CN111234800A - Emulsified crosslinked acid and preparation method thereof - Google Patents
Emulsified crosslinked acid and preparation method thereof Download PDFInfo
- Publication number
- CN111234800A CN111234800A CN201811444315.XA CN201811444315A CN111234800A CN 111234800 A CN111234800 A CN 111234800A CN 201811444315 A CN201811444315 A CN 201811444315A CN 111234800 A CN111234800 A CN 111234800A
- Authority
- CN
- China
- Prior art keywords
- acid
- parts
- crosslinking agent
- crosslinking
- emulsified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims abstract description 169
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 65
- 238000004132 cross linking Methods 0.000 claims abstract description 56
- 239000003921 oil Substances 0.000 claims abstract description 49
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000005260 corrosion Methods 0.000 claims abstract description 24
- 230000007797 corrosion Effects 0.000 claims abstract description 24
- 239000003112 inhibitor Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 239000002562 thickening agent Substances 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 8
- 239000002199 base oil Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 33
- -1 iron ion Chemical class 0.000 claims description 24
- 239000000839 emulsion Substances 0.000 claims description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 239000002283 diesel fuel Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 229920002401 polyacrylamide Polymers 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- 229960001484 edetic acid Drugs 0.000 claims description 7
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 7
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 claims description 6
- 229920005615 natural polymer Polymers 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 229960005078 sorbitan sesquioleate Drugs 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 239000010779 crude oil Substances 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 229920001059 synthetic polymer Polymers 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229940031709 peg-30-dipolyhydroxystearate Drugs 0.000 claims description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 229960004106 citric acid Drugs 0.000 claims description 2
- 229940100515 sorbitan Drugs 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims 1
- 239000000665 guar gum Substances 0.000 claims 1
- 229960002154 guar gum Drugs 0.000 claims 1
- 235000010417 guar gum Nutrition 0.000 claims 1
- 230000000979 retarding effect Effects 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 17
- 238000011160 research Methods 0.000 description 13
- 238000007789 sealing Methods 0.000 description 13
- 239000003208 petroleum Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000011435 rock Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 229920013818 hydroxypropyl guar gum Polymers 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000001370 static light scattering Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/725—Compositions containing polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Colloid Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses an emulsified crosslinked acid which comprises the following components in parts by volume: 60-80 parts of crosslinking acid base liquid, preferably 65-75 parts; 40-20 parts of an oil phase, preferably 35-25 parts; 0.6 to 1.5 parts of cross-linking agent, preferably 0.8 to 1.2 parts. The crosslinking acid base solution comprises the following components in parts by weight: 90-98 parts of hydrochloric acid solution, 1.5-2 parts of corrosion inhibitor, 1-1.5 parts of iron ion stabilizer and 0.6-0.9 part of acid thickener; the oil phase comprises the following components in parts by weight: 3-5 parts of a high-efficiency emulsifier, preferably 3.5-4.5 parts; 95-97 parts of base oil, preferably 95.5-96.5 parts. The emulsified crosslinked acid is a novel acid solution system combining crosslinked acid and emulsified acid, is simple in preparation method, and has the advantages of small particle size, high apparent viscosity, good temperature stability, good retarding effect and the like.
Description
Technical Field
The invention relates to an emulsified crosslinked acid and a preparation method thereof, belonging to the field of acid fracturing production increase of carbonate reservoirs.
Background
With the continuous deepening of the exploration and development of the high-temperature carbonate reservoir, higher requirements are put forward on the performance of an acid liquor system, and a novel high-temperature-resistant retarded acid liquor system needs to be developed urgently.
The cross-linking acid and the emulsified acid are two common retarding acid liquid systems for the acid fracturing modification of the low-permeability carbonate reservoir. The crosslinked acid is prepared by adding thickener (or gelling agent) into acid (such as hydrochloric acid) to increase acid solution viscosity, adding crosslinking agent to form adjustable gel system, and further reducing H+The diffusion rate is transferred, the fluid loss is reduced, the acid liquid action distance is prolonged, and the acid fracturing effect is improved. The emulsified acid is an acid-in-oil emulsion formed by mixing an oil phase and an acid phase, and has the advantages of good retarding performance, small filtration loss, low corrosion rate and the like. The common emulsified acid internal phase is a common hydrochloric acid (or hydrofluoric acid) acid system, and when the emulsion is broken, the acid internal phase does not reduce H+The ordinary acid solution reacts with the rock quickly, and meanwhile, the lactic acid system has poor temperature resistance and stability and is not suitable for high-temperature carbonate reservoir acid fracturing application.
Chinese patent with publication number CN104194767A mentions a high temperature resistant emulsified acid solution, and the technical scheme thereof forms a high temperature emulsified acid system by selecting a high-efficiency emulsifier, but has the problems of poor temperature resistance, poor high temperature retarding effect and the like, so that a novel high temperature retarding acid system is continuously developed.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an emulsified cross-linked acid with a novel structure. In particular to an emulsified crosslinked acid and a preparation method thereof. The invention combines the excellent performance of the crosslinking acid and the emulsifying acid into oneAnd a novel acid liquor system with excellent performance is obtained by utilizing the binary synergistic effect. The cross-linked acid is wrapped by the oil phase to form an acid-in-oil emulsified acid system with a novel structure. Internal phase crosslinking acid moderating H without breaking emulsion structure+The ion diffusion coefficient reduces the concentration of H + ions contacting with rocks through an oil phase, thereby reducing acid rock reaction; when the emulsion is damaged by shearing or high temperature, the cross-linked acid flows out of the solution and directly contacts with rocks for reaction, and the acid rock reaction is reduced due to the retarding effect of the cross-linked acid, so that the emulsified cross-linked acid has better retarding effect than the emulsified acid. Meanwhile, when the acid internal phase is crosslinked, the emulsion stability is further improved, the temperature stability of the emulsion is increased, and the penetration depth of the acid solution is further increased. Compared with the conventional emulsified acid liquid system, the emulsified crosslinked acid obtained by the technical scheme of the invention has the characteristics of better retarding performance, stability, temperature resistance and the like, and has a good acidification effect after being injected into a stratum.
According to one aspect of the present invention, there is provided an emulsified crosslinked acid comprising a crosslinking acid base fluid, an oil phase and a crosslinking agent.
According to the preferred embodiment of the present invention, the content of each component is, in parts by volume: 60-80 parts of crosslinking acid base liquid, preferably 65-75 parts; 20-40 parts of an oil phase, preferably 25-35 parts; 0.6 to 1.5 parts of cross-linking agent, preferably 0.8 to 1.2 parts.
According to some embodiments of the invention, the crosslinking agent comprises a surface crosslinking acid crosslinking agent and/or a subsurface crosslinking acid crosslinking agent; preferably, the crosslinking agent for surface crosslinking acid comprises at least one of an organic zirconium crosslinking agent, an organic titanium crosslinking agent and a phenolic resin crosslinking agent, and the crosslinking agent for subsurface crosslinking acid comprises at least one of an organic zirconium crosslinking agent, an organic titanium crosslinking agent, an organic aluminum crosslinking agent and an iron ion crosslinking agent.
According to some embodiments of the invention, the crosslinking acid-based fluid comprises the following components in parts by weight:
90-98 parts of hydrochloric acid solution, preferably 92-97.0 parts; 1.5-2 parts of corrosion inhibitor, preferably 1.2-1.8 parts; 1-1.5 parts of iron ion stabilizer, preferably 1.2-1.4 parts; 0.6-0.9 part of thickening agent for acid, preferably 0.7-0.8 part.
According to a preferred embodiment of the invention, the concentration of the hydrochloric acid solution is between 15% and 30% by weight, preferably between 15% and 20% by weight.
According to a preferred embodiment of the present invention, the iron ion stabilizer is selected from at least one of citric acid, ethylenediaminetetraacetic acid, ascorbic acid and acetic acid.
According to some embodiments of the invention, the corrosion inhibitor is a high temperature corrosion inhibitor; the high-temperature corrosion inhibitor is at least one of imidazoline corrosion inhibitors and Mannich base corrosion inhibitors.
According to some embodiments of the invention, the acid thickener is at least one of a synthetic polymer and a natural polymer.
According to a preferred embodiment of the invention, the synthetic polymer is chosen from thickeners for polyacrylamide acids and the natural polymer is chosen from natural polymers of the guar type.
According to a preferred embodiment of the invention, the oil phase comprises the following components in parts by weight: 3-5 parts of a high-efficiency emulsifier, preferably 3.5-4.5 parts; 95-97 parts of base oil, preferably 95.5-96.5 parts.
According to some embodiments of the invention, the high efficiency emulsifier is selected from at least one of PEG-30 dipolyhydroxystearate, sorbitan sesquioleate, sorbitan fatty acid esters, polyoxyethylene octylphenol ether-10, dodecylamine, tetradecylamine, and hexadecylamine.
According to some embodiments of the invention, the base oil is selected from at least one of diesel, kerosene, white oil, and light crude oil.
According to another aspect of the present invention, there is provided a method for preparing the above emulsified crosslinked acid, comprising mixing a crosslinking acid base solution, an oil phase and a crosslinking agent.
According to a preferred embodiment of the present invention, the method for preparing the emulsified crosslinked acid may comprise the steps of:
A1. dropwise adding the crosslinking acid groups into the oil phase to obtain a mixture;
A2. to the mixture obtained in step A1, a ground crosslinking agent is added.
According to some embodiments of the invention, the cross-linking acid-based fluid is prepared by: preparing the hydrochloric acid solution, adding a thickening agent for acid, an iron ion stabilizer and a corrosion inhibitor under full stirring, uniformly stirring, sealing, and standing at room temperature to obtain the cross-linked acid base solution.
According to a specific embodiment of the present invention, the method for preparing the crosslinking acid-based fluid may include the steps of:
1) preparing the hydrochloric acid solution;
2) stirring the hydrochloric acid solution at a stirring speed of not less than 500 r/min;
3) adding a thickening agent for acid under the stirring condition, and continuously stirring for 30-50 minutes;
4) and then sequentially adding an iron ion stabilizer and a corrosion inhibitor, uniformly stirring, sealing, standing at room temperature for 4-6 hours, and obtaining the cross-linked acid base solution.
According to some embodiments of the invention, the method of preparing the oil phase may comprise the steps of: taking at least one of diesel oil, kerosene, white oil and light crude oil according to the dosage, adding the high-efficiency emulsifier, stirring for dissolving, and sealing for later use.
According to a preferred embodiment of the present invention, the step a1 can be implemented as follows: dropwise adding the crosslinking acid groups into the oil phase according to the dosage, and stirring during and after the dropwise adding process, wherein the stirring speed is 1000-3000 r/min, preferably 1500-2500 r/min; after the dropwise addition is finished, stirring is continuously carried out for 10-30 min, preferably for 15-25 min.
According to an embodiment of the present invention, the step a2 can be implemented as follows: dripping the ground cross-linking agent into the mixture obtained in the step A1, and stirring at the speed of 1000-3000 r/min, preferably 1500-2500 r/min during and after the dripping process; and after the dropwise addition is finished, continuously stirring for 3-5 min.
According to some embodiments of the present invention, the method of preparing the emulsified crosslinked acid may also include the steps of:
B1. adding an underground cross-linking agent into a cross-linking acid base solution to obtain a mixed emulsion;
B2. and (3) dropwise adding the mixed emulsion obtained in the step B1 into the oil phase.
According to some embodiments of the invention, the cross-linking acid-based fluid is prepared by: preparing the hydrochloric acid solution, adding a thickening agent for acid, an iron ion stabilizer and a corrosion inhibitor under full stirring, uniformly stirring, sealing, and standing at room temperature to obtain the cross-linked acid base solution.
According to a specific embodiment of the present invention, the method for preparing the crosslinking acid-based fluid may include the steps of:
1) preparing the hydrochloric acid solution;
2) stirring the hydrochloric acid solution at a stirring speed of not less than 500 r/min;
3) adding a thickening agent for acid under the stirring condition, and continuously stirring for 30-50 minutes;
4) and then sequentially adding an iron ion stabilizer and a corrosion inhibitor, uniformly stirring, sealing, standing at room temperature for 4-6 hours, and obtaining the cross-linked acid base solution.
According to some embodiments of the invention, the method of preparing the oil phase may comprise the steps of: taking at least one of diesel oil, kerosene, white oil and light crude oil according to the dosage, adding the high-efficiency emulsifier, stirring for dissolving, and sealing for later use.
According to a preferred embodiment of the present invention, the step B1 can be performed as follows: dripping an underground cross-linking agent into the cross-linking acid base solution, and stirring during and after the dripping at the speed of 1000-3000 r/min, preferably 1500-2500 r/min; and after the dropwise addition is finished, continuously stirring for 3-5 min.
According to an embodiment of the present invention, the step B2 can be implemented as follows: b1, dropwise adding the mixed emulsion obtained in the step B1 into an oil phase according to the dosage, and stirring during and after the dropwise adding process, wherein the stirring speed is 1000-3000 r/min, preferably 1500-2500 r/min; after the dropwise addition is finished, stirring is continuously carried out for 10-30 min, preferably for 15-25 min.
In the present invention, there is no particular requirement for the dropping speed in each step, and it is sufficient to add the liquid to be dropped in the form of droplets visible to the naked eye to the liquid to be added.
The emulsified crosslinked acid provided by the invention integrates the advantages of the crosslinked acid and the emulsified acid, has excellent performance, and is a novel emulsified crosslinked acid. The novel emulsified crosslinked acid is different from the conventional emulsified acid, and the crosslinked acid is used for replacing the common acid internal phase, so that the viscosity of the acid internal phase is increased, and the H is reduced+The diffusion rate, and further the stability of the emulsified acid and the acidification retarding effect are increased. And the cross-linking agent is added, so that the slowing effect and the fluid loss reducing effect are better after the emulsion is broken.
Detailed Description
The present invention will be described in further detail with reference to specific examples below:
example 1
1) Preparing a cross-linking acid base solution from the following components in parts by weight: taking 94.8 parts of hydrochloric acid solution (the concentration is 15 percent by weight), slowly adding 0.6 part of polyacrylamide thickening agent SRAP-1 for acid (produced by China petrochemical engineering technical research institute, SRAP-1) at the rotating speed of 500r/min, stirring for half an hour to form uniform solution, then adding 1.2 parts of iron ion stabilizer (ethylenediamine tetraacetic acid, Tianjin photochemical reagent plant) and 1.7 parts of ketoaldehyde amine condensate corrosion inhibitor (produced by China petrochemical engineering technical research institute), stirring uniformly, sealing, standing at room temperature for 1 hour;
2) preparing an oil phase from the following components in parts by weight: heating and dissolving 3 parts of sorbitan fatty acid ester and 0.5 part of dodecylamine in 96.5 parts of diesel oil, uniformly stirring, and cooling to room temperature for later use;
3) preparing an emulsion according to the following components in parts by volume: slowly dripping the prepared crosslinking acid base liquid into an oil phase under the condition that the stirring speed is 2500r/min, wherein the volume ratio of the dosage of the two phases is that of the crosslinking acid base liquid: the oil phase is 70:30, and stirring is continued for 15min after the dripping is finished;
4) 0.8 part of organic zirconium crosslinking agent (produced by China petrochemical petroleum engineering technical research institute) is slowly added into the emulsion, and the emulsion crosslinking acid is obtained after slow stirring for 3 minutes.
Example 2
1) Preparing a cross-linking acid base solution from the following components in parts by weight: taking 95.7 parts of hydrochloric acid solution with the concentration of 15 percent by weight, slowly adding 0.7 part of polyacrylamide thickening agent SRAP-1 (SRAP-1 produced by China petrochemical petroleum engineering technical research institute) for acid at the rotating speed of 500r/min, stirring for half an hour to form uniform solution, then adding 1.1 part of iron ion stabilizer (ethylenediamine tetraacetic acid, Tianjin photochemical reagent factory) and 1.6 parts of imidazoline corrosion inhibitor (sold in the market), stirring uniformly, sealing, standing at room temperature for 1 hour;
2) preparing an oil phase from the following components in parts by weight: heating and dissolving 3 parts of sorbitan sesquioleate and 0.5 part of tetradecylamine in 96.5 parts of diesel oil, uniformly stirring, and cooling to room temperature for later use;
3) preparing the emulsified crosslinking acid according to the following components in parts by volume: slowly dripping the prepared crosslinking acid base liquid into an oil phase under the condition that the stirring speed is 2000r/min, wherein the volume ratio of the dosage of the two phases is that of the crosslinking acid base liquid: the oil phase is 80:20, and stirring is continued for 15min after the dripping is finished;
4) 0.9 part of organic titanium crosslinking agent (produced by China petrochemical petroleum engineering technical research institute) is slowly added into the emulsion, and the emulsion crosslinking acid is obtained after slow stirring for 3 minutes.
Example 3
1) Preparing a cross-linking acid base solution from the following components in parts by weight: taking 96.5 parts of hydrochloric acid solution with the concentration of 15 percent by weight, slowly adding 0.7 part of polyacrylamide thickening agent SRAP-1 (produced by China petrochemical petroleum engineering technical research institute, SRAP-1) for acid at the rotating speed of 500r/min, stirring for half an hour to form uniform solution, then adding 1.2 parts of iron ion stabilizer (ethylenediamine tetraacetic acid, Tianjin photochemical reagent factory) and 1.6 parts of imidazoline corrosion inhibitor (sold in the market), stirring uniformly, sealing, standing at room temperature for 1 hour;
2) preparing an oil phase from the following components in parts by weight: heating and dissolving 3 parts of sorbitan sesquioleate and 1 part of tetradecylamine in 96.5 parts of diesel oil, uniformly stirring, and cooling to room temperature for later use;
3) preparing the emulsified crosslinking acid according to the following components in parts by volume: slowly dripping the prepared crosslinking acid base liquid into an oil phase under the condition that the stirring speed is 2000r/min, wherein the volume ratio of the dosage of the two phases is that of the crosslinking acid base liquid: the oil phase is 70:30, and stirring is continued for 20min after the dripping is finished;
4) slowly adding 1.0 part of organic titanium crosslinking agent (produced by China petrochemical petroleum engineering technical research institute) into the emulsion, and slowly stirring for 3 minutes to obtain the emulsified crosslinking acid.
Example 4
The procedure was the same as in example 3 except that 0.8 part of the organic titanium crosslinking agent was added.
Example 5
The procedure was the same as in example 3 except that 1.2 parts of the organic titanium crosslinking agent was added.
Example 6
The procedure was the same as in example 3 except that 0.8 parts of the organic zirconium crosslinking agent was added.
Example 7
The procedure was the same as in example 3 except that 1.0 part of the organic zirconium crosslinking agent was added.
Example 8
The procedure was the same as in example 3 except that 1.2 parts of the organozirconium cross-linking agent was added.
Example 9
The procedure was the same as in example 3 except that 0.8 part of a phenolic resin crosslinking agent was added.
Example 10
The procedure was the same as in example 3 except that 1.0 part of a phenolic resin crosslinking agent was added.
Example 11
The procedure was the same as in example 3 except that 1.2 parts of a phenolic resin crosslinking agent was added.
Example 12
1) Preparing a cross-linking acid base solution from the following components in parts by weight: taking 93.6 parts of 15% wt hydrochloric acid solution, slowly adding 0.8 part of polyacrylamide thickening agent SRAP-1 for acid (SRAP-1 produced by China petrochemical engineering technical institute), stirring for half an hour at the rotating speed of 500r/min to form a uniform solution, then adding 1.3 parts of iron ion stabilizer (produced by acetic acid, Tianjin photoreplication chemical reagent factory) and 1.6 parts of quinoline quaternary ammonium salt (sold in the market), stirring uniformly, sealing, standing at room temperature and standing for 1 hour;
2) slowly adding 1.0 part of organic titanium crosslinking agent (produced by China petrochemical petroleum engineering technical research institute) into the crosslinking acid base solution;
3) preparing an oil phase from the following components in parts by weight: heating and dissolving 3 parts of PEG-30 dipolyhydroxystearate and 1 part of dodecylamine in 96.0 parts of diesel oil, uniformly stirring, and cooling to room temperature for later use;
4) preparing an emulsified cross-linked acid system according to the following components in parts by volume: slowly dripping the prepared crosslinking acid base liquid added with the crosslinking agent into an oil phase under the condition that the stirring speed is 1500r/min, wherein the volume ratio of the dosage of two phases is that of the crosslinking acid base liquid: the oil phase is 65:35, and the emulsified cross-linked acid is obtained after stirring for 25min after the dripping is finished.
Example 13
1) Preparing a cross-linking acid base solution from the following components in parts by weight: taking 96.5 parts of hydrochloric acid solution with the concentration of 15 percent by weight, slowly adding 0.6 part of hydroxypropyl guar gum (produced by Kyoho Kunshan Jingkun oilfield science and technology company in Jiangsu Kunshan) at the rotating speed of 500r/min, stirring for half an hour to form uniform solution, then adding 1.2 parts of iron ion stabilizer (citric acid, produced by Tianjin photoresistance chemical reagent factory) and 1.7 parts of imidazoline corrosion inhibitor (sold in market), stirring uniformly, sealing, standing at room temperature and standing for 1 hour;
2) slowly adding 0.9 part of a phenolic resin crosslinking agent (sold in the market) into the crosslinking acid base solution;
3) preparing an oil phase from the following components in parts by weight: heating and dissolving 3 parts of sorbitan fatty acid ester 0 and 1.0 part of dodecylamine in 96.0 parts of diesel oil, uniformly stirring, and cooling to room temperature;
3) preparing the emulsified crosslinking acid according to the following components in parts by volume: slowly dripping the prepared crosslinking acid base liquid added with the crosslinking agent into an oil phase under the condition that the stirring speed is 1500r/min, wherein the volume ratio of the dosage of two phases is that of the crosslinking acid base liquid: the oil phase is 70:30, and the emulsified cross-linked acid is obtained after stirring for 25min after the dripping is finished.
Example 14
1) Preparing a cross-linking acid base solution from the following components in parts by weight: taking 96.5 parts of hydrochloric acid solution with the concentration of 15 percent by weight, slowly adding 0.7 part of polyacrylamide thickening agent SRAP-1 for acid (SRAP-1 produced by China petrochemical petroleum engineering technical research institute) at the rotating speed of 500r/min, stirring for half an hour to form uniform solution, then adding 1.2 parts of iron ion stabilizer (produced by ethylene diamine tetraacetic acid and Tianjin photochemical reagent factory) and 1.6 parts of imidazoline corrosion inhibitor (sold in market), stirring uniformly, sealing, standing at room temperature for 1 hour;
2) slowly adding 1.0 part of organic titanium crosslinking agent (produced by China petrochemical petroleum engineering technical research institute) into the crosslinking acid base solution;
3) preparing an oil phase from the following components in parts by weight: heating and dissolving 3 parts of sorbitan sesquioleate and 1 part of tetradecylamine in 96.5 parts of diesel oil, uniformly stirring, and cooling to room temperature for later use;
4) preparing an emulsified cross-linked acid system according to the following components in parts by volume: slowly dripping the prepared crosslinking acid base liquid added with the crosslinking agent into an oil phase under the condition that the stirring speed is 2000r/min, wherein the volume ratio of the dosage of two phases is that of the crosslinking acid base liquid: the oil phase is 70:30, and the emulsified cross-linked acid is obtained after the dripping is finished and the stirring is continued for 20 min.
Example 15
The procedure was as in example 14 except that 0.8 part of the organic titanium crosslinking agent was added.
Example 16
The procedure was as in example 14 except that 1.2 parts of the organotitanium crosslinking agent was added.
Example 17
The procedure was the same as in example 14 except that 0.8 parts of the organic zirconium crosslinking agent was added.
Example 18
The procedure was the same as in example 14, except that 1.0 part of the organic zirconium crosslinking agent was added.
Example 19
The procedure was the same as in example 14 except that 1.2 parts of the organozirconium cross-linking agent was added.
Example 20
The procedure was the same as in example 14 except that 0.8 parts of an organoaluminum crosslinking agent was added.
Example 21
The procedure was the same as in example 14 except that 1.0 part of the organoaluminum crosslinking agent was added.
Example 22
The procedure was the same as in example 14 except that 1.2 parts of the organoaluminum crosslinking agent was added.
Comparative example 1
1) Preparing gelled acid from the following components in parts by weight: taking 96.5 parts of hydrochloric acid solution with the concentration of 15 percent by weight, slowly adding 0.7 part of polyacrylamide thickening agent SRAP-1 for acid (SRAP-1 produced by China petrochemical petroleum engineering technical research institute) at the rotating speed of 500r/min, stirring for half an hour to form uniform solution, then adding 1.2 parts of iron ion stabilizer (produced by ethylene diamine tetraacetic acid and Tianjin photochemical reagent factory) and 1.6 parts of imidazoline corrosion inhibitor (sold in market), stirring uniformly, sealing, standing at room temperature for 1 hour;
2) preparing an oil phase from the following components in parts by weight: heating and dissolving 3 parts of sorbitan sesquioleate and 1 part of tetradecylamine in 96.5 parts of diesel oil, uniformly stirring, and cooling to room temperature for later use;
3) preparing an emulsified gelled acid system according to the following components in parts by volume: slowly dripping the prepared gelled acid into an oil phase under the condition that the stirring speed is 2000r/min, wherein the volume ratio of the two phases is gelled acid base liquid: the oil phase is 70:30, and the emulsified gelled acid is obtained after continuously stirring for 20min after the dripping is finished.
Comparative example 2
The procedure was the same as in example 1, except that no thickener and no crosslinking agent were added.
Performance testing
(1) The stability at 120 ℃ of the products prepared in examples 1-22 and comparative examples 1-2 was tested (the test method is from the literature: indoor research on improving stability of emulsified acid nanoparticles, drilling process, 2015,38(6):72-74), and the results are shown in table 1, and the emulsion breaking rate of the emulsified crosslinked acid prepared in examples 1-22 at 120 ℃ is lower than that of the products prepared in comparative examples 1-2, and the emulsion breaking rate shows good temperature stability.
TABLE 1 demulsification Rate versus time at high temperature for the products prepared in the examples and comparative examples
(2) The apparent viscosities of the products prepared in examples 1-22 and comparative examples 1-2 at room temperature (25 ℃) and 120 ℃ are measured (the test method is from the literature: indoor research on the nano-particle material with improved stability of the emulsified acid, drilling and production process 2015,38(6):72-74), and the results are shown in table 2, the apparent viscosities of the emulsified cross-linked acids prepared in examples 1-22 at room temperature and high temperature are both greater than those of comparative examples 1-2, and the emulsified cross-linked acids prepared in examples 1-22 have good temperature resistance stability and viscosities at room temperature and high temperature.
TABLE 2 comparison of apparent viscosity of products prepared in examples and comparative examples
(3) The particle Size of the emulsion of the crosslinked emulsified acid prepared in examples 1-22 and comparative examples 1-2 at room temperature (25 ℃) was measured (from SPE-178978-MS, Stability Determination of emulsions by traction library Size modification With Static Light Scattering), and the results are shown in Table 3, wherein the particle Size of the crosslinked emulsified acid prepared in examples 1-22 at room temperature is significantly smaller than that of comparative examples 1-2, and the smaller the particle Size of the emulsified acid, the higher the viscosity, the better the Stability at room temperature and under heating, and the better the performance of the crosslinked emulsified acid.
TABLE 3 comparison of particle size distribution of products prepared in examples and comparative examples
| Particle size (mum) of emulsified crosslinked acid system | |
| Example 1 | 2.0～1.5 |
| Example 2 | 2.1～1.2 |
| Example 3 | 2.0～1.5 |
| Example 4 | 2.3～1.2 |
| Example 5 | 2.0～1.5 |
| Example 6 | 2.2～1.2 |
| Example 7 | 2.0～1.5 |
| Example 8 | 1.2～0.8 |
| Example 9 | 2.3～1.2 |
| Example 10 | 2.0～1.5 |
| Example 11 | 2.2～1.2 |
| Example 12 | 2.2～1.0 |
| Example 13 | 2.0～1.5 |
| Example 14 | 2.0～1.5 |
| Example 15 | 2.2～1.2 |
| Example 16 | 2.2～1.0 |
| Example 17 | 2.0～1.5 |
| Example 18 | 2.0～1.5 |
| Example 19 | 2.2～1.2 |
| Example 20 | 2.2～1.0 |
| Example 21 | 2.0～1.5 |
| Example 22 | 2.0～1.5 |
| Comparative example 1 | 2.2～1.2 |
| Comparative example 2 | 3.0～5.0 |
(4) The acid rock reaction rate of the emulsified crosslinked acids prepared in the examples 1-22 and the comparative examples 1-2 at 120 ℃ is tested (the measurement method is from SY/T6526-.
TABLE 4 comparison of the reaction rates of the products prepared in the examples and comparative examples
| Reaction velocity (mol/m)2·s) | |
| Example 1 | 1.30×10-5 |
| Example 2 | 1.38×10-5 |
| Example 3 | 1.35×10-5 |
| Example 4 | 1.38×10-5 |
| Example 5 | 1.31×10-5 |
| Example 6 | 1.36×10-5 |
| Example 7 | 1.30×10-5 |
| Example 8 | 1.0×10-5 |
| Example 9 | 1.32×10-5 |
| Example 10 | 1.38×10-5 |
| Example 11 | 1.30×10-5 |
| Example 12 | 1.41×10-5 |
| Example 13 | 1.40×10-5 |
| Example 14 | 1.32×10-5 |
| Example 15 | 1.38×10-5 |
| Example 16 | 1.30×10-5 |
| Example 17 | 1.41×10-5 |
| Example 18 | 1.40×10-5 |
| Example 19 | 1.32×10-5 |
| Example 20 | 1.38×10-5 |
| Example 21 | 1.30×10-5 |
| Example 22 | 1.41×10-5 |
| Comparative example 1 | 2.0×10-5 |
| Comparative example 2 | 2.47×10-5 |
As can be seen from the comparison of the four performances, the emulsified crosslinked acid has the advantages of small particle size, high apparent viscosity, good temperature stability, good retarding effect and the like, and the preparation method is simple and is worthy of popularization and application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. An emulsified crosslinked acid comprising a crosslinked acid base fluid, an oil phase, and a crosslinking agent.
2. The emulsified crosslinked acid according to claim 1, wherein the contents of the components are, in parts by volume: 60-80 parts of crosslinking acid base liquid, preferably 65-75 parts; 20-40 parts of an oil phase, preferably 25-35 parts; 0.6 to 1.5 parts of cross-linking agent, preferably 0.8 to 1.2 parts.
3. The emulsified crosslinked acid of claim 1 or 2, wherein the crosslinking agent comprises a surface crosslinking acid crosslinking agent and/or a subsurface crosslinking acid crosslinking agent; preferably, the crosslinking agent for surface crosslinking acid comprises at least one of an organic zirconium crosslinking agent, an organic titanium crosslinking agent and a phenolic resin crosslinking agent, and the crosslinking agent for subsurface crosslinking acid comprises at least one of an organic zirconium crosslinking agent, an organic titanium crosslinking agent, an organic aluminum crosslinking agent and an iron ion crosslinking agent.
4. The emulsified crosslinked acid according to any one of claims 1 to 3, wherein the crosslinked acid base fluid comprises the following components in parts by weight:
90-98 parts of hydrochloric acid solution, preferably 92-97.0 parts; 1.5-2 parts of corrosion inhibitor, preferably 1.2-1.8 parts; 1-1.5 parts of iron ion stabilizer, preferably 1.2-1.4 parts; 0.6-0.9 part of thickening agent for acid, preferably 0.7-0.8 part.
5. An emulsified crosslinked acid according to any of claims 1-4, characterized in that the concentration of the hydrochloric acid solution is 15-30% wt, preferably 15-20% wt; and/or the iron ion stabilizer is selected from at least one of citric acid, ethylene diamine tetraacetic acid, ascorbic acid and acetic acid; and/or the corrosion inhibitor is a high temperature corrosion inhibitor; the high-temperature corrosion inhibitor is selected from at least one of imidazoline corrosion inhibitors and Mannich base corrosion inhibitors; and/or the acid thickener is at least one of a synthetic polymer and a natural polymer; the synthetic polymer is selected from thickening agents for polyacrylamide acids, and the natural polymer is selected from natural polymers such as guar gum.
6. The emulsified crosslinked acid according to any one of claims 1-5, wherein the oil phase comprises the following components in parts by weight: 3-5 parts of a high-efficiency emulsifier, preferably 3.5-4.5 parts; 95-97 parts of base oil, preferably 95.5-96.5 parts; and/or the high-efficiency emulsifier is at least one selected from PEG-30 dipolyhydroxystearate, sorbitan sesquioleate, sorbitan fatty acid ester, polyoxyethylene octyl phenol ether-10, dodecylamine, tetradecylamine and hexadecylamine; and/or the base oil is selected from at least one of diesel oil, kerosene, white oil and light crude oil.
7. The method for preparing an emulsified crosslinked acid according to any one of claims 1 to 6, which comprises mixing a crosslinking acid base solution, an oil phase and a crosslinking agent.
8. The method of claim 7, comprising the steps of:
A1. dropwise adding the crosslinking acid groups into the oil phase to obtain a mixture;
A2. to the mixture obtained in step A1, a ground crosslinking agent is added.
9. The method of claim 7, comprising the steps of:
B1. adding an underground cross-linking agent into a cross-linking acid base solution to obtain a mixed emulsion;
B2. and (3) dropwise adding the mixed emulsion obtained in the step B1 into the oil phase.
10. The method according to claim 8 or 9, wherein stirring is assisted during and after the addition of the cross-linked acid-based fluid or the mixed emulsion dropwise to the oil phase; the stirring speed is 1000-3000 r/min, preferably 1500-2500 r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811444315.XA CN111234800A (en) | 2018-11-29 | 2018-11-29 | Emulsified crosslinked acid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811444315.XA CN111234800A (en) | 2018-11-29 | 2018-11-29 | Emulsified crosslinked acid and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111234800A true CN111234800A (en) | 2020-06-05 |
Family
ID=70862693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811444315.XA Pending CN111234800A (en) | 2018-11-29 | 2018-11-29 | Emulsified crosslinked acid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111234800A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140329725A1 (en) * | 2013-05-06 | 2014-11-06 | Halliburton Energy Services, Inc. | Dual Retarded Acid System for Well Stimulation |
| US20150141302A1 (en) * | 2012-06-18 | 2015-05-21 | Akzo Nobel Chemicals International B.V. | Composition Containing An Emulsified Chelating Agent And Process To Treat A Subterreanean Formation |
| CN111117590A (en) * | 2018-11-01 | 2020-05-08 | 中国石油化工股份有限公司 | Crosslinked emulsified acid, preparation method and application |
-
2018
- 2018-11-29 CN CN201811444315.XA patent/CN111234800A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150141302A1 (en) * | 2012-06-18 | 2015-05-21 | Akzo Nobel Chemicals International B.V. | Composition Containing An Emulsified Chelating Agent And Process To Treat A Subterreanean Formation |
| US20140329725A1 (en) * | 2013-05-06 | 2014-11-06 | Halliburton Energy Services, Inc. | Dual Retarded Acid System for Well Stimulation |
| CN111117590A (en) * | 2018-11-01 | 2020-05-08 | 中国石油化工股份有限公司 | Crosslinked emulsified acid, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 中国石油学会: "《石油技术辞典》", 31 August 1996 * |
| 王业飞: "《油田化学工程与应用》", 31 March 2018, 石油大学出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3302717A (en) | Selective plugging of subterranean formations to inhibit intrusion of water | |
| CN104710969B (en) | A kind of oil-based drilling fluid viscosifier and preparation method thereof | |
| US3934651A (en) | Method of acidizing subterranean formations | |
| CN108285784B (en) | Gelled emulsified acid and preparation method thereof | |
| AU2019257441A1 (en) | Delayed gelation of polymers | |
| CN111410949B (en) | A kind of integrated variable viscosity salt-resistant drag-reducing agent and preparation method thereof | |
| CN110358522B (en) | Composite resistance-reducing and speed-reducing acid for deep well acid fracturing | |
| CN104017131B (en) | Polymer microgel oil-displacing agent and its preparation method and application | |
| CN106467736A (en) | A kind of fracturing fluid for shale pressure break and preparation method thereof | |
| CN107556996B (en) | CO (carbon monoxide)2Response in-situ gel channeling sealing agent and preparation method and application thereof | |
| CN117285920A (en) | Synthetic fracturing fluid for reservoir protection and preparation method thereof | |
| CN102120929A (en) | Preparation method of gas-well water controlling agent | |
| CN115109181A (en) | Supermolecule leaking stoppage gel polymer for oil-based drilling fluid, preparation method and application thereof, and drilling fluid | |
| EA016322B1 (en) | Method of reducing production of water from a water and oil or gas producing subterranean formation | |
| CN111117590A (en) | Crosslinked emulsified acid, preparation method and application | |
| CN110724514B (en) | Nano high-temperature emulsified gelled acid and preparation method thereof | |
| CN104263346B (en) | A kind of acidic aggravated fracturing fluid and its preparation method and application | |
| CN108219761A (en) | Foam gel plugging agent for sealing air cone and its construction method | |
| CN111234800A (en) | Emulsified crosslinked acid and preparation method thereof | |
| US4666957A (en) | Gel for retarding water flow | |
| EP0295877A2 (en) | Method and composition for viscosifying hydrocarbons | |
| CN108715757A (en) | A kind of preparation method of acidproof thickening agent and its application in multifunctional acid and acid-resistant pressing crack liquid | |
| CN111117591B (en) | Cross-linked emulsified self-generated acid and preparation method thereof | |
| CN114426824B (en) | Clay stabilizer for preventing water-sensitive damage and preparation method and application thereof | |
| CN110317289B (en) | Polyacrylamide nano-microsphere profile control agent for oilfield chemical oil extraction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200605 |
|
| RJ01 | Rejection of invention patent application after publication |