CN113216910B - Chemical heat generating agent for natural gas hydrate exploitation and application thereof - Google Patents
Chemical heat generating agent for natural gas hydrate exploitation and application thereof Download PDFInfo
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- CN113216910B CN113216910B CN202110667543.9A CN202110667543A CN113216910B CN 113216910 B CN113216910 B CN 113216910B CN 202110667543 A CN202110667543 A CN 202110667543A CN 113216910 B CN113216910 B CN 113216910B
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 73
- 239000000126 substance Substances 0.000 title claims abstract description 39
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000006260 foam Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 239000004088 foaming agent Substances 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 13
- 239000003381 stabilizer Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 6
- 125000002091 cationic group Chemical group 0.000 claims abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims abstract description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 5
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 24
- 235000010288 sodium nitrite Nutrition 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000012141 concentrate Substances 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical group ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 239000001741 Ammonium adipate Substances 0.000 claims description 6
- 235000019293 ammonium adipate Nutrition 0.000 claims description 6
- 238000005065 mining Methods 0.000 claims description 6
- 239000003345 natural gas Substances 0.000 claims description 5
- -1 natural gas hydrates Chemical class 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 25
- 238000010438 heat treatment Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 239000012530 fluid Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- ZRSKSQHEOZFGLJ-UHFFFAOYSA-N ammonium adipate Chemical group [NH4+].[NH4+].[O-]C(=O)CCCCC([O-])=O ZRSKSQHEOZFGLJ-UHFFFAOYSA-N 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002595 cold damage Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003832 thermite Substances 0.000 description 1
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Classifications
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/01—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells specially adapted for obtaining from underwater installations
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B36/00—Heating, cooling or insulating arrangements for boreholes or wells, e.g. for use in permafrost zones
- E21B36/008—Heating, cooling or insulating arrangements for boreholes or wells, e.g. for use in permafrost zones using chemical heat generating means
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/164—Injecting CO2 or carbonated water
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/166—Injecting a gaseous medium; Injecting a gaseous medium and a liquid medium
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- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing Of Micro-Capsules (AREA)
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Abstract
The invention discloses a chemical heat generating agent for natural gas hydrate exploitation and application thereof, wherein the heat generating agent comprises: a main agent I, a main agent II and an auxiliary agent; the main agent I comprises the following components in percentage by mass and volume: 10 to 32% of NaNO 2 1-7.5% of foaming agent, 2-7.5% of foam stabilizer and the balance of water; the foaming agent is cationic Gemini quaternary ammonium salt; the foam stabilizer is nano-particles; the auxiliary agent is acid gas selected from CO 2 And/or SO 2 And the volume ratio of the main agent I to the auxiliary agent is 1: 4-40, mixing the main agent I and the auxiliary agent according to the volume ratio to obtain foam liquid; the main agent II is NH 4 Aqueous Cl solution. The chemical heat generating agent system can release a large amount of heat, can regulate and control the release speed of the heat, and meets the requirement of deep energy transmission of a reservoir stratum in the exploitation of the natural gas hydrate.
Description
Technical Field
The invention relates to a chemical heat generating agent, in particular to a chemical heat generating agent for natural gas hydrate exploitation and application thereof.
Background
Natural gas hydrates are solid compounds like ice formed by natural gas (methane as a main component) and water under certain high pressure and low temperature conditions. The natural gas hydrate exploitation process is a strong heat absorption process, and in the exploitation process, the temperature of a hydrate layer is rapidly reduced, so that the problems of reduction of gas production rate, blockage of pore channels and the like are caused.
In order to solve the problems, the conventional solution at present adopts methods such as hot water injection and hot steam injection to heat, however, the methods all have a very common problem that most of heat of hot fluid is consumed in a near-well area, so that the heat supply required by the decomposition of the hydrate in the deep part of a reservoir is insufficient, and the overall exploitation effect of the hydrate is finally influenced. In order to improve the heat supply in the process of hydrate exploitation, a chemical heat generating agent is proposed to carry heat to the far end of a stratum in the form of chemical energy, the chemical heat generating agent releases heat in the deep part of the stratum, and the consumption of heat in the near well end is reduced to improve the heat supply in the deep part of the reservoir.
For example, the existing autogenous hot fracturing fluid system at home and abroad is a nitrite and ammonium salt system, which can generate a great amount of heat through chemical reaction under acidic conditions and generate friendly and stable N 2 And the like. However, current autogenous systems all have difficulty with peak temperature control. Research shows that the most main influence factor of the heat generating capacity of the chemical heat generating system is the concentration of a chemical agent, and the higher the concentration is, the stronger the heat generating capacity of the reaction is, and the larger the heat generation quantity is. However, increasing the concentration of the chemical agent results in an increase in the rate of heat release, and this rapid heat release is extremely detrimental to the heat transport to deep portions of the reservoir, and balancing the two is a key issue for the application of chemical heat generating systems. In recent years, the temperature control of the self-heating liquid has been extensively studied at home and abroad, for example, chinese patent CN11849451A discloses a peak-controllable self-heating fracturing fluid, and a preparation method and an application thereof, wherein the self-heating fracturing fluid is prepared from a self-heating fracturing fluid base fluid and an activator solution according to a mass ratio of (18-22): (0.8-1.2), and when the use concentration of the self-generated thermal fracturing fluid in the activator solution is 0.005% -0.04%, the time for reaching the peak temperature is adjustable within 1-5 h, and the peak temperature can reach 48-105 ℃. Chinese patent CN112322270A discloses a continuous self-heating production period system for point fracturing fluid and a preparation method thereof, the catalyst hydrochloric acid, cyclohexane and Span-80 emulsifier form an emulsifier to achieve the purpose of slowing down reaction heat generation, and the continuous self-heating of the system can be maintained at more than 50 ℃ within 40 min. Chinese patent CN109281643A disclosesA system for delaying self-heating is composed of an ammonium chloride aqueous solution and water-in-oil type sodium nitrite, and the sodium nitrite is prepared into a water-in-oil type emulsion to fulfill the aim of slowing down the contact of the ammonium chloride aqueous solution and the water-in-oil type sodium nitrite.
In addition, the ambient temperature is also an important influence factor that affects the heat generation rate. However, most of the current patents are directed to fracturing systems, mainly used for solving the problem of cold damage of a fracturing fluid to a bottom layer, and the reaction temperature of the fracturing fluid is 30-50 ℃. However, the formation temperature of natural gas hydrates is generally below 20 ℃, the temperature during production can even drop below zero, and the current invention about the method for controlling the heat release rate of hydrates under low temperature conditions is not reported.
Disclosure of Invention
The invention aims to provide a chemical heat generating agent for natural gas hydrate exploitation and application thereof, and solves the problem that the heat of the conventional chemical heat generating agent is uncontrollable.
In order to achieve the above object, the present invention provides a chemical heat generating agent for natural gas hydrate production, the heat generating agent comprising: a main agent I, a main agent II and an auxiliary agent; the main agent I comprises the following components in percentage by mass and volume: 10 to 32% of NaNO 2 1-7.5% of foaming agent, 2-7.5% of foam stabilizer and the balance of water; the foaming agent is cationic Gemini quaternary ammonium salt, and the cationic Gemini quaternary ammonium salt is biquaternary ammonium adipate; the foam stabilizer is a nanoparticle; the auxiliary agent is acid gas selected from CO 2 And/or SO 2 And the volume ratio of the main agent I to the auxiliary agent is 1: 4-40, mixing the main agent I and the auxiliary agent according to the volume ratio to obtain a foam liquid; the main agent II is NH 4 Aqueous solution of Cl, said NH 4 The molar concentration of the Cl aqueous solution is equal to that of sodium nitrite in the foam concentrate, and the NH is 4 The volume of the aqueous Cl solution was equal to the volume of the foam concentrate.
The invention relates to a chemical heat generating agent for natural gas hydrate exploitation, which utilizes a novel self-heating system of acid gas as a catalyst, wherein the system utilizes acid gas and solution to form foam liquid, the exothermic reaction process is as follows, and CO is used 2 The gas is exemplified as follows:
first, CO 2 The weak acid is generated by the reaction with water,
secondly, sodium nitrite and ammonium chloride are subjected to exothermic reaction under the condition of an acid catalyst,
because the two reactions are connected in series, the final heat release rate is determined by the reaction equation (1) and the reaction equation (2), and the two reactions work together to achieve the purpose of slowing down the reaction rate.
Preferably, the nanoparticles are nanosilica particles.
The invention also aims to provide the application of the chemical heat generating agent in the aspect of exploiting natural gas hydrates.
Preferably, the auxiliary agent and the main agent I are mixed under the pressure of 4-6 MPa to form foam liquid; and injecting the equal volume of the foam liquid and the main agent II into a hydrate layer simultaneously to perform a hydrate thermal recovery process.
The chemical heat generating agent for natural gas hydrate exploitation and the application thereof solve the problem that the heat of the existing chemical heat generating agent is uncontrollable, and have the following advantages:
the chemical heat generating agent for natural gas hydrate exploitation can not only meet the function of releasing a large amount of heat in a low-temperature environment, but also regulate (delay) the release speed of the heat and meet the requirement of deep energy transmission of a reservoir stratum in the natural gas hydrate exploitation. Meanwhile, when the chemical heat generating agent provided by the invention is used for hydrate exploitation, injection is carried out only at room temperature without heating the solution in advance, so that the heat consumption is greatly reduced.
Drawings
FIG. 1 is a graph comparing the heat release rate during hydrate production of a chemical heat generating agent of the present invention (example 1) with an acetic acid catalyst heat generating system.
FIG. 2 is a graph comparing the rate of heat release during hydrate production by the chemical heat generating agent of the present invention (example 3) and an acetic acid catalyst heat generating system.
FIG. 3 is a graph comparing the heat release rate of the heat generating agent of the present invention with hot water and a conventional acetic acid heat generating system.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A chemical heat generating agent for natural gas hydrate exploitation is disclosed, wherein a main agent I of the heat generating agent comprises the following components in percentage by mass and volume (W/V, g/mL): 1% of foaming agent, 2% of foam stabilizer, 10% of sodium nitrite and the balance of water; wherein, the foaming agent adopts biquaternary ammonium adipate, and the foam stabilizer adopts nano silicon dioxide particles. The auxiliary agent of the heat generating agent is CO 2 Main agents I and CO 2 Is 1: and 4, mixing the main agent I and the auxiliary agent according to the volume ratio to obtain the foam liquid. The main agent II of the heat generating agent is NH 4 Aqueous Cl solution, NH 4 The molar concentration of the Cl aqueous solution is equal to the molar concentration of the sodium nitrite in the foam concentrate.
The preparation of the main agent I comprises the following steps: adding part of water into a reaction vessel I, heating to 60 ℃, and then sequentially adding 100g of NaNO into the reaction vessel I under the stirring condition 2 10g of diquaternium adipate surfactant, 20g of silica particles, the remaining water was added to the total volume1000mL, and after the addition, stirring is continued for 1h at 60 ℃ until the components are uniformly dissolved to obtain a main agent I.
The preparation of the main agent II comprises the following steps: according to NaNO in the foam liquid 2 Concentration preparation of NH 4 Adding water into the reaction vessel II, heating to 60 ℃, and then adding NH into the reaction vessel II under the condition of stirring 4 And Cl, and continuously stirring for 1h at the temperature of 60 ℃ after the addition is finished to obtain a main agent II.
The method for using the chemical heat generating agent in the hydrate exploitation process comprises the following steps: under the pressure of 4-6 MPa, CO is introduced 2 Gas is mixed with the main agent I by a mixing pump according to a predetermined volume ratio to form foam liquid; simultaneously pumping the equal-volume foam liquid and the main agent II into a hydrate layer by a high-pressure pump, and performing a hydrate thermal recovery process.
The mixing condition of the main agent I and the auxiliary agent in the embodiment 1 is specifically as follows:
300mL of the main agent I is added into a high-pressure sapphire kettle, and CO is introduced under the condition of continuous stirring 2 Gas 1200mL, the pressure is 4-6 MPa, the foam volume is read after stirring for 30min, the mixture is kept stand, and then the foam volume corresponding to the change along with the time is recorded. Through research, the time for the foam concentrate bottom layer liquid adopting biquaternary ammonium adipate in the example 1 to appear at 1/4 height is 2.5h; and the half-life time of the foaming agent consisting of the span 80 and the Tween80 with the same concentration is 0.5h, which shows that the foaming agent has excellent foaming effect.
Example 2
A chemical heat generating agent for natural gas hydrate exploitation, wherein a main agent I of the heat generating agent comprises the following components in percentage by mass and volume (W/V, g/mL): 7.5% of foaming agent, 7.5% of foam stabilizer, 32% of sodium nitrite and the balance of water; wherein, the foaming agent adopts biquaternary ammonium adipate, and the foam stabilizer adopts nano silicon dioxide particles. The auxiliary agent of the heat generating agent is CO 2 Host I and CO 2 Is 1: and 40, mixing the main agent I and the auxiliary agent according to the volume ratio to obtain the foam liquid. The main agent II of the heat generating agent is NH 4 Aqueous Cl solution, NH 4 Molar concentration of Cl aqueous solution and in foam concentrateThe molar concentration of sodium nitrite is equal.
The preparation of the main agent I comprises the following steps: adding part of water into a reaction vessel I, heating to 60 ℃, and then sequentially adding 320g of NaNO into the reaction vessel I under the stirring condition 2 75g of biquaternary ammonium salt adipate surfactant and 75g of silicon dioxide particles, adding the rest water till the total volume is 1000mL, and continuously stirring for 1h at 60 ℃ after the addition is finished till the components are uniformly dissolved to obtain the main agent I.
The preparation of the main agent II comprises the following steps: according to NaNO in the foam liquid 2 Concentration preparation of NH 4 Adding water into the reaction vessel II, heating to 60 ℃, and then adding NH into the reaction vessel II under the condition of stirring 4 And Cl, and continuously stirring for 1h at the temperature of 60 ℃ after the addition is finished to obtain a main agent II.
The method for using the chemical heat generating agent in the hydrate exploitation process comprises the following steps: under the pressure of 4-6 MPa, CO is introduced 2 The gas is mixed with the main agent I by a mixing pump according to a preset volume ratio to form foam liquid; simultaneously pumping the equal-volume foam liquid and the main agent II into a hydrate layer by a high-pressure pump, and performing a hydrate thermal recovery process.
The mixing condition of the main agent I and the auxiliary agent in this example 2 is as follows:
300mL of the main agent I is added into a high-pressure sapphire kettle, and CO is introduced under the condition of continuous stirring 2 12000mL of gas and 4-6 MPa of pressure are stirred for 30min, the foam volume is read, the mixture is kept stand, and then the foam volume corresponding to the change along with the time is recorded. Through research, the half-life time of the foam concentrate adopting biquaternary ammonium adipate in the embodiment 2 is 4h; and the half-life time of the foaming agent consisting of the span 80 and the Tween80 with the same concentration is 0.8h, which shows that the foaming agent has excellent foaming effect.
Example 3
A chemical heat generating agent for natural gas hydrate exploitation is disclosed, wherein a main agent I of the heat generating agent comprises the following components in percentage by mass and volume (W/V, g/mL): 1% of foaming agent, 2% of foam stabilizer, 10% of sodium nitrite and the balance of water; wherein the foaming agent is selected from bis-quaternary ammoniumAdipate salt and foam stabilizer are nano silicon dioxide particles. The auxiliary agent of the heat generating agent is SO 2 Main agents I and SO 2 Is 1:10, mixing the main agent I and the auxiliary agent according to the volume ratio to obtain the foam liquid. The main agent II of the heat generating agent is NH 4 Aqueous Cl solution, NH 4 The molar concentration of the Cl aqueous solution is equal to the molar concentration of the sodium nitrite in the foam concentrate.
The preparation of the main agent I comprises the following steps: adding part of water into a reaction vessel I, heating to 60 ℃, and then sequentially adding 100g of NaNO into the reaction vessel I under the stirring condition 2 10g of biquaternary ammonium salt adipate surfactant and 20g of silicon dioxide particles, adding the rest water till the total volume is 1000mL, and continuously stirring for 1h at 60 ℃ after the addition is finished till the components are uniformly dissolved to obtain the main agent I.
The preparation of the main agent II comprises the following steps: according to the NaNO in the foam liquid 2 Concentration preparation of NH 4 Adding water into a reaction vessel II, heating to 60 ℃, and then adding NH into the reaction vessel II under the condition of stirring 4 And Cl, and stirring at 60 ℃ for 1h after the addition is finished to obtain a main agent II.
The method for using the chemical heat generating agent in the hydrate exploitation process comprises the following steps: SO under the pressure of 4-6 MPa 2 The gas is mixed with the main agent I by a mixing pump according to a preset volume ratio to form foam liquid; and simultaneously pumping the foam liquid and the main agent II with the same volume into a hydrate layer by a high-pressure pump, thus carrying out the thermal recovery process of the hydrate.
Example 4
A chemical heat generating agent for natural gas hydrate mining, substantially as in example 3, except that: main agent I and SO 2 Is 1:40.
the performance tests were performed on the chemical heat generating agents of examples 1 to 4, specifically as follows:
the following hydrate mining experiments for heat release performance testing were conducted using samples synthesized in situ in the room. The saturation of hydrate phase in the hydrate sample is 30%, the saturation of gas phase is 70%, and the deposit adopts 70-100 mesh quartz sand.
1. Heat Release Rate comparison
The same concentration of the chemical heat generating agent (selected from example 1) and the acetic acid catalyst heat generating system are used for carrying out hydrate exploitation experiment, and the heat release rate of the chemical heat generating agent and the acetic acid catalyst heat generating system is compared, and the result is shown in figure 1. As can be seen from the figure, the peak of heat release of the chemical heat generating agent of the example 1 of the invention appears at a time which is obviously later than that of the acetic acid catalyst heat generating system, and the characteristic is more favorable for the deep energy supply of the hydrate exploitation process.
The same concentration of the chemical heat generating agent (example 3) and the sulfuric acid catalyst heat generating system were used to perform hydrate mining experiments, and the heat release rates of the two were compared, and the results are shown in fig. 2. It can be seen from the figure that the peak of heat release of the chemical heat generating agent of example 3 of the invention occurs at a time significantly slower than that of the sulfuric acid catalyst heat generating system, which is more favorable for the deep energy supply of the hydrate exploitation process.
2. Comparison of temperature changes in hydrate reservoirs under different thermal injection modes
Hydrate mining experiments were conducted using the same concentration of the chemical heat generating agent of the present invention (example 1 was selected), the acetic acid catalyst heat generating system, and hot water. The temperature change of the deep part of the reservoir in the hydrate generation kettle is shown in figure 3, the heat release of the embodiment 3 of the invention shows obvious slow release effect, and the heating effect is better, which is shown in the well shut-in stage, the chemical heat generating agent of the embodiment 3 can still generate chemical reaction and gradually reach the heat release peak value, the temperature rise amplitude in the hydrate reservoir is obviously higher than that of a conventional acetic acid catalyst heat generating system and a hot water injection mode, and the chemical heat generating agent of the invention has very obvious in-situ heating effect on the deep part of the reservoir.
3. Comparison of hydrate production efficiencies under different injection modes
The results of measuring and comparing the production efficiencies of the examples 1 to 4 of the present invention, the conventional acetic acid catalyst heat generating system, and the hot water hydrate are shown in table 1. As can be seen from the table, the production efficiency of each of examples 1 to 4 is significantly higher than that of the conventional heat generating system and the injection of hot water, wherein the production efficiency of example 3 is as high as 84%.
TABLE 1 hydrate recovery efficiency with different thermite injection modes
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (4)
1. A chemical heat generating agent for natural gas hydrate mining, the heat generating agent comprising: a main agent I, a main agent II and an auxiliary agent;
the main agent I comprises the following components in percentage by mass and volume: 10 to 32% of NaNO 2 1-7.5% of foaming agent, 2-7.5% of foam stabilizer and the balance of water; the foaming agent is cationic Gemini quaternary ammonium salt, and the cationic Gemini quaternary ammonium salt is biquaternary ammonium adipate; the foam stabilizer is a nanoparticle;
the auxiliary agent is acid gas selected from CO 2 And/or SO 2 And the volume ratio of the main agent I to the auxiliary agent is 1: 4-40, mixing the main agent I and the auxiliary agent according to the volume ratio to obtain a foam liquid;
the main agent II is NH 4 Aqueous solution of Cl, said NH 4 The molar concentration of the Cl aqueous solution is equal to that of sodium nitrite in the foam concentrate, and the NH is 4 The volume of the Cl aqueous solution is equal to the volume of the foam concentrate.
2. The chemothermic agent for natural gas hydrate mining of claim 1, wherein the nanoparticles are nanosilica particles.
3. Use of a chemothermic agent according to claim 1 or 2 for the recovery of natural gas hydrates.
4. The use according to claim 3, wherein the auxiliary agent and the main agent I are mixed under the pressure of 4-6 MPa to form a foam concentrate; and injecting the equal volume of the foam liquid and the main agent II into a hydrate layer simultaneously to perform a hydrate thermal recovery process.
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| CN104017556A (en) * | 2014-06-26 | 2014-09-03 | 中国石油大学(华东) | Self-heating foam system, and preparation method and application thereof |
| CA2989297A1 (en) * | 2015-07-24 | 2017-02-02 | Halliburton Energy Services, Inc. | Microbubbles for heat and/or gas generation in subterranean formations |
| US11236580B2 (en) * | 2019-09-04 | 2022-02-01 | Saudi Arabian Oil Company | Methods for improving oil recovery within a subterranean formation |
| CN211287645U (en) * | 2019-12-09 | 2020-08-18 | 聊城大学 | Large depth hydrate exploitation simulator |
| CN111849451B (en) * | 2020-07-24 | 2022-11-18 | 中国石油天然气集团有限公司 | Peak temperature controllable self-generated thermal fracturing fluid and preparation method and application thereof |
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