CN112251213B - Compound Chemical Stimulants in Geothermal Systems - Google Patents
Compound Chemical Stimulants in Geothermal Systems Download PDFInfo
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- 239000000126 substance Substances 0.000 title claims abstract description 33
- 150000001875 compounds Chemical class 0.000 title claims description 11
- 239000000021 stimulant Substances 0.000 title abstract description 3
- 239000002253 acid Substances 0.000 claims abstract description 49
- 239000002245 particle Substances 0.000 claims abstract description 35
- 239000003381 stabilizer Substances 0.000 claims abstract description 34
- 239000013530 defoamer Substances 0.000 claims abstract description 30
- 239000002689 soil Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 12
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 125000002091 cationic group Chemical group 0.000 claims description 20
- 150000003863 ammonium salts Chemical group 0.000 claims description 16
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 4
- -1 polyoxypropylene oxyethylene glycerol Polymers 0.000 claims description 4
- 239000004088 foaming agent Substances 0.000 claims description 2
- 239000011435 rock Substances 0.000 abstract description 23
- 230000035699 permeability Effects 0.000 abstract description 16
- 230000000638 stimulation Effects 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010453 quartz Substances 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 3
- 229910052656 albite Inorganic materials 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 3
- 239000006260 foam Substances 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 238000004090 dissolution Methods 0.000 description 6
- 239000004927 clay Substances 0.000 description 5
- 229920000289 Polyquaternium Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 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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- 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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Abstract
本发明涉及高温地热资源开采技术领域，特别涉及一种地热系统中的复合化学刺激剂，包括15％HCl+1％HF的土酸、颗粒稳定剂和强酸体系消泡剂，强酸体系消泡剂包括聚醚类消泡剂、聚醚酯类消泡剂和/或无硅消泡剂。该发明采用适宜的土酸配方，使得岩心中的钾长石、钠长石和石英发生溶蚀作用。加入了颗粒稳定剂，避免了化学刺激过程中加剧岩体颗粒脱落并堵塞流动通道，保持低浓度土酸优异的化学刺激效果，并且可显著提高化学刺激剂在热储层岩体中的渗透率，同时，消泡剂的作用下，将HCl与碳酸盐反应后生成物的大量泡沫实时消除，增强岩体人工裂隙的连通性，从而提高化学刺激剂在热储层岩体中的渗透率。The invention relates to the technical field of high-temperature geothermal resource exploitation, in particular to a composite chemical stimulant in a geothermal system, comprising 15% HCl+1% HF soil acid, a particle stabilizer, a strong acid system defoamer, and a strong acid system defoamer Including polyether defoamer, polyether ester defoamer and/or silicone-free defoamer. The invention adopts a suitable soil acid formula, so that the potassium feldspar, albite and quartz in the core are dissolved. The particle stabilizer is added to avoid the aggravation of rock mass particles falling off and block the flow channel during the chemical stimulation process, maintaining the excellent chemical stimulation effect of low concentration soil acid, and can significantly improve the permeability of chemical stimulation agent in thermal reservoir rock mass At the same time, under the action of the defoaming agent, a large amount of foam produced by the reaction of HCl and carbonate will be eliminated in real time, and the connectivity of artificial fractures in the rock mass will be enhanced, thereby improving the permeability of chemical stimulants in the thermal reservoir rock mass. .
Description
技术领域technical field
本发明涉及高温地热资源开采技术领域，特别涉及一种地热系统中的复合化学刺激剂。The invention relates to the technical field of high-temperature geothermal resource exploitation, in particular to a compound chemical stimulant in a geothermal system.
背景技术Background technique
在全球气候变暖的背景下，各国政府都非常重视节能减排。地热能作为一种可再生清洁新能源，而且这种能源非常丰富，有很大的开发利用潜力，已成为传统化石能源的有效替代品。研究表明，利用增强型地热系统(EGS Enhanced Geothermal Systems)发电，几乎不受外界环境影响，且几乎不对人类环境产生污染和破坏。增强型地热系统是从地下深部低渗透性干热岩体通过人工压裂技术后，经济地采出相当数量地热能的人工地热系统。在EGS工程中，经常会遇到生产井/注入井与人工地热储层裂隙网络的水力联系较差，无法满足EGS的产能需求。为了拓展裂隙网络，增大热储层渗透性，有研究报道利用EGS化学刺激，即以低于地层破裂压力的注入压力向井附近热储层裂隙注入化学刺激液，依靠其化学溶蚀作用使岩石矿物溶解来增加地层的渗透性。In the context of global warming, governments around the world attach great importance to energy conservation and emission reduction. As a renewable and clean new energy, geothermal energy is very abundant and has great potential for development and utilization, and has become an effective substitute for traditional fossil energy. Studies have shown that the use of enhanced geothermal systems (EGS Enhanced Geothermal Systems) to generate electricity is almost unaffected by the external environment, and hardly causes pollution and damage to the human environment. Enhanced geothermal system is an artificial geothermal system that can economically produce a considerable amount of geothermal energy from deep underground low-permeability dry-hot rock mass through artificial fracturing technology. In EGS engineering, it is often encountered that the hydraulic connection between production wells/injection wells and the fracture network of artificial geothermal reservoirs is poor, which cannot meet the production capacity requirements of EGS. In order to expand the fracture network and increase the permeability of thermal reservoirs, some studies reported using EGS chemical stimulation, that is, injecting chemical stimulation fluid into the fractures of thermal reservoirs near the well at an injection pressure lower than the formation fracture pressure, and relying on its chemical dissolution to make rock minerals dissolve to increase the permeability of the formation.
目前，常用的化学刺激剂是盐酸和氢氟酸混合而成的土酸，石油天然气领域常用12％HCl+3％HF的常规土酸(酸含量以质量分数计)开展储层增产工艺，但有前人研究表明高浓度的土酸对岩体矿物溶蚀剧烈，极容易在储层中形成二次沉淀，因此，有学者选用10％HCl+0.5％HF的低浓度土酸进行研究，但是，低浓度土酸又不利于渗透率的提高。因此，一方面需避免化学刺激剂对岩体矿物溶蚀程度剧烈造成储层二次沉淀，同时，另一方面需提高化学刺激剂在岩体中的渗透率，则需优化化学刺激剂的配方。At present, the commonly used chemical stimulant is soil acid mixed with hydrochloric acid and hydrofluoric acid. Conventional soil acid of 12% HCl + 3% HF (acid content is calculated by mass fraction) is commonly used in the oil and gas field to carry out the reservoir stimulation process. Previous studies have shown that high concentrations of soil acid have severe dissolution of rock minerals, and it is very easy to form secondary precipitation in the reservoir. Therefore, some scholars choose low concentration soil acid of 10% HCl + 0.5% HF for research, but, Low concentration of soil acid is not conducive to the improvement of permeability. Therefore, on the one hand, it is necessary to avoid the secondary precipitation of the reservoir caused by the severe dissolution of the chemical stimulant on the rock mass, and on the other hand, to improve the permeability of the chemical stimulant in the rock mass, the formulation of the chemical stimulant needs to be optimized.
发明内容SUMMARY OF THE INVENTION
本发明为了克服上述技术问题，提供了一种地热系统中的复合化学刺激剂，找到适宜的土酸配方，即15％HCl+1％HF的土酸，使得岩心中的钾长石、钠长石和石英发生溶蚀作用。加入了颗粒稳定剂，避免了化学刺激过程中加剧岩体颗粒脱落并堵塞流动通道，保持低浓度土酸优异的化学刺激效果，并且可显著提高热储层岩体的渗透率，同时，消泡剂使HCl与碳酸盐反应后生成物的大量泡沫实时消除，进一步提高热储层岩体渗透率。In order to overcome the above technical problems, the present invention provides a compound chemical stimulator in a geothermal system, and finds a suitable soil acid formula, that is, 15% HCl+1% HF soil acid, so that the potassium feldspar and sodium in the core grow longer Dissolution of stone and quartz occurs. The particle stabilizer is added to avoid the aggravation of rock mass particles falling off and block the flow channel during the chemical stimulation process, maintaining the excellent chemical stimulation effect of low concentration soil acid, and can significantly improve the permeability of thermal reservoir rock mass, and at the same time, defoaming The agent can eliminate a large amount of foam in real time after the reaction of HCl and carbonate, and further improve the permeability of the thermal reservoir rock mass.
解决上述技术问题的技术方案如下：The technical solutions to solve the above technical problems are as follows:
地热系统中的复合化学刺激剂，包括15％HCl+1％HF的土酸、颗粒稳定剂和强酸体系消泡剂，所述的强酸体系消泡剂包括聚醚类消泡剂、聚醚酯类消泡剂和/或无硅消泡剂，所述的颗粒稳定剂加入量为土酸质量的1.5-2％；所述的强酸体系消泡剂的加入量为土酸质量的15-20％。The compound chemical stimulant in the geothermal system includes 15% HCl+1% HF soil acid, particle stabilizer and strong acid system defoamer, and the strong acid system defoamer includes polyether defoamer, polyether ester Antifoaming agent and/or silicon-free antifoaming agent, the added amount of the particle stabilizer is 1.5-2% of the mass of the soil acid; the amount of the antifoaming agent of the strong acid system is 15-20% of the mass of the soil acid %.
进一步地说，所述的颗粒稳定剂通过环氧氯丙烷和聚季铵盐反应制得的粘土稳定剂。Further, the particle stabilizer is a clay stabilizer prepared by the reaction of epichlorohydrin and polyquaternary ammonium salt.
进一步地说，所述的颗粒稳定剂的制备方法是将环氧氯丙烷和短链多电荷阳离子聚季铵盐按摩尔比为1～2:1溶于溶剂中置于反应釜内，添加引发剂，升温至30～100℃，反应2～5小时，即得颗粒稳定剂。Further, the preparation method of the particle stabilizer is to dissolve epichlorohydrin and short-chain multi-charged cationic polyquaternary ammonium salts in a solvent in a molar ratio of 1 to 2:1 and place them in a reactor, and add a The temperature is raised to 30-100° C., and the reaction is carried out for 2-5 hours to obtain the particle stabilizer.
进一步地说，所述的溶剂的添加量为环氧氯丙烷和短链多电荷阳离子聚季铵盐总量的10-20倍，所述的引发剂添加量为混合溶液总质量的1-2％。Further, the addition of the solvent is 10-20 times the total amount of epichlorohydrin and short-chain multi-charged cationic polyquaternary ammonium salts, and the initiator addition is 1-2 times the total mass of the mixed solution %.
进一步地说，所述的短链多电荷阳离子聚季铵盐是分子量为2-10万的白色粉末或颗粒，阳离子度为10-20％。Further, the short-chain multi-charged cationic polyquaternary ammonium salt is a white powder or particle with a molecular weight of 20,000 to 100,000, and a cationic degree of 10-20%.
进一步地说，所述的聚醚类消泡剂中含有不低于96％质量含量的聚氧丙烯氧乙烯甘油醚。Further, the polyether defoamer contains polyoxypropylene oxyethylene glycerol ether with a mass content of not less than 96%.
进一步地说，所述的聚醚酯类消泡剂中含有不低于20％质量含量的有机硅改性聚醚酯类化合物。More specifically, the polyetherester defoamer contains no less than 20% by mass of the organosilicon-modified polyetherester compound.
本发明的有益效果是：The beneficial effects of the present invention are:
该发明提供了一种复合化学刺激剂，采用适宜的土酸配方，即15％HCl+1％HF，使得岩心中的钾长石、钠长石和石英发生溶蚀作用。加入了颗粒稳定剂，避免了化学刺激过程中加剧岩体颗粒脱落并堵塞流动通道，保持低浓度土酸优异的化学刺激效果，并且可显著提高热储层岩体的渗透率，同时，消泡剂使HCl与碳酸盐反应后生成物的大量泡沫实时消除，进一步提高热储层岩体的渗透率。The invention provides a compound chemical stimulant, which adopts a suitable soil acid formula, namely 15% HCl+1% HF, to cause the dissolution of potassium feldspar, albite and quartz in the core. The particle stabilizer is added to avoid the aggravation of rock mass particles falling off and block the flow channel during the chemical stimulation process, maintaining the excellent chemical stimulation effect of low concentration soil acid, and can significantly improve the permeability of thermal reservoir rock mass, and at the same time, defoaming The agent can eliminate a large amount of foam in the reaction product of HCl and carbonate in real time, and further improve the permeability of the thermal reservoir rock mass.
具体实施方式Detailed ways
下面结合具体实施方式对本发明作进一步详细的说明。The present invention will be described in further detail below in conjunction with specific embodiments.
实施例1：Example 1:
地热系统中的复合化学刺激剂，包括15％HCl+1％HF的土酸、颗粒稳定剂和强酸体系消泡剂，颗粒稳定剂加入量为土酸质量的1.5％；强酸体系消泡剂的加入量为土酸质量的15％，强酸体系消泡剂包括质量比为3:2:1的聚醚类消泡剂、聚醚酯类消泡剂和无硅消泡剂。聚醚类消泡剂中含有98％质量含量的聚氧丙烯氧乙烯甘油醚。聚醚酯类消泡剂中含有35％质量含量的有机硅改性聚醚酯类化合物。颗粒稳定剂通过环氧氯丙烷和聚季铵盐反应制得的粘土稳定剂。颗粒稳定剂的制备方法是将环氧氯丙烷和短链多电荷阳离子聚季铵盐按摩尔比为1:1溶于溶剂中置于反应釜内，添加引发剂，升温至30～100℃，反应5小时，即得颗粒稳定剂。溶剂的添加量为环氧氯丙烷和短链多电荷阳离子聚季铵盐总量的10-20倍，引发剂添加量为混合溶液总质量的1-2％。短链多电荷阳离子聚季铵盐是分子量为2-10万的白色粉末或颗粒，阳离子度为10-20％。The compound chemical stimulator in the geothermal system includes 15% HCl+1% HF soil acid, particle stabilizer and strong acid system defoamer. The amount of particle stabilizer added is 1.5% of the mass of soil acid; The added amount is 15% of the mass of earth acid, and the strong acid system defoamer includes polyether defoamer, polyether ester defoamer and silicon-free defoamer with a mass ratio of 3:2:1. The polyether defoamer contains 98% by mass of polyoxypropylene oxyethylene glycerol ether. The polyetherester defoamer contains 35% by mass of the organosilicon-modified polyetherester compound. The particle stabilizer is a clay stabilizer prepared by the reaction of epichlorohydrin and polyquaternium. The preparation method of the particle stabilizer is to dissolve epichlorohydrin and a short-chain multi-charged cationic polyquaternary ammonium salt with a molar ratio of 1:1 in a solvent and place it in a reactor, add an initiator, and heat up to 30-100° C., After 5 hours of reaction, the particle stabilizer was obtained. The added amount of the solvent is 10-20 times of the total amount of epichlorohydrin and the short-chain multi-charged cationic polyquaternary ammonium salt, and the added amount of the initiator is 1-2% of the total mass of the mixed solution. Short-chain multi-charged cationic polyquaternary ammonium salts are white powders or granules with a molecular weight of 20,000 to 100,000, and a cationic degree of 10-20%.
实施例2：Example 2:
地热系统中的复合化学刺激剂，包括15％HCl+1％HF的土酸、颗粒稳定剂和强酸体系消泡剂，颗粒稳定剂加入量为土酸质量的2％；所述的强酸体系消泡剂的加入量为土酸质量的20％，强酸体系消泡剂包括质量比为2:1的聚醚类消泡剂和无硅消泡剂。聚醚类消泡剂中含有96％质量含量的聚氧丙烯氧乙烯甘油醚。颗粒稳定剂通过环氧氯丙烷和聚季铵盐反应制得的粘土稳定剂。颗粒稳定剂的制备方法是将环氧氯丙烷和短链多电荷阳离子聚季铵盐按摩尔比为2:1溶于溶剂中置于反应釜内，添加引发剂，升温至30～100℃，反应2～5小时，即得颗粒稳定剂。溶剂的添加量为环氧氯丙烷和短链多电荷阳离子聚季铵盐总量的10-20倍，引发剂添加量为混合溶液总质量的1-2％。短链多电荷阳离子聚季铵盐是分子量为2-10万的白色粉末或颗粒，阳离子度为10-20％。The composite chemical stimulant in the geothermal system includes 15% HCl+1% HF soil acid, particle stabilizer and strong acid system defoamer, and the amount of particle stabilizer added is 2% of the mass of the soil acid; the strong acid system eliminates the The added amount of the foaming agent is 20% of the mass of the soil acid, and the strong acid system defoaming agent includes a polyether defoaming agent and a silicon-free defoaming agent with a mass ratio of 2:1. The polyether defoamer contains 96% by mass of polyoxypropylene oxyethylene glycerol ether. The particle stabilizer is a clay stabilizer prepared by the reaction of epichlorohydrin and polyquaternium. The preparation method of the particle stabilizer is to dissolve epichlorohydrin and a short-chain multi-charged cationic polyquaternary ammonium salt with a molar ratio of 2:1 in a solvent, place them in a reactor, add an initiator, and heat up to 30-100° C., After 2-5 hours of reaction, the particle stabilizer is obtained. The added amount of the solvent is 10-20 times of the total amount of epichlorohydrin and the short-chain multi-charged cationic polyquaternary ammonium salt, and the added amount of the initiator is 1-2% of the total mass of the mixed solution. Short-chain multi-charged cationic polyquaternary ammonium salts are white powders or granules with a molecular weight of 20,000 to 100,000, and a cationic degree of 10-20%.
实施例3：Example 3:
地热系统中的复合化学刺激剂，包括15％HCl+1％HF的土酸、颗粒稳定剂和强酸体系消泡剂，颗粒稳定剂加入量为土酸质量的1.75％；强酸体系消泡剂的加入量为土酸质量的18％，强酸体系消泡剂包括质量比为2:1的聚醚酯类消泡剂和无硅消泡剂。聚醚酯类消泡剂中含有不低于20％质量含量的有机硅改性聚醚酯类化合物。颗粒稳定剂通过环氧氯丙烷和聚季铵盐反应制得的粘土稳定剂。颗粒稳定剂的制备方法是将环氧氯丙烷和短链多电荷阳离子聚季铵盐按摩尔比为1.5:1溶于溶剂中置于反应釜内，添加引发剂，升温至30～100℃，反应2～5小时，即得颗粒稳定剂。溶剂的添加量为环氧氯丙烷和短链多电荷阳离子聚季铵盐总量的10-20倍，引发剂添加量为混合溶液总质量的1-2％。短链多电荷阳离子聚季铵盐是分子量为2-10万的白色粉末或颗粒，阳离子度为10-20％。The compound chemical stimulator in the geothermal system includes 15% HCl+1% HF soil acid, particle stabilizer and strong acid system defoamer. The amount of particle stabilizer added is 1.75% of the mass of soil acid; The added amount is 18% of the mass of earth acid, and the strong acid system defoamer includes polyetherester defoamer and silicon-free defoamer with a mass ratio of 2:1. The polyetherester defoamer contains not less than 20% by mass of the organosilicon-modified polyetherester compound. The particle stabilizer is a clay stabilizer prepared by the reaction of epichlorohydrin and polyquaternium. The preparation method of the particle stabilizer is to dissolve epichlorohydrin and a short-chain multi-charged cationic polyquaternary ammonium salt with a molar ratio of 1.5:1 in a solvent, place them in a reaction kettle, add an initiator, and heat up to 30-100° C., After 2-5 hours of reaction, the particle stabilizer is obtained. The added amount of the solvent is 10-20 times of the total amount of epichlorohydrin and the short-chain multi-charged cationic polyquaternary ammonium salt, and the added amount of the initiator is 1-2% of the total mass of the mixed solution. Short-chain multi-charged cationic polyquaternary ammonium salts are white powders or granules with a molecular weight of 20,000 to 100,000, and a cationic degree of 10-20%.
对比例1：Comparative Example 1:
采用常规土酸配方(12％HCl+3％HF)。A conventional earth acid formulation (12% HCl+3% HF) was used.
对比例2：Comparative Example 2:
采用10％HCl+0.5％HF土酸配方，为了抑制细小颗粒运移堵塞仪器管线，在土酸中加入了2％的NH4Cl粘土稳定剂，为削弱化学刺激剂对仪器的腐蚀作用，加入了4％的CBS-TA型金属缓蚀剂。Using the formula of 10% HCl+0.5% HF soil acid, in order to inhibit the migration of fine particles to block the pipeline of the instrument, 2% NH 4 Cl clay stabilizer was added to the soil acid. 4% CBS-TA type metal corrosion inhibitor.
参照庄亚芹老师的硕士毕业论文中记载的实验方法对上述实施例1-3和对比例1-2的化学刺激剂进行岩体矿物溶蚀实验和化学刺激剂在岩体的渗透率实验，结果如下：With reference to the experimental method recorded in the master's thesis of Mr. Zhuang Yaqin, the chemical stimulants of the above-mentioned examples 1-3 and comparative examples 1-2 were subjected to rock mass mineral dissolution experiments and chemical stimulant permeability experiments in rock mass. The results are as follows:
由上表可知，本发明提供的复合化学刺激剂，岩石渗透率均有提高，反应前后岩石渗透率的比值数据较大，说明本发明提供的复合化学刺激剂对岩石渗透率的提高效果明显。采用适宜的土酸配方，即15％HCl+1％HF，使得岩心中的钾长石、钠长石和石英发生溶蚀作用，加入了颗粒稳定剂，避免了化学刺激过程中加剧岩体颗粒脱落并堵塞流动通道，保持低浓度土酸优异的化学刺激效果，并且可显著提高热储层岩体的渗透率，同时，消泡剂使HCl与碳酸盐反应后生成物的大量泡沫实时消除，进一步提高热储层岩体的渗透率。It can be seen from the above table that the composite chemical stimulant provided by the present invention has improved rock permeability, and the ratio of rock permeability before and after the reaction is larger, indicating that the composite chemical stimulant provided by the present invention has an obvious effect on improving rock permeability. A suitable soil acid formula, namely 15% HCl+1% HF, is used to dissolve the potassium feldspar, albite and quartz in the core, and a particle stabilizer is added to avoid the aggravation of the rock mass particles falling off during the chemical stimulation process. Block the flow channel, maintain the excellent chemical stimulation effect of low-concentration soil acid, and can significantly improve the permeability of the thermal reservoir rock mass. Improve the permeability of thermal reservoir rock mass.
以上所述，仅是本发明的较佳实施例，并非对本发明做任何形式上的限制，凡是依据本发明的技术实质上对以上实施例所作的任何简单修改、等同变化，均落入本发明的保护范围之内。The above are only preferred embodiments of the present invention, and do not limit the present invention in any form. Any simple modifications and equivalent changes made to the above embodiments according to the technical essence of the present invention all fall into the present invention. within the scope of protection.
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