CN102936493B - Hydrogenation thermochemical yield increase solution composition for low-permeability gas well - Google Patents
Hydrogenation thermochemical yield increase solution composition for low-permeability gas well Download PDFInfo
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- CN102936493B CN102936493B CN201210479956.5A CN201210479956A CN102936493B CN 102936493 B CN102936493 B CN 102936493B CN 201210479956 A CN201210479956 A CN 201210479956A CN 102936493 B CN102936493 B CN 102936493B
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 title claims abstract 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 31
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 20
- 230000035699 permeability Effects 0.000 claims abstract description 15
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012280 lithium aluminium hydride Substances 0.000 claims abstract description 12
- -1 lithium aluminum hydride Chemical compound 0.000 claims abstract description 12
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 11
- 229930006000 Sucrose Natural products 0.000 claims abstract description 11
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 11
- 239000005720 sucrose Substances 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910010082 LiAlH Inorganic materials 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 41
- 239000011435 rock Substances 0.000 abstract description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003345 natural gas Substances 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract description 3
- 235000013877 carbamide Nutrition 0.000 abstract 2
- 230000002708 enhancing effect Effects 0.000 abstract 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract 2
- 229910010084 LiAlH4 Inorganic materials 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 abstract 1
- 235000010344 sodium nitrate Nutrition 0.000 abstract 1
- 239000004317 sodium nitrate Substances 0.000 abstract 1
- 229950011008 tetrachloroethylene Drugs 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 43
- 238000004519 manufacturing process Methods 0.000 description 10
- 208000010392 Bone Fractures Diseases 0.000 description 6
- 206010017076 Fracture Diseases 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 230000000638 stimulation Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Gas Separation By Absorption (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of natural gas extraction, and particularly relates to a hydrogenation thermochemical yield increase solution composition capable of enhancing near-well-bore permeability of a gas well and enhancing single well productivity. The composition is composed of a solution 1 and a solution 2 in a mass ratio of 1:1, wherein the solution 1 is composed of ammonium nitrate NH4NO3, urea CO(NH2)2, ammonium chloride NH4Cl, sucrose C12H22O11 and water H2O; and the solution 2 is composed of sodium nitrate NaNO2, lithium aluminum hydride LiAlH4, sodium bromide NaBr and tetrachloroethylene C2Cl4. The reaction between the solution 1 and the solution 2 can generate heat and release abundant high-pressure gas; and the impact of the abundant high-temperature high-pressure gas is beneficial to forming microcracks in the near-well-bore rock stratum, thereby solving the problem of yield decrease due to lowered near-well-bore permeability in the extraction process.
Description
Technical field
The invention belongs to Natural gas extraction technical field.Be specifically related to a kind ofly can improve the component that gas well near-well-bore permeability can improve again the heat from hydrogenation chemistry Sweet natural gas volume increase solution of single well productivity.
Background technology
Low permeability gas field reserves occupy sizable ratio in the total proven reserve of China, because low permeability gas reservoir reservoir properties is poor, nonuniformity is strong, cause that Single Gas Well stable yields situation is poor, recovery ratio is low.Therefore,, in order to improve single well productivity, just must carry out High Efficiency Reform to reservoir.At present, fracture acidizing technology is conventional low permeability gas reservoir renovation technique.
Fracture acidizing technology is that full-bodied liquid is injected into stratum by high pressure, in stratum behind the artificial crack that forms high conduction, then acid solution is clamp-oned to kluftkarren wall in stratum, can transform from pressure break and two aspects of acidifying the penetrating quality of reservoir.Low permeability gas reservoir fracture acidizing volume increase transformation, can improve the seepage flow condition of immediate vicinity of wellbore, removes immediate vicinity of wellbore and pollutes, and improves output and the recovery ratio of low permeability gas reservoirs.But the zone thickness that fracture acidizing one-stop operation is processed is unsuitable blocked up, generally should be in 20m; And acid solution character temperature influence is larger, the applicable formation temperature of this technology should not be higher than 140 ℃, and well depth should be in 4000m; In addition, need to employ large-scale implement, construction is complicated, and cost is expensive.
The heat from hydrogenation chemistry method for increasing yield of low permeability gas reservoir is to utilize the chemical reaction be injected between two kinds of working solutions in the well physics chemical action to gas well immediate vicinity of wellbore, thereby improves the rate of permeation of immediate vicinity of wellbore, improves single well productivity.Compare with fracture acidizing technique, heat from hydrogenation chemistry method technique is simple, cost is low, be not subject to the impact of zone thickness and well depth condition, the volume increase time length is long, recovery ratio is higher, can application in low permeability gas reservoir exploitation.
Summary of the invention
The object of this invention is to provide and a kind ofly can improve the component that gas well near-well-bore permeability can improve again the heat from hydrogenation chemistry Sweet natural gas volume increase solution of single well productivity.
The present invention is achieved in that
First, according to structural parameter preparations two kinds of working solutions (No. 1 solution, No. 2 solution) of gasser, guarantee that No. 1 solution and No. 2 liquor capacity sums are less than the volume of gas well reaction zone.The space (see figure 1) of reaction zone in referring to from artificial bottom of a well to perforation district upper surface sleeve pipe farthest.
No. 1 solution, calculates the ammonium nitrate NH by 55.0～58.0% by quality and 100%
4nO
3, 16.2～18.2% urea CO (NH
2)
2, 10.3～11.5% ammonium chloride NH
4cI, 0.5～1.0% sucrose C
12h
22o
11with 14.0～16.0% water H
2o forms.
The preparation method of No. 1 solution:
1.1 first to the ammonium nitrate that adds 55～58% in container, pours subsequently 14.0～16.0% water into, stirs ten minutes;
1.2 add 16.2～18.2% urea afterwards, stir ten minutes;
1.3 add 10.3～11.5% ammonium chloride again to the solution obtaining, stir ten minutes;
1.4 finally add 0.5～1.0% sucrose, fully stir ten minutes, have so just made solution No. 1.
No. 2 solution, calculate the Sodium Nitrite NaNO by 40.5～45.0% by quality and 100%
2, 22.8～31.5% lithium aluminum hydride LiAlH
4(in Shanghai, Zi Yi chemical reagent work buys), 2.0～5.0% Sodium Bromide NaBr and 26.0～28.0% zellon C
2cl
4(in Shanghai, Zi Yi chemical reagent work buys) forms.
The preparation method of No. 2 solution:
2.1 first to the Sodium Nitrite that adds 40.5～45.0% in container;
2.2 then to the zellon of toppling over 26.0～30.0% in container, stirs;
2.3 again to the lithium aluminum hydride that adds 22.8～31.5% in container;
In 2.3 the most backward containers, add 2.0～5.0% Sodium Bromide, stir, this has just made solution No. 2.
No. 1 solution and No. 2 solution that prepare are injected in well by oil pipe successively, No. 1 solution and No. 2 solution sink to artificial bottom of a well (No. 1 solution and No. 2 solution 1:1 inputs in mass ratio) by self gravitation effect, and two kinds of solution start to occur chemical reaction in shaft bottom.The effect of sucrose both can reduce the thermostability of ammonium nitrate, can be used as again the stablizer of whole reaction process, and Sodium Bromide is the conditioning agent of speed of response.
First, lithium aluminum hydride and water react and put out heat:
LiAlH
4+4H
2O=LiOH+Al(OH)
3+4H
2+Q ①
The carrying out that the heat that 1. reaction discharged has been accelerated following reaction:
NaNO
2+NH
4CI=NaCI+N
2+2H
2O+Q ②
NaNO
2+CO(NH
2)
2+H
+=2N
2+CO
2+3H
2O+Na
++Q ③
4NaNO
2=2Na
2O+4NO+O
2 ④
The sour environment that reacts required is hydrolyzed acquisition by ammonium nitrate, and reaction equation is as follows:
NH
4NO
3+H
2O=H
++NO
3 -+NH
4OH ⑤
The generation of above-mentioned reaction can cause solution dehydrates No. 1, makes ammonium nitrate generation pyrolysis, generates a large amount of gas and heat, and reaction equation is as follows:
NH
4NO
3=N
2O+2H
2O+Q ⑥
NH
4NO
3=2N
2+4H
2O+O
2+Q ⑦
No. 1 solution and No. 2 solution reactions also can discharge a large amount of high pressure gas when producing heat, mainly contain H
2, N
2, CO
2, NO, O
2deng.As everyone knows, H under normal temperature condition
2the mean motion speed of molecule be other gas molecules 4-6 doubly, and along with the rising H of temperature
2molecular motion faster.Therefore, hydrogen can lead other gases by the perforation of sleeve pipe, to enter into rapidly the microporosity of rock stratum, under the continuous impact of a large amount of high temperature and high pressure gas, contributes to form tiny crack in nearly well band rock stratum.When high temperature and high pressure gas is penetrated in the hole of rock stratum and tiny crack within the short period of time, can cause local tiny crack place that microburst occurs, form large crack and be connected with other cracks, increase flaw area, improve the seepage flow condition of rock stratum.
The crack that microburst forms is communicated with original seepage channel, and this has improved the rate of permeation of gas well immediate vicinity of wellbore greatly.Continuous intensification along with reaction, have increasing gas and heat and constantly enter into rock stratum, make pressure sharply increase, can on the basis that expands primary fracture, can produce more new crack, thereby solve in recovery process because near-well-bore permeability reduces the production declining problem causing.
Accompanying drawing explanation
Fig. 1: gas well structural representation;
Wherein: well head 1; Oil pipe 2; Sleeve pipe 3; Perf 4; Artificial bottom of a well 5; Gas-bearing formation 6;
Embodiment
Embodiment 1: No. 1 gas well heat from hydrogenation chemistry volume increase test in Zhongyuan Oil Field
The geologic condition of No. 1 gas well and correlation parameter: reservoir lithology is mainly siltstone, also have more mud stone, calcareous silt rock; Average pore 5.8%, rate of permeation 0.8 * 10
-3μ m
2; Casing diameter
artificial bottom of a well 3982.83m; Perforation scope 3703.2～3967.7m; Stimulation work production fluid day before yesterday 0.4t, day produce oil 0.1t, daily gas 153m
3; By above data, show that reaction zone volume is 2590L.Prepare No. 1 solution 1040kg, No. 2 solution 1040kg.
No. 1 solution comprises: ammonium nitrate NH
4nO
3, urea CO (NH
2)
2, ammonium chloride NH
4cI, sucrose C
12h
22o
11, water H
2o, separately shared mass percent: 55%, 18.2%, 10.3%, 0.5%, 16.0%; The quality of each component is respectively: ammonium nitrate 572kg, urea 189.28kg, ammonium chloride 107.12kg, sucrose 5.2kg, water 166.4kg.
No. 2 solution comprises: Sodium Nitrite NaNO
2, lithium aluminum hydride LiAlH
4, Sodium Bromide NaBr, zellon C
2cl
4, shared mass percent separately: 40.5%, 31.5%, 2.0%, 26.0%.The quality of each component is respectively: Sodium Nitrite 421.2kg, lithium aluminum hydride 327.6kg, Sodium Bromide 20.8kg, zellon 270.4kg.
On December 23rd, 2011, is injected into No. 1 solution and No. 2 solution in well by oil pipe successively, and closing well reaction was resumed production after 12 hours.
After processing by the well stimulation of heat from hydrogenation chemistry, day production fluid, day produce oil, daily gas are respectively by original 0.4t, 0.1t, 153m
3bring up to 2.7t, 1.0t, 1408m
3, to effective producing days 135 days on May 8th, 2012, accumulative total increases 102 tons of oil, increases gas 150872m
3, continuous and effective still at present.
Embodiment 2: No. 2 gas well heat from hydrogenation chemistry volume increase tests in Zhongyuan Oil Field
The geologic condition of No. 2 gas wells and correlation parameter: reservoir lithology is mainly siltstone, also have more mud stone, calcareous silt rock; Average pore 6.7%, rate of permeation 0.85 * 10
-3μ m
2; Casing diameter
artificial bottom of a well 3792.62m; Perforation scope 3564.1～3774.6m; Stimulation work production fluid day before yesterday 0.6t, day produce oil 0.2t, daily gas 460m
3; By above data, show that reaction zone volume is 2513L.Prepare No. 1 solution 1040kg, No. 2 solution 1040kg.
No. 1 solution comprises: ammonium nitrate NH
4nO
3, urea CO (NH
2)
2, ammonium chloride NH
4cI, sucrose C
12h
22o
11, water H
2o, separately shared mass percent: 58%, 16.2%, 11%, 0.8%, 14.0%; The quality of each component is respectively: ammonium nitrate 603.2kg, urea 168.48kg, ammonium chloride 114.4kg, sucrose 8.32kg, water 145.6kg.
No. 2 solution comprises: Sodium Nitrite NaNO
2, lithium aluminum hydride LiAlH
4, Sodium Bromide NaBr, zellon C
2cl
4, shared mass percent separately: 45%, 22.8%, 5.0%, 27.2%.The quality of each component is respectively: Sodium Nitrite 468kg, lithium aluminum hydride 237.12kg, Sodium Bromide 52kg, zellon 282.88kg.
On December 23rd, 2011, is injected into No. 1 solution and No. 2 solution in well by oil pipe successively, and closing well reaction was resumed production after 12 hours.
After processing by the well stimulation of heat from hydrogenation chemistry, day production fluid, day produce oil, daily gas are respectively by original 0.6t, 0.2t, 460m
3bring up to 3.6t, 1.5t, 6987.2m
3, to effective producing days 141 days on May 8th, 2012, accumulative total increases 189 tons of oil, increases gas 932000m
3, continuous and effective still at present.
Embodiment 3: No. 3 gas well heat from hydrogenation chemistry volume increase tests in Zhongyuan Oil Field
The geologic condition of No. 3 gas wells and correlation parameter: reservoir lithology is mainly siltstone, also have more mud stone, calcareous silt rock; Average pore 4.7%, rate of permeation 0.68 * 10
-3μ m
2; Casing diameter
artificial bottom of a well 3914.00; Perforation scope 3751.2～3889.1m; Stimulation work production fluid day before yesterday 0.2t, day produce oil 0.05t, daily gas 95m
3; By above data, show that reaction zone volume is 1508L.Prepare No. 1 solution 780kg, No. 2 solution 780kg.
No. 1 solution comprises: ammonium nitrate NH
4nO
3, urea CO (NH
2)
2, ammonium chloride NH
4cI, sucrose C
12h
22o
11, water H
2o, separately shared mass percent: 56%, 17%, 11.5%, 0.5%, 15%; The quality of each component is respectively: ammonium nitrate 436.8kg, urea 132.6kg, ammonium chloride 89.7kg, sucrose 3.9kg, water 117kg.
No. 2 solution comprises: Sodium Nitrite NaNO
2, lithium aluminum hydride LiAlH
4, Sodium Bromide NaBr, zellon C
2cl
4, shared mass percent separately: 42%, 27%, 3%, 28%.The quality of each component is respectively: Sodium Nitrite 327.6kg, lithium aluminum hydride 210.6kg, Sodium Bromide 23.4kg, zellon 218.4kg.
On December 23rd, 2011, is injected into No. 1 solution and No. 2 solution in well by oil pipe successively, and closing well reaction was resumed production after 12 hours.
After processing by the well stimulation of heat from hydrogenation chemistry, day production fluid, day produce oil, daily gas are respectively by original 0.2t, 0.05t, 95m
3bring up to 1.5t, 0.2t, 1174.3m
3, to effective producing days 140 days on May 8th, 2012, accumulative total increases 19.8 tons of oil, increases gas 125064.8m
3, continuous and effective still at present.
Claims (2)
1. for a solution component for Low Permeability Gas Well heat from hydrogenation chemistry volume increase, it is characterized in that: No. 1 solution and No. 2 solution compositions that by mass ratio, are 1:1, by quality and 100% calculating, No. 1 solution is by 55.0～58.0% ammonium nitrate NH
4n О
3, 16.2～18.2% urea CO (NH
2)
2, 10.3～11.5% ammonium chloride NH
4cI, 0.5～1.0% sucrose C
12h
22o
11with 14.0～16.0% water H
2o forms; No. 2 solution is by 40.5～45.0% Sodium Nitrite NaNO
2, 22.8～31.5% lithium aluminum hydride LiAlH
4, 2.0～5.0% Sodium Bromide NaBr and 26.0～28.0% zellon C
2cl
4form; And be that No. 1 solution and No. 2 solution that prepare are injected in well by oil pipe successively, No. 1 solution and No. 2 solution sink to artificial bottom of a well by self gravitation effect, and two kinds of solution start to occur chemical reaction in shaft bottom.
2. a kind of solution component for the volume increase of Low Permeability Gas Well heat from hydrogenation chemistry as claimed in claim 1, is characterized in that: the volume sum of No. 1 solution and No. 2 solution is less than the volume of gas well reaction zone.
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| CN105672963B (en) * | 2016-01-06 | 2017-11-21 | 吉林冠通能源科技有限公司 | A kind of well production increment method that hydrogen component is released using hydration reaction |
| CN111808590B (en) * | 2020-08-12 | 2022-07-29 | 延安市永科石油工程技术服务有限公司 | Environment-friendly energy-increasing oil and water well blocking remover capable of rapidly reacting at normal temperature |
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| CA1233410A (en) * | 1984-06-28 | 1988-03-01 | Mobil Oil Corporation | Method and apparatus for plugging a wellbore in high impulse fracturing |
| US4590997A (en) * | 1985-01-28 | 1986-05-27 | Mobil Oil Corporation | Controlled pulse and peroxide fracturing combined with a metal containing proppant |
| US4787456A (en) * | 1987-04-10 | 1988-11-29 | Mobil Oil Corporation | Method to improve matrix acidizing in carbonates |
| US4917185A (en) * | 1987-04-10 | 1990-04-17 | Mobil Oil Corporation | Method to improve matrix acidizing in carbonates |
| US4982792A (en) * | 1989-12-29 | 1991-01-08 | Mobil Oil Corporation | Method to reduce movement of a CPF device via a shear-thickening fluid |
| CN101113669B (en) * | 2007-07-18 | 2011-09-07 | 中国石油集团川庆钻探工程有限公司 | Fracturing method for improving low permeability reservoir productivity |
| CN101230261A (en) * | 2008-01-09 | 2008-07-30 | 韩炜 | New method for oil well yield increasing and hydrogen release active reagent components |
| CN101560131B (en) * | 2009-05-31 | 2012-01-25 | 西安石油大油气科技有限公司 | Suspending detonator and preparation method thereof |
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