charge cationic polyquaternary ammonium salt in a solvent according to a molar ratio of 1:1, placing the solution in a reaction kettle, adding an initiator, heating to 30-100 ℃, and reacting for 5 hours to obtain the particle stabilizer. The addition amount of the solvent is 10-20 times of the total amount of the epichlorohydrin and the short-chain multi-charge cationic polyquaternium, and the addition amount of the initiator is 1-2% of the total mass of the mixed solution. The short-chain multi-charge cationic polyquaternium is white powder or particles with the molecular weight of 2-10 ten thousand, and the cationic degree is 10-20%.
Example 2:
the composite chemical stimulant in the geothermal system comprises 15% HCl + 1% HF earth acid, a particle stabilizer and a strong acid system defoamer, wherein the addition amount of the particle stabilizer is 2% of the mass of the earth acid; the addition amount of the strong acid system defoaming agent is 20% of the mass of the earth acid, and the strong acid system defoaming agent comprises a polyether defoaming agent and a silicon-free defoaming agent in a mass ratio of 2: 1. The polyether defoaming agent contains 96 mass percent of polyoxypropylene ethylene glycol glyceryl ether. The particle stabilizer is a clay stabilizer prepared by reacting epichlorohydrin with polyquaternium. The preparation method of the particle stabilizer comprises the steps of dissolving epoxy chloropropane and short-chain multi-charge cationic polyquaternary ammonium salt in a solvent according to the molar ratio of 2:1, placing the solution in a reaction kettle, adding an initiator, heating to 30-100 ℃, and reacting for 2-5 hours to obtain the particle stabilizer. The addition amount of the solvent is 10-20 times of the total amount of the epichlorohydrin and the short-chain multi-charge cationic polyquaternium, and the addition amount of the initiator is 1-2% of the total mass of the mixed solution. The short-chain multi-charge cationic polyquaternium is white powder or particles with the molecular weight of 2-10 ten thousand, and the cationic degree is 10-20%.
Example 3:
the composite chemical stimulant in the geothermal system comprises 15% HCl + 1% HF earth acid, a particle stabilizer and a strong acid system defoamer, wherein the addition amount of the particle stabilizer is 1.75% of the mass of the earth acid; the addition amount of the strong acid system defoaming agent is 18% of the mass of the earth acid, and the strong acid system defoaming agent comprises a polyether ester defoaming agent and a silicon-free defoaming agent in a mass ratio of 2: 1. The polyether ester defoaming agent contains not less than 20 mass percent of organosilicon modified polyether ester compounds. The particle stabilizer is a clay stabilizer prepared by the reaction of epichlorohydrin and polyquaternium. The preparation method of the particle stabilizer comprises the steps of dissolving epoxy chloropropane and short-chain multi-charge cationic polyquaternary ammonium salt in a solvent according to a molar ratio of 1.5:1, placing the solution in a reaction kettle, adding an initiator, heating to 30-100 ℃, and reacting for 2-5 hours to obtain the particle stabilizer. The addition amount of the solvent is 10-20 times of the total amount of the epichlorohydrin and the short-chain multi-charge cationic polyquaternium, and the addition amount of the initiator is 1-2% of the total mass of the mixed solution. The short-chain multi-charge cationic polyquaternium is white powder or particles with the molecular weight of 2-10 ten thousand, and the cationic degree is 10-20%.
Comparative example 1:
a conventional earth acid formulation (12% HCl + 3% HF) was used.
Comparative example 2:
adopting a formula of 10% HCl + 0.5% HF earth acid, and adding 2% NH into the earth acid in order to inhibit fine particles from moving to block the pipeline of the instrument 4 The Cl clay stabilizer is added with 4 percent of CBS-TA type metal corrosion inhibitor in order to weaken the corrosion of a chemical stimulant on instruments.
The chemical stimulants of examples 1 to 3 and comparative examples 1 to 2 above were subjected to rock mass mineral corrosion tests and permeability tests of the chemical stimulants in rock masses with reference to the experimental methods described in master graduate paper by the banksian mr, and the results were as follows:
the above table shows that the permeability of the rock is improved by the composite chemical stimulant provided by the invention, and the ratio data of the permeability of the rock before and after reaction is larger, which shows that the composite chemical stimulant provided by the invention has obvious effect of improving the permeability of the rock. The proper formula of the earth acid, namely 15% HCl + 1% HF, is adopted, so that potassium feldspar, albite and quartz in the rock core are subjected to corrosion, the particle stabilizer is added, the aggravation of rock particle shedding and flow channel blockage in the chemical stimulation process is avoided, the excellent chemical stimulation effect of the low-concentration earth acid is kept, the permeability of the thermal reservoir rock mass can be obviously improved, and meanwhile, the defoaming agent enables a large amount of foams of products generated after the reaction of the HCl and the carbonate to be eliminated in real time, so that the permeability of the thermal reservoir rock mass is further improved.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiment according to the present invention are within the scope of the present invention.
Claims (3)
1. The composite chemical stimulant in the geothermal system is characterized by comprising earth acid of 15% HCl + 1% HF, a particle stabilizer and a strong acid system defoaming agent, wherein the strong acid system defoaming agent comprises a polyether defoaming agent, a polyether ester defoaming agent and/or a silicon-free defoaming agent, and the addition amount of the particle stabilizer is 1.5-2% of the mass of the earth acid; the addition amount of the strong acid system defoaming agent is 15-20% of the mass of the soil acid;
dissolving epoxy chloropropane and short-chain multi-charge cationic polyquaternary ammonium salt in a solvent according to a molar ratio of 1-2: 1, placing the solution in a reaction kettle, adding an initiator, heating to 30-100 ℃, and reacting for 2-5 hours to obtain the particle stabilizer;
the addition amount of the solvent is 10-20 times of the total amount of the epichlorohydrin and the short-chain multi-charge cationic polyquaternium, and the addition amount of the initiator is 1-2% of the total mass of the mixed solution;
the short-chain multi-charge cationic polyquaternium is white powder or particles with the molecular weight of 2-10 ten thousand, and the cationic degree is 10-20%.
2. The complex chemical stimulant in a geothermal system according to claim 1, wherein the polyether defoamer contains not less than 96% by mass of polyoxypropylene ethylene glycol glyceryl ether.
3. The composite chemical stimulant in a geothermal system according to claim 1, wherein the polyether ester defoaming agent contains not less than 20% by mass of organosilicon modified polyether ester compounds.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011103701.XA CN112251213B (en) | 2020-10-15 | 2020-10-15 | Composite chemical stimulant in geothermal system |
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| CN202011103701.XA CN112251213B (en) | 2020-10-15 | 2020-10-15 | Composite chemical stimulant in geothermal system |
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| CN112251213B true CN112251213B (en) | 2022-09-23 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4031959A (en) * | 1976-01-09 | 1977-06-28 | Permeator Corporation | Method of maintaining the permeability of hydrocarbon reservoir rock |
| CN103571449A (en) * | 2013-11-08 | 2014-02-12 | 中国石油天然气股份有限公司 | Long-acting clay stabilizer for oil well and preparation and application thereof |
| CN104293326A (en) * | 2014-10-09 | 2015-01-21 | 中国石油大学(华东) | Composite natural gas hydrate inhibitor for drilling fluid |
| CN105174860A (en) * | 2015-08-21 | 2015-12-23 | 徐德龙 | High thermal conductive cementing material capable of enhancing heat exchange performance of heat exchange system of floor heating |
| CN105332681A (en) * | 2015-10-28 | 2016-02-17 | 吉林大学 | Thermal stimulation and chemical stimulation combined process of hot-dry-rock thermal reservoir |
| CN105385426A (en) * | 2015-11-20 | 2016-03-09 | 南京云越新材料科技有限公司 | Efficient composite defoaming agent for oil well cement and preparation method thereof |
| CN108431169A (en) * | 2015-12-23 | 2018-08-21 | 阿格拉纳控股股份有限公司 | Purposes of the process fluid with the compatible biostability of environment in geothermal borehole |
-
2020
- 2020-10-15 CN CN202011103701.XA patent/CN112251213B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4031959A (en) * | 1976-01-09 | 1977-06-28 | Permeator Corporation | Method of maintaining the permeability of hydrocarbon reservoir rock |
| CN103571449A (en) * | 2013-11-08 | 2014-02-12 | 中国石油天然气股份有限公司 | Long-acting clay stabilizer for oil well and preparation and application thereof |
| CN104293326A (en) * | 2014-10-09 | 2015-01-21 | 中国石油大学(华东) | Composite natural gas hydrate inhibitor for drilling fluid |
| CN105174860A (en) * | 2015-08-21 | 2015-12-23 | 徐德龙 | High thermal conductive cementing material capable of enhancing heat exchange performance of heat exchange system of floor heating |
| CN105332681A (en) * | 2015-10-28 | 2016-02-17 | 吉林大学 | Thermal stimulation and chemical stimulation combined process of hot-dry-rock thermal reservoir |
| CN105385426A (en) * | 2015-11-20 | 2016-03-09 | 南京云越新材料科技有限公司 | Efficient composite defoaming agent for oil well cement and preparation method thereof |
| CN108431169A (en) * | 2015-12-23 | 2018-08-21 | 阿格拉纳控股股份有限公司 | Purposes of the process fluid with the compatible biostability of environment in geothermal borehole |
Non-Patent Citations (1)
| Title |
|---|
| 土酸注入速率对EGS 热储层改造效果影响的实验研究;吴永东等;《可再生资源》;20151130;第33卷(第11期);第1674-1678页 * |
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Effective date of registration: 20220826 Address after: 050000 No. 268 Zhonghua North Street, Shijiazhuang City, Hebei Province Applicant after: THE INSTITUTE OF HYDROGEOLOGY AND ENVIRONMENTAL GEOLOGY (IHEG), CHINESE ACADEMY OF GEOSCIENCES (CAGS) Applicant after: Jilin University Applicant after: Hebei aijiayuan Geothermal Energy Technology Co.,Ltd. Address before: 050000 No. 268 Zhonghua North Street, Shijiazhuang City, Hebei Province Applicant before: THE INSTITUTE OF HYDROGEOLOGY AND ENVIRONMENTAL GEOLOGY (IHEG), CHINESE ACADEMY OF GEOSCIENCES (CAGS) Applicant before: Jilin University |
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