CN104877660A - Preparation method of stratum authigenic clean latent acids CAP for construction of nanometer apertures - Google Patents
Preparation method of stratum authigenic clean latent acids CAP for construction of nanometer apertures Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 57
- 238000010276 construction Methods 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title claims abstract 4
- 150000007513 acids Chemical class 0.000 title abstract 3
- 238000005260 corrosion Methods 0.000 claims abstract description 70
- 230000007797 corrosion Effects 0.000 claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000011435 rock Substances 0.000 claims abstract description 23
- 150000007524 organic acids Chemical class 0.000 claims abstract description 19
- 238000003795 desorption Methods 0.000 claims abstract description 8
- 238000003860 storage Methods 0.000 claims abstract description 4
- 150000007522 mineralic acids Chemical class 0.000 claims abstract 2
- 230000015572 biosynthetic process Effects 0.000 claims description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 45
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 38
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 26
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 26
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 238000006073 displacement reaction Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 14
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 235000019253 formic acid Nutrition 0.000 claims description 13
- 235000019260 propionic acid Nutrition 0.000 claims description 13
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 13
- 239000013543 active substance Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
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- 150000001412 amines Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004891 communication Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 2
- 238000005342 ion exchange Methods 0.000 claims 2
- 239000011707 mineral Substances 0.000 claims 2
- 229910000831 Steel Inorganic materials 0.000 claims 1
- 150000001242 acetic acid derivatives Chemical class 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 239000002734 clay mineral Substances 0.000 claims 1
- 239000008139 complexing agent Substances 0.000 claims 1
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- 230000001629 suppression Effects 0.000 claims 1
- 238000009736 wetting Methods 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 11
- 239000003079 shale oil Substances 0.000 abstract description 6
- 150000003863 ammonium salts Chemical class 0.000 abstract description 5
- 230000009466 transformation Effects 0.000 abstract description 5
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 229920008347 Cellulose acetate propionate Polymers 0.000 abstract 3
- 238000009470 controlled atmosphere packaging Methods 0.000 abstract 3
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 25
- 230000002269 spontaneous effect Effects 0.000 description 24
- 239000004575 stone Substances 0.000 description 16
- 239000003245 coal Substances 0.000 description 14
- 239000010430 carbonatite Substances 0.000 description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 9
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 9
- 235000011054 acetic acid Nutrition 0.000 description 8
- 230000003321 amplification Effects 0.000 description 7
- 229910001919 chlorite Inorganic materials 0.000 description 7
- 229910052619 chlorite group Inorganic materials 0.000 description 7
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 7
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 7
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 7
- 229910052901 montmorillonite Inorganic materials 0.000 description 7
- 238000003199 nucleic acid amplification method Methods 0.000 description 7
- 229940080314 sodium bentonite Drugs 0.000 description 7
- 229910000280 sodium bentonite Inorganic materials 0.000 description 7
- 239000012530 fluid Substances 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- 239000002817 coal dust Substances 0.000 description 4
- 239000010433 feldspar Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- SVMCDCBHSKARBQ-UHFFFAOYSA-N acetic acid;cobalt Chemical compound [Co].CC(O)=O SVMCDCBHSKARBQ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
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- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of stratum authigenic clean latent acid CAPs for construction of nanometer apertures and belongs to underground energy development reservoir transformation. According to rock components and principles of maximal rock corrosion rate, maximal fracturing pressure and construction pressure decreasing, and best nanometer apertures, an inorganic acid and an organic acid are intelligently prepared from stratum authigenic latent aldehyde, inorganic ammonium salt, organic ammonium and a surfactant under stratum conditions. The preparation method realizes acidification without tubular column replacement. The stratum authigenic clean latent acids CAP realize construction of nanometer aperture-based multi-stage netty cracks of filling area stratum, improve adsorbed gas and oil desorption speeds, improve a diversion capability and improve a storage capability and a yield. The stratum authigenic clean latent acids CAP are especially suitable for strong water-sensitive, coalbed methane, shale oil and gas and ultradense oil and gas stratum fracturing.
Description
Technical field:
The invention belongs to underground energy exploitation increasing the storage volume increase reservoir reconstruction, provide the stratum self-generating building nanoporous seam to clean potential sour CAP compound method especially.
Technical background:
Existing acidizing fluid speed of response is fast especially, and EFFECTIVE RANGE is extremely short, and easily forms sand plug, and acidizing effect is poor.Acidifying heavy corrosion shaft column, acidifying must replace tubes post.Replace tubes post needs week age, spends more than 10 ten thousand yuan.
The potential hydrochlorate acid of a kind of LZR that Zhang Huaixiang etc. are generated under certain condition by formaldehyde and halogen ammonium salt.Shengli Oil Field makes potential acid with ammonium halide-formaldehyde in 1994, generates hydrochloric acid on stratum.Southwest Petrol University develops and postpones sour RA system (liquid type): react rear obtained R-2 under certain condition by alkenes compounds, chlorine and catalyzer and postpone host, be oxidized the secondary agent of rear obtained R-3 delayed-action activator under certain condition by arene compounds, form R-4 solubility promoter by inorganic matter and surfactant compound.R-2, R-3, R-4 tri-kinds of materials add water to be mixed with and postpone acid, slowly generate hydrochloric acid at the formation temperature.Liu Youquan etc. with 28% (A+B)+18% chloracetate I have developed a kind of spontaneous acid system of compound being applicable to carbonate reservoir transformation under 150 DEG C of high temperature and generate HCl.
the use such as Yang Qimethyl-formiate+ammonium chloride generates hydrochloric acid on stratum.
Existing potential acid can only be used for compact reservoir transformation, improves flow conductivity, increase yield.Existing potential acid expands nanoporous seam for super tight reservoir, improve adsorbed gas, adsorbed oil the effect of desorption rate little, super tight reservoir adsorbed gas, the reserves of adsorbed oil and output can not be increased.
Existing fracturing liquid is difficult to the reservoir crushing super densification, high water-sensitive, high parting pressure.Even if crush reservoir also can only crush reservoir and make single seam, reservoir can be polluted.The stratum self-generating also not building nanoporous seam at present both at home and abroad cleans potential acid.
Summary of the invention:
The object of this invention is to provide a kind of construction, communication, expansion nanoporous seam stratum self-generating clean potential sour CAP compound method.The injection fluid that stratum self-generating cleans potential sour CAP is not acid on ground, is not acid at pit shaft, and injecting stratum neither be sour, and stopping just generating acid after reacting for some time after injecting under formation temperature, pressure.Stratum self-generating cleans potential sour CAP and does not corrode or low corrosion acid filling system device and shaft column, can not carry out stratum self-generating and clean potential sour CAP and inject construction operation by replace tubes post.Stratum self-generating cleans potential sour CAP makes the region of injection fluid process can the cementing matter of Denudation pore and wall, builds, links up, expands nanoaperture, greatly improve EFFECTIVE RANGE.The effect that stratum self-generating cleans potential sour CAP is the nanometer bullport seam forming guide, form the multistage network cracks such as nanometer, micron, millimeter for follow-up pressure break and establish good basis, the real desorption rate realizing raising adsorbed gas, adsorbed oil, increases reserves, increase yield simultaneously.Stratum self-generating cleans potential sour CAP and can also realize developing hot dry rock heat energy power-generating at earth any place.Cleaning potential sour CAP by injecting stratum self-generating, building, expanding nanoaperture, improving adsorbed gas, adsorbed oil desorption rate, realize the suitability for industrialized production of adsorbed gas, adsorbed oil.
Stratum self-generating cleans potential sour CAP and builds, links up, expands nanoaperture, improves based on desorption rate.Stratum self-generating cleans potential sour CAP and the seepage flow petroleum engineering based on seepage flow is transform as desorb petroleum engineering based on desorb.
Innovative point:
First generate formaldehyde under formation conditions; Then generate hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, carbonic acid under formation conditions simultaneously; Stratum alkane wisdom is utilized to generate formic acid, acetic acid, butyric acid, propionic acid; The potential sour CAP series of the comprehensive complete generating clean of system, belongs to international innovation, reaches the international leading level.
Stratum self-generating cleans one of them invention that potential sour CAP is inventor's wisdom nanometer pressure break, the invention of wisdom nanometer oil recovery series.
Practicality:
Hyper-tight sandstone hydrocarbon-bearing pool, super tight carbonate oil gas pool reservoir reconstruction need stratum self-generating to clean potential sour CAP.Develop the suction in sandstone reservoir, carbonate rock hydrocarbon reservoir in-depth exploitation basement rock, adsorbed oil, all needed stratum self-generating to clean potential sour CAP and carry out reservoir reconstruction.The pressure break of coal-seam gas, shale gas, shale oil, all needs stratum self-generating to clean potential sour CAP.The exploitation of hot dry rock heat energy is built and is manually stored up fluid layer, also needs stratum self-generating to clean potential sour CAP.Stratum self-generating cleans that potential sour CAP demand is large, market is large, required time has persistence.Stratum self-generating cleans the economic benefit of potential sour CAP, social benefit is all difficult to the appraisal.Stratum self-generating cleans potential sour CAP can increasing the storage volume increase, makes the oil gas energy industrialized developing of difficult exploitation, and the energy of China completely can self-sufficiency through productive labour fast, and break through and blocks the world of CNPC, the Chinese speed reformed can walk quickening greatly; A large amount of employment can be solved; More importantly ensure the energy demand that national all trades and professions grow at top speed, and be that country creates a large amount of income.
Stratum self-generating cleans potential sour CAP and has practicality widely, can organize production in enormous quantities.
Stratum self-generating cleans potential sour CAP and may be used for coal bed gas well, and hyper-tight sandstone, shale oil air water, grouan, carbonatite, mud stone, Sandy Silt oil gas water well, as table 1.
Table 1 stratum self-generating cleans potential sour CAP classification, model, feature
| Stratum self-generating cleans potential sour CAP | Model | Feature |
| The spontaneous clean potential acid of coal bearing seams | CAPco | Cementing matter in emphasis corrosion coal dust, hole seam and charges |
| The spontaneous clean potential acid of sandstone formation | CAPsa | Cementing matter in emphasis corrosion feldspar, sandstone, hole seam and charges |
| The spontaneous clean potential acid of shale formation | CAPsh | Cementing matter in emphasis corrosion shale, hole seam and charges |
| The spontaneous clean potential acid of granitic formation | CAPgr | Cementing matter in emphasis corrosion grouan, hole seam and charges |
| The spontaneous clean potential acid of carbonate formation | CAPca | Cementing matter in emphasis corrosion carbonatite, hole seam and charges |
| The spontaneous clean potential acid of mudstone stratum | CAPmu | Cementing matter in emphasis corrosion mud stone, hole seam and charges |
| Sandy Silt stratum self-generating cleans potential acid | CAPsm | Cementing matter in emphasis corrosion Sandy Silt, hole seam and charges |
Clean potential acid produced by example 1 ammonium salt
Reservoir temperature is less than 60 DEG C, and water soluble salt of ammonia, organic ammonium, proper catalyst solid organic acid, tensio-active agent generate hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, carbonic acid etc.
Example 2 urotropine produces clean potential acid
Reservoir temperature is greater than 60 DEG C, and urotropine, water soluble salt of ammonia, organic amine, proper catalyst solid organic acid, tensio-active agent generate hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, carbonic acid etc.Urotropine resolves into formaldehyde and ammonia in the weak acid of formation condition.Spontaneous formaldehyde reacts with ammonium salt under formation conditions and generates hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, carbonic acid etc.
Example 3 methyl alcohol produces clean potential acid.
Formation temperature is greater than 90 DEG C, catalyzer Cr
2o
3: V
2o
5be 4.5 ~ 5.5: 9.0 ~ 9.9, urea.Methanol oxidation produces formaldehyde.Formaldehyde reacts with ammonium salt under formation conditions and generates hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, carbonic acid etc.
Methyl alcohol, water soluble salt of ammonia, organic ammonium, proper catalyst solid organic acid, tensio-active agent generate hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid etc.
Example 4 methane produces clean potential acid
Ammonium nitrate fertilizer, water soluble salt of ammonia, organic amine, proper catalyst solid organic acid, tensio-active agent generate hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid etc.
Formation temperature is greater than 160 DEG C,
Nitrous oxide is resolved on the stratum that ammonium nitrate is greater than 160 DEG C in temperature.
MoO
3, Pa, Al
2o
3, urea etc. makes catalyzer, stratum methane CH
4by N
2o oxidation generates formaldehyde.
Spontaneous formaldehyde reacts with ammonium salt under formation conditions and generates hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, carbonic acid etc.
The spontaneous clean potential organic acid of example 5 oil and gas reservoir
With catalyst acetic acid cobalt, manganese acetate, and inject the air lower than 20% to stratum, under formation temperature, pressure, utilize the organism on stratum, inorganics to generate organic acid, as formic acid, acetic acid, propionic acid etc.
The alkane such as methane, ethane, propane on stratum, generates organic acid, as formic acid, acetic acid, propionic acid etc. with the dioxygen oxidation injecting air under catalyst acetic acid cobalt, manganese acetate effect.
Example 6 is for the spontaneous clean potential sour CAPco of coal bearing seams of CBM Fracturing acidifying
Feature is corrosion coal dust.Hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid etc. are generated, the cementing matter in corrosion coal dust, coal petrography hole seam and slotted wall face, hole with water soluble salt of ammonia, organic ammonium, proper catalyst solid organic acid, tensio-active agent.Coal petrography cleans the concrete composition of potential acid and content is specifically determined by general principle, general objective, coal petrography lithology, the water-soluble of base-material.
The performance of the spontaneous clean potential sour CAPco of 1% coal bearing seams is as follows: coal dust corrosion rate is greater than 1%, kaolinic corrosion rate is greater than 1%, the corrosion rate of montmorillonite is greater than 1.5%, illitic corrosion rate is greater than 0.5%, the corrosion rate of chlorite is greater than 0.5%, the corrosion rate of quartz is greater than 0.5%, the indoor displacement pressure resistance-reducing yield 20% ~ 70% of coal rock core, coal petrography core nanoporous seam amplification degree 10% ~ 100%, coal petrography drill core permeability rate increment rate 100% ~ 300%, coal bed gas well pressure break parting pressure reduces by 8% ~ 20%, coal bed gas well Fracturing Pressure reduces by 8% ~ 20%, sodium bentonite anti-dilative 100% ~ 200%, coal petrography water sensitive index-0.1 ~-10, the acid-sensitive index-0.1 ~-5 of coal petrography.
Example 7 is for the spontaneous clean potential sour CAPsa of sandstone formation of hyper-tight sandstone oil gas water well fracture acidizing
Feature is corrosion feldspar, quartz.Hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid etc. are generated, the cementing matter in corrosion feldspar, quartz, sandstone hole seam and slotted wall face, hole with the methane in urotropine, methyl alcohol or reservoir and corresponding catalyzer, water soluble salt of ammonia, organic ammonium, proper catalyst solid organic acid, tensio-active agent.Sandstone cleans the concrete composition of potential acid and content is specifically determined by general principle, general objective, formation lithology, stratum organic hydrocarbon, formation temperature, reservoir pressure, the water-soluble of base-material.
The performance of the spontaneous clean potential sour CAPsa of 1% sandstone formation is as follows:
Feldspar corrosion rate is greater than 1%, the corrosion rate of quartz is greater than 1%, kaolinic corrosion rate is greater than 1%, the corrosion rate of montmorillonite is greater than 1.5%, illitic corrosion rate is greater than 0.5%, the corrosion rate of chlorite is greater than 0.5%, the indoor displacement pressure resistance-reducing yield 20% ~ 70% of Sandstone Cores, sandstone core nanoporous seam amplification degree 10% ~ 100%, Permeability of Sandstone increment rate 100% ~ 300%, sandstone oil gas water well pressure break parting pressure reduces by 8% ~ 20%, sandstone oil gas water well Fracturing Pressure reduces by 8% ~ 20%, sodium bentonite anti-dilative 100% ~ 200%, sandstone water sensitive index-0.1 ~-10, the acid-sensitive index-0.1 ~-5 of sandstone.
Example 8 is for the spontaneous clean potential sour CAPsh of shale formation of shale gas well, shale oil well fracture acidizing
Feature is corrosion shale.Hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid etc. are generated, the cementing matter in corrosion shale, hole seam and slotted wall face, hole with the methane in urotropine, methyl alcohol or reservoir and corresponding catalyzer, water soluble salt of ammonia, organic ammonium, proper catalyst solid organic acid, tensio-active agent.Shale cleans the concrete composition of potential acid and content is specifically determined by general principle, general objective, formation lithology, stratum organic hydrocarbon, formation temperature, reservoir pressure, the water-soluble of base-material.
The performance of the spontaneous clean potential sour CAPsh of 1% shale formation is as follows: page stone corrosion rate is greater than 1%, kaolinic corrosion rate is greater than 1%, the corrosion rate of montmorillonite is greater than 1.5%, illitic corrosion rate is greater than 0.5%, the corrosion rate of chlorite is greater than 0.5%, the indoor displacement pressure resistance-reducing yield 20% ~ 70% of shale core, shale core nanoporous seam amplification degree 10% ~ 100%, shale rate of permeation increment rate 100% ~ 300%, shale oil gas-water well pressure break parting pressure reduces by 8% ~ 20%, shale oil gas-water well Fracturing Pressure reduces by 8% ~ 20%, sodium bentonite anti-dilative 100% ~ 200%, shale water sensitive index-0.1 ~-10, the acid-sensitive index-0.1 ~-5 of shale.
Example 9 is for the spontaneous clean potential sour CAPca of carbonate formation of carbonatite oil gas water well fracture acidizing
Feature is corrosion carbonatite.Hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid etc. are generated, the cementing matter in corrosion shale, hole seam and slotted wall face, hole with the methane in urotropine, methyl alcohol or reservoir and corresponding catalyzer, water soluble salt of ammonia, organic ammonium, proper catalyst solid organic acid, tensio-active agent.Carbonatite cleans the concrete composition of potential acid and content is specifically determined by general principle, general objective, formation lithology, stratum organic hydrocarbon, formation temperature, reservoir pressure, the water-soluble of base-material.
The spontaneous clean potential sour CAPca performance of 1% carbonate formation is as follows: carbonatite corrosion rate is greater than 1%, kaolinic corrosion rate is greater than 1%, the corrosion rate of montmorillonite is greater than 1.5%, illitic corrosion rate is greater than 0.5%, the corrosion rate of chlorite is greater than 0.5%, displacement pressure resistance-reducing yield 20% ~ 70% in carbonatite core chamber, carbonatite rock core nanoporous seam amplification degree 10% ~ 100%, carbonatite rate of permeation increment rate 100% ~ 300%, carbonatite oil gas water well pressure break parting pressure reduces by 8% ~ 20%, carbonatite oil gas water well Fracturing Pressure reduces by 8% ~ 20%, sodium bentonite anti-dilative 100% ~ 200%, carbonatite water sensitive index-0.1 ~-10, the acid-sensitive index-0.1 ~-5 of carbonatite.
Example 10 is for the spontaneous clean potential sour CAPgr of granitic formation of hot dry rock heat energy power-generating injection-production well fracture acidizing
Feature is corrosion grouan.Hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid etc. are generated, the cementing matter in corrosion shale, hole seam and slotted wall face, hole with the methane in urotropine, methyl alcohol or reservoir and corresponding catalyzer, water soluble salt of ammonia, organic ammonium, proper catalyst solid organic acid, tensio-active agent.Grouan cleans the concrete composition of potential acid and content is specifically determined by general principle, general objective, formation lithology, stratum organic hydrocarbon, formation temperature, reservoir pressure, the water-soluble of base-material.
The performance of the spontaneous clean potential sour CAPgr of 1% granitic formation is as follows: grouan corrosion rate is greater than 1%, kaolinic corrosion rate is greater than 1%, the corrosion rate of montmorillonite is greater than 1.5%, illitic corrosion rate is greater than 0.5%, the corrosion rate of chlorite is greater than 0.5%, displacement pressure resistance-reducing yield 20% ~ 70% in grouan core chamber, grouan rock core nanoporous seam amplification degree 10% ~ 100%, grouan rate of permeation increment rate 100% ~ 300%, grouan heat energy exploitation injection-production well pressure break parting pressure reduces by 8% ~ 20%, grouan heat energy exploitation injection-production well Fracturing Pressure reduces by 8% ~ 20%, sodium bentonite anti-dilative 100% ~ 200%, grouan water sensitive index-0.1 ~-10, the acid-sensitive index-0.1 ~-5 of grouan.
Example 11 is for the spontaneous clean potential sour CAPmu of mudstone stratum of mud stone oil gas water well fracture acidizing
Feature is corrosion mud stone.Hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid etc. are generated, the cementing matter in corrosion mud stone, hole seam and slotted wall face, hole with the methane in urotropine, methyl alcohol or reservoir and corresponding catalyzer, water soluble salt of ammonia, organic ammonium, proper catalyst solid organic acid, tensio-active agent.Mud stone cleans the concrete composition of potential acid and content is specifically determined by general principle, general objective, formation lithology, stratum organic hydrocarbon, formation temperature, reservoir pressure, the water-soluble of base-material.
The spontaneous clean potential sour CAPmu performance of 1% mudstone stratum is as follows: mud stone corrosion rate is greater than 1%, kaolinic corrosion rate is greater than 1%, the corrosion rate of montmorillonite is greater than 1.5%, illitic corrosion rate is greater than 0.5%, the corrosion rate of chlorite is greater than 0.5%, displacement pressure resistance-reducing yield 20% ~ 70% in mud stone core chamber, mud stone rock core nanoporous seam amplification degree 10% ~ 100%, mud stone rate of permeation increment rate 100% ~ 300%, mud stone oil gas water well pressure break parting pressure reduces by 8% ~ 20%, mud stone oil gas water well Fracturing Pressure reduces by 8% ~ 20%, sodium bentonite anti-dilative 100% ~ 200%, mud stone water sensitive index-0.1 ~-10, the acid-sensitive index-0.1 ~-5 of mud stone.
Example 12 cleans potential sour CAPsm for the Sandy Silt stratum self-generating of Sandy Silt oil gas water well fracture acidizing
Feature is corrosion Sandy Silt.Hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid etc. are generated, the cementing matter in corrosion mud stone, hole seam and slotted wall face, hole with the methane in urotropine, methyl alcohol or reservoir and corresponding catalyzer, water soluble salt of ammonia, organic ammonium, proper catalyst solid organic acid, tensio-active agent.Sandy Silt cleans the concrete composition of potential acid and content is specifically determined by general principle, general objective, formation lithology, stratum organic hydrocarbon, formation temperature, reservoir pressure, the water-soluble of base-material.
The performance that 1% Sandy Silt stratum self-generating cleans potential sour CAPsm is as follows: Sandy Silt corrosion rate is greater than 1%, kaolinic corrosion rate is greater than 1%, the corrosion rate of montmorillonite is greater than 1.5%, illitic corrosion rate is greater than 0.5%, the corrosion rate of chlorite is greater than 0.5%, displacement pressure resistance-reducing yield 20% ~ 70% in Sandy Silt core chamber, Sandy Silt rock core nanoporous seam amplification degree 10% ~ 100%, Sandy Silt rate of permeation increment rate 100% ~ 300%, Sandy Silt oil gas water well pressure break parting pressure reduces by 8% ~ 20%, Sandy Silt oil gas water well Fracturing Pressure reduces by 8% ~ 20%, sodium bentonite anti-dilative 100% ~ 200%, Sandy Silt water sensitive index-0.1 ~-10, the acid-sensitive index-0.1 ~-5 of Sandy Silt.
The potential acid of other rocks by that analogy.
With reference to non-patent literature:
1.
the research and apply of Zhang Huaixiang: LZR potential acid, rate of oil and gas recovery technology,1997 (1): 57-61
2.
pan Baofeng;
yang Dongmei;
liu Xuhui;
chen Ying Groceries;
li Hongbo: carbonate reservoir transformation uses spontaneous technic acid, Guangdong chemical industry, 2013 (7): 84,90
3. Gao Yu army. dioxide peroxide, retarded acid Compound-acid dissolve plugging technique [J]. Inner Mongol petrochemical complex, 2009 (5): 93-94.
4. bent rhythm flood, Li Jianbo. retarded acid acidifying experimental study [J]. Speciality Petrochemicals is in progress, and 2011,1 (1): 9-12.
5. king appoints virtue, Lan Di, Li Fuqiang. the development [J] of Novel retarding acid. and Changjiang University's journal, 2009,6 (3): 33-36.
6. in Chen Ping, Ma Guangyang. Acidizing fluid Study and appliance present situation [J]. Inner Mongol oil work, 2006 (6): 76-79.
7. Liu You power, Wang Lin, Xiong Ying. the spontaneous sour acid fluid system research [J] of high temperature carbonate rock. oil and gas chemical industry, 2011,40 (4): 367-369.
8.
yang Qi etc.: the potential sour desk research of carbonate rock reservoir deep transformation, science and technology and engineering,2012,12 (36): 9824-9827
Claims (9)
1. prepare the compound method that stratum self-generating cleans potential sour CAP, it is characterized in that to clean potential sour CAP at stratum self-generating mineral acid and organic acid stratum self-generating by the water-soluble preparation of general principle, general objective, formation lithology, formation temperature and base-material.The general principle that stratum self-generating cleans potential sour CAP is that rock corrosion rate is maximum, acidifying raffinate level of residue is minimum, EFFECTIVE RANGE is the longest, pressure break parting pressure and operation pressure decline maximum, nano level, micron order, millimeter grade hole seam is built best, nanoaperture adsorbed gas, adsorbed oil desorption rate are maximum, and flow conductivity increases maximum, and increasing the storage effect of increasing production is best.The general objective that 1% stratum self-generating cleans potential sour CAP is: rock corrosion inhibition rate 20% ~ 70%, acidifying raffinate level of residue 0mg/L ~ 200mg/L, rock corrosion EFFECTIVE RANGE improves 1 ~ 10 times, nanoporous seam expands 20%-100%, rate of permeation increases by 30% ~ 300%, displacement pressure declines maximum 10% ~ 60%, resistance-reducing yield is maximum, anti-dilative maximum (80% ~ 150%), water sensitive index-0.01 ~-10, acid-sensitive index-0.01 ~-10, Jia Min resistance, water seal resistance, hollow billet resistance drop low drop-out 8% ~ 20%.N-80 steel disc 90 DEG C of static etch rate are less than 2g/ (m
2 *h); 90 DEG C of Dynamic Corrosion speed are less than 10g/ (m
2 *h).
Note:
Jia Min resistance reduced rate=(oily expelling water inlet pressure-potential sour displacement of reservoir oil inlet pressure)/oily expelling water inlet pressure * 100%.
The pressure * 100% of water lock resistance reduced rate=(pressure of the pressure-potential sour displacement of local water displacement)/local water displacement.
Hollow billet resistance reduced rate=(capillary force P of local water displacement
50the capillary force P of-potential sour displacement
50the capillary force P of)/local water displacement
50* 100%.
Wetting phase phase relative permeability
Non-wetted phase phase relative permeability
Capillary pressure
Water drive method can be adopted, calculate capillary pressure with formula 1-4.
2., according to described in claim 1, it is characterized in that stratum self-generating cleans potential sour CAP and is easy to build nanoporous seam, improve desorption rate, make adsorbed gas, adsorbed oil energy industrialization exploitation.It is soluble in water and relative molecular mass is less than 500 that stratum self-generating cleans potential sour CAP, through liquid distributing vehicle or high-duty pump cycle balance water-soluble, molecular diameter 0.08nm ~ 0.27nm, be easy to enter clay mineral 6, surface Sauerstoffatom and surround empty suppression ion-exchange in diameter 0.28nm, link up nanoporous seam; And the hole seam being easy to enter basement rock 0.38nm suppresses ion-exchange, corrosion nanoporous slotted wall face rock simultaneously expands nanoporous seam.Stratum self-generating cleans potential sour CAP and had both been easy to corrosion construction, and linked up, has expanded nano grade pore seam; Can link up again, expand micron order, millimeter grade hole seam; Build the volume map cracking of nano level, micron order, grade, centimetre-sized, improve desorption rate, velocity of diffusion and seepage velocity simultaneously, make adsorbed gas, adsorbed oil energy industrialization exploitation.
3., according to described in claim 1,2, it is characterized in that the base-material that stratum self-generating cleans potential sour CAP is divided into two classes.The first kind is the potential aldehydes of stratum self-generating, water soluble salt of ammonia, organic amine, proper catalyst solid organic acid, tensio-active agent etc.These base-materials generate mineral acid hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, carbonic acid under formation conditions.Equations of The Second Kind base-material is a small amount of acetic acid salt, propionate compound, Sulfates catalyzer.These catalyzer utilize the organic hydrocarbon of stratum self enrichment (without the need to manually adding), formation temperature, reservoir pressure, using stratum as wisdom Reaktionsofen, generate organic acid formic acid, acetic acid, butyric acid, propionic acid etc. on stratum.Stratum self-generating cleans potential sour CAP makes acidifying raffinate level of residue reach minimum by complexing agent, dirt dispersion agent.
4. according to described in claim 1-3, it is characterized in that can be used alone first kind base-material, also can be used alone Equations of The Second Kind base-material, also can use first kind base-material and Equations of The Second Kind base-material simultaneously.
5., according to described in claim 1-4, it is characterized in that the composition that stratum self-generating cleans potential sour CAP is relative with content, specifically determined by general principle, general objective, formation lithology, stratum organic hydrocarbon, formation temperature, reservoir pressure, the water-soluble of base-material.The composition of clean potential sour CAP and be containing method for determination of amount: the first step, does rock corrosion and tests with hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, carbonic acid, formic acid, acetic acid, butyric acid, propionic acid, according to the descending sequence of rock corrosion rate respectively; Second step, does displacement test, the descending sequence of the resistance-reducing yield declined by displacement pressure with hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, carbonic acid, formic acid, acetic acid, butyric acid, propionic acid formation core respectively under formation temperature, reservoir pressure; 3rd step, tentatively determines hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, carbonic acid, formic acid, acetic acid, butyric acid, propionic acid consumption, prepares first formula; 4th step, does core flooding experiment with first formula, calculates resistance-reducing yield.5th step, revises formula repeatedly, until resistance-reducing yield is minimum.6th step, according to optimum formula, the more anti-consumption pushing away the first kind, Equations of The Second Kind base-material.
6. according to described in claim 1-5, it is characterized in that stratum self-generating clean potential sour CAP on ground, pit shaft be not acid, or the weak acid that corrodibility is very weak, using stratum as wisdom Reaktionsofen, inorganic acid and organic acid is generated, the corrosion petrographic formation of overlength distance, communication, expansion nano level, micron order, millimeter grade hole seam under formation temperature, reservoir pressure.
7., according to described in claim 1-6, it is characterized in that acidizing treatment not replace tubes post acidifying.
8. according to described in claim 1-7, it is characterized in that stratum self-generating cleans potential sour CAP and clean retarded acid compound use, effect doubles.See declaring patent: the clean retarded acid compound method of rock nanoporous seam do not built by replace tubes post.
9., according to described in claim 1-8, after it is characterized in that first using dissolving pressure break hydraulic pressure to split, then compound use stratum self-generating cleans potential sour CAP and clean retarded acid pressure break, builds nano level, the netted seam effect of micron order volume is good especially.See declaring patent: the clean dissolving pressure break liquid making method dissolving petrographic formation nanoporous seam.
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