CN116948082B - Liquid rubber plug temporary plugging agent with controllable glue forming speed and synthesis method thereof - Google Patents
Liquid rubber plug temporary plugging agent with controllable glue forming speed and synthesis method thereof Download PDFInfo
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- CN116948082B CN116948082B CN202311219617.8A CN202311219617A CN116948082B CN 116948082 B CN116948082 B CN 116948082B CN 202311219617 A CN202311219617 A CN 202311219617A CN 116948082 B CN116948082 B CN 116948082B
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- temporary plugging
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- liquid rubber
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 69
- 239000007788 liquid Substances 0.000 title claims abstract description 64
- 239000003292 glue Substances 0.000 title claims abstract description 24
- 238000001308 synthesis method Methods 0.000 title claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 38
- 239000011325 microbead Substances 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 230000003111 delayed effect Effects 0.000 claims abstract description 21
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 20
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 12
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- 239000000337 buffer salt Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000004925 Acrylic resin Substances 0.000 claims description 15
- 229920000178 Acrylic resin Polymers 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 8
- 238000003892 spreading Methods 0.000 claims description 8
- 230000007480 spreading Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 8
- 239000012530 fluid Substances 0.000 description 10
- 230000035699 permeability Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 8
- 239000003431 cross linking reagent Substances 0.000 description 7
- 238000005553 drilling Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Abstract
The invention belongs to the technical field of tertiary oil recovery, and particularly relates to a liquid rubber plug temporary plugging agent with controllable gelling speed and a synthesis method thereof. The synthesis method comprises the following steps: adding hollow ceramic microbeads into a beaker, adding potassium persulfate solution, soaking, drying and crushing to obtain a delayed initiator; sequentially adding 2-allyloxymethyl-2-hydroxymethyl propane-1, 3-diol, butenedioic acid, 1-vinyl-2-pyrrolidone, 2,4, 6-triallyloxy-1, 3, 5-triazine, fumed silica, buffer salt and water, stirring and dissolving, and regulating pH to obtain a base solution; heating the base liquid while stirring, rapidly adding a delayed initiator, stopping stirring when the viscosity of the base liquid is increased, and then shaking the four-neck flask at random, thus obtaining the product when the base liquid has no fluidity. The temporary plugging agent has the advantages of simple synthesis, controllable glue forming speed, high plugging rate, high plugging removal rate and high plugging strength.
Description
Technical Field
The invention belongs to the technical field of tertiary oil recovery, and particularly relates to a liquid rubber plug temporary plugging agent with controllable gelling speed and a synthesis method thereof.
Background
In the middle and later stages of oil field development, excessive water production of an oil well is one of the serious problems faced by oil field exploitation, the average water content of the oil field is more than 80%, the water content of the eastern part of the old oil field is more than 90%, the high water content brings a plurality of damages to oil field development and production, the difficulty is increased to the secondary and tertiary development of low-permeability and ultra-low-permeability oil wells, the complexity of hydraulic fracture is gradually the key point of hydraulic fracture construction design, temporary plugging and turning is one of the methods for improving the complexity of the hydraulic fracture, and the principle is that the temporary plugging agent is used for temporarily plugging the original channel of the fracturing fluid, changing the flow direction of the fracturing fluid and forcing the generation of new fracture, thereby improving the complexity of the hydraulic fracture.
The temporary plugging agent is a chemical agent with a temporary plugging effect and is used for protecting an unintended layer from operation injury in the operation of an oil-water well. The temporary plugging agent is added into the stratum in real time in the construction process, particles enter the stratum, the principle that fluid flows in the direction with minimum resistance is followed, filter cake bridge plugging cracks or high permeable layers can be formed in a high permeable zone, which is higher than the cracking pressure of the cracks, so that subsequent working fluid cannot enter the cracks and the high permeable zone, the fracturing fluid enters a high stress zone or a pressure difference value promotes the generation of new cracks.
20110343106. X discloses a Microsoft granule oil-soluble temporary plugging agent which consists of water, carboxymethyl modified cellulose, low-viscosity PAC, linear paraffin oil, linear alkyl polyoxyethylene ether, glycerol and calcareous clay in parts by weight. The temporary plugging agent is used as a protective agent for a hydrocarbon reservoir in water-based drilling fluid of an oil field. The product utilizes the functional groups of the product to enable the drilling fluid to generate a molecular film (isolation film) on the well wall, and simultaneously oil-soluble and water-dispersible particles can form shielding temporary plugging on the well wall under a certain pressure difference in the well shaft, so that two oil layer protection technologies are organically combined, a firm protection layer is formed on the periphery of the well wall, filtrate and the drilling fluid are prevented from entering the stratum, hydration expansion of the stratum is effectively prevented, stratum layer cracks are plugged, migration of clay particles in the stratum is prevented, the problem of poor plugging effect caused by mismatch of stratum temperature and product softening point is effectively solved, and damage of drilling construction operation to an oil-gas layer is further reduced.
200710049168.1A temporary plugging agent for oil and gas reservoir cracks is prepared by mixing the following components: 40-85% of 60-1100 mesh superfine calcium carbonate, 10-40% of plant fiber and 5-20% of oxidized asphalt. After the temporary plugging agent enters the stratum along with drilling fluid, a layer of compact and tough mud cake is quickly formed near the well wall, so that the original permeability of the stratum near the well wall is reduced to be close to zero, and the invasion of drilling fluid filtrate, various treating agents, rock debris and the like in the drilling process is prevented, so that the reduction of oil and gas yield and the reduction of productivity are caused. The temporary plugging agent has a temporary plugging rate of more than 99% for the fractured rock core, a pressure flowback rate and an acidizing flowback rate of more than 80%, and a temporary plugging range is wide, so that the temporary plugging agent is an ideal fractured reservoir protecting agent. The agent has the characteristics of small dosage, low cost and no pollution.
201810899545.9A method for realizing temporary plugging and steering fracturing by utilizing differential pressure polymerization temporary plugging agent comprises the steps of firstly determining the type of the temporary plugging and steering agent according to the stratum pressure coefficient, the reservoir temperature, the pressure and the depth of a target well reservoir; then, the adding amount of temporary plugging agent is designed according to the number of the pore canals; on the basis of the pressed crack, adding a powder type differential pressure polymerization temporary plugging agent and a particle temporary plugging agent into slickwater or guanidine gum base liquid, displacing the temporary plugging liquid in place by using the slickwater or the guanidine gum base liquid, and observing and recording oil pressure change during the displacement; and analyzing the spreading layer position and direction of the new crack by analyzing the fracturing crack monitoring graph to judge the temporary plugging turning fracturing construction effect. According to the invention, the pressure differential polymerizable powder temporary plugging agent and the particle temporary plugging agent are used in a combined way to effectively plug the original cracks, so that the bearing capacity of the cracks is improved, the control area of the cracks is increased, meanwhile, the complexity of the cracks is improved through steering among clusters and in the cracks, the volume fracturing effect that the main cracks are communicated with the natural cracks is formed, and finally, the purpose of improving the production of the oil-gas well is achieved.
However, the temporary plugging agent in the patent is glued on the ground or underground, but the glue time is fixed, so that the application range of the temporary plugging agent is limited, and the report of the temporary plugging agent capable of controlling the glue time is less.
Disclosure of Invention
The invention provides a liquid rubber plug temporary plugging agent with controllable glue forming speed and a synthesis method thereof aiming at the defects of the prior art. The temporary plugging agent has the advantages of simple synthesis, controllable glue forming speed, high plugging rate, high plugging removal rate and high plugging strength.
The invention discloses a liquid rubber plug temporary plugging agent with controllable glue forming speed, which has the following molecular structural formula:
，
wherein:
a=300-3000；
b=5000-50000；
c=3000-30000；
d=3000-30000；
e=300-3000；
f=5000-50000；
g=3000-30000；
h=3000-30000；
i=300-3000；
j=5000-50000；
k=3000-30000；
l=3000-30000。
preferably, the viscosity average molecular weight 20000000-40000000 of the liquid rubber plug temporary plugging agent.
The invention further discloses a synthesis method of the temporary plugging agent for the liquid rubber plug, which has controllable glue forming speed, and comprises the following specific steps:
(1) Preparation of delayed initiator
(1) Adding hollow ceramic microbeads into a beaker, adding potassium persulfate solution, soaking the hollow ceramic microbeads for more than 2 hours;
(2) spreading the soaked hollow ceramic microbeads on a tray, and drying by using an oven at 80-85 ℃;
(3) soaking the hollow ceramic microbeads dried in the step (2) in an ethanol solution of BR-116 type Mitsubishi acrylic resin for 10-15min;
(4) taking out the hollow ceramic microbeads in the step (3), drying in a baking oven at 40-45 ℃, crushing, and screening out the 100-150 mesh delayed initiator.
(2) Preparation of base liquid
Purging the four-neck flask for 2-3min by nitrogen, sequentially adding 2-allyloxymethyl-2-hydroxymethyl propane-1, 3-diol, butenedioic acid, 1-vinyl-2-pyrrolidone, 2,4, 6-triallyloxy-1, 3, 5-triazine, fumed silica, buffer salt and water, stirring and dissolving, ensuring that the silica is in a suspension state in water, and regulating the pH value to 7-8 by using a sodium hydroxide solution to obtain a base solution;
(3) Synthesis of temporary plugging agent for liquid rubber plug
Heating the base solution to 70-75 ℃ while stirring, adding a delay initiator, stopping stirring when the viscosity of the base solution is increased, then shaking the four-neck flask at random, and obtaining the product liquid rubber plug temporary plugging agent when no fluidity exists.
In the present invention, preferably, the hollow ceramic microbeads in step (1) have a particle size of 800-900 mesh, and are preferably purchased from Shanghai Runfan nanomaterials Co.
In the present invention, preferably, the potassium persulfate solution in step (1) has a concentration of 10 to 25wt%.
In the present invention, it is preferable that the alcoholic solution concentration of the BR-116 type Mitsubishi acrylic resin in the step (1) is 4 to 10% by weight.
In the present invention, it is preferable that the butenedioic acid, 1-vinyl-2-pyrrolidone, 2,4, 6-triallyloxy-1, 3, 5-triazine is used in an amount of 0.2 to 1 part by mole, and 0.02 to 0.1 part by mole, respectively, based on 1 part by mole of 2-allyloxymethyl-2-hydroxymethyl propane-1, 3-diol in the step (2).
In the present invention, preferably, the mass ratio of the fumed silica, the buffer salt, water and the 2-allyloxymethyl-2-hydroxymethylpropane-1, 3-diol in the step (2) is 0.2-1:0.03-0.05:80-100:1.
in the present invention, preferably, the buffer salt in the step (2) is one of sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, and dipotassium hydrogen phosphate.
In the present invention, preferably, the mass ratio of the delayed initiator to 2-allyloxymethyl-2-hydroxymethylpropane-1, 3-diol in step (3) is 0.1 to 0.5:1.
the synthesis reaction equation of the temporary plugging agent for the liquid rubber plug is as follows:
，
，
the temporary plugging agent for the liquid rubber plug is a water-phase quaternary high polymer taking 2-allyloxymethyl-2-hydroxymethyl propane-1, 3-diol, butenedioic acid and 1-vinyl-2-pyrrolidone as polymer raw materials and taking 2,4, 6-triallyloxy-1, 3, 5-triazine as a cross-linking agent. Wherein, the 2-allyloxymethyl-2-hydroxymethyl propane-1, 3-diol and the butenedioic acid have better water absorption and are easy to gel; the 1-vinyl-2-pyrrolidone can improve the rigid structure of molecules and the blocking strength; 2,4, 6-triallyloxy-1, 3, 5-triazine can play a role in crosslinking, so that the molecular weight is greatly improved, and the blocking strength is improved; the delayed crosslinking agent can control the glue forming speed on one hand and can improve the blocking strength of the temporary plugging agent due to the high hardness of the delayed crosslinking agent on the other hand; on one hand, the fumed silica plays a role in dispersing in the synthesis process, and on the other hand, the plugging strength of the product can be greatly improved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The temporary plugging agent for the liquid rubber plug has the advantages of easily available synthetic raw materials, simple process and no byproducts;
(2) The glue forming time of the temporary plugging agent for the liquid rubber plug is controllable, and the glue forming time is between 62 and 260 minutes;
(3) The temporary plugging rate of the temporary plugging agent for the liquid rubber plug is higher, and reaches more than 98%, and the recovery rate is higher, and reaches more than 97%;
(4) The temporary plugging agent for the liquid rubber plug has higher plugging strength and has the permeability of 0.314 mu m 2 The breakthrough pressure gradient of the artificial sealed rock core reaches more than 200 MPa/m.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Example 1: 1. preparation of delayed initiator
(1) Adding 50g of hollow ceramic microbeads into a beaker, adding 10wt% of potassium persulfate solution, soaking the hollow ceramic microbeads for more than 2 hours;
(2) Spreading the soaked hollow ceramic microbeads on a tray, and drying by using an oven at 80 ℃;
(3) Placing the ceramic microbeads dried in the step (2) into an ethanol solution of 4wt% BR-116 type Mitsubishi acrylic resin to be soaked for 10min;
(4) And (3) taking out the ceramic microbeads in the step (3), drying in a baking oven at 45 ℃, crushing, and screening out the 100-150-mesh delayed initiator.
2. Preparation of base liquid
Purging the four-necked flask for 2min by nitrogen, sequentially adding 0.05mol of 2-allyloxymethyl-2-hydroxymethyl propane-1, 3-diol, 0.05mol of butenedioic acid, 0.01mol of 1-vinyl-2-pyrrolidone, 0.001mol of 2,4, 6-triallyloxy-1, 3, 5-triazine, 1.76g of fumed silica, 0.26g of sodium dihydrogen phosphate and 818g of water, stirring and dissolving, ensuring that the silica is in a suspension state in the water, and regulating the pH value to 7-8 by using a sodium hydroxide solution to obtain a base solution;
3. synthesis of temporary plugging agent for liquid rubber plug
Heating the base liquid to 70deg.C under stirring, adding 4.4g of the delayed initiator in step 1, starting timing, stopping stirring when the viscosity of the base liquid is observed to increase, and recording time T 1 Standing and observing, shaking the four-neck flask at random, and recording time T when no fluidity exists 2 And (3) the glue forming time is obtained, and meanwhile, the product liquid rubber plug temporary plugging agent is obtained.
Example 2: the only difference was that the 10wt% potassium persulfate solution was replaced with a 15wt% potassium persulfate solution as in example 1.
Example 3: the only difference was that the 10wt% potassium persulfate solution was replaced with a 20wt% potassium persulfate solution as in example 1.
Example 4: the only difference was that the 10wt% potassium persulfate solution was replaced with a 25wt% potassium persulfate solution as in example 1.
Example 5: the only difference was that the ethanol solution of 4wt% of the type BR-116 Mitsubishi acrylic resin was changed to the ethanol solution of 6wt% of the type BR-116 Mitsubishi acrylic resin, as in example 1.
Example 6: the only difference was that the ethanol solution of 4wt% of the type BR-116 Mitsubishi acrylic resin was changed to that of 8wt% of the type BR-116 Mitsubishi acrylic resin, as in example 1.
Example 7: the only difference was that the ethanol solution of 4wt% of the type BR-116 Mitsubishi acrylic resin was changed to the ethanol solution of 10wt% of the type BR-116 Mitsubishi acrylic resin, as in example 1.
Example 8: 1. preparation of delayed initiator
(1) Adding 50g of hollow ceramic microbeads into a beaker, adding 15wt% of potassium persulfate solution, soaking the hollow ceramic microbeads for more than 2 hours;
(2) Spreading the soaked hollow ceramic microbeads on a tray, and drying by using an oven at 85 ℃;
(3) Placing the ceramic microbeads dried in the step (2) into an ethanol solution of 6wt% BR-116 type Mitsubishi acrylic resin to be soaked for 15min;
(4) And (3) taking out the ceramic microbeads in the step (3), drying in a baking oven at 40 ℃, crushing, and screening out the 100-150-mesh delayed initiator.
2. Preparation of base liquid
Purging the four-necked flask for 3min by nitrogen, sequentially adding 0.05mol of 2-allyloxymethyl-2-hydroxymethyl propane-1, 3-diol, 0.04mol of butenedioic acid, 0.02mol of 1-vinyl-2-pyrrolidone, 0.002mol of 2,4, 6-triallyloxy-1, 3, 5-triazine, 2.44g of fumed silica, 0.31g of dipotassium hydrogen phosphate and 880g of water, stirring and dissolving, ensuring that the silica is in a suspension state in the water, and regulating the pH value to 7-8 by using a sodium hydroxide solution to obtain a base solution;
3. synthesis of temporary plugging agent for liquid rubber plug
Heating the base liquid to 72 ℃ while stirring, adding 3.88g of the delay initiator in the step 1, starting timing, stopping stirring when the viscosity of the base liquid is observed to be increased, and recording the time T 1 Standing and observing, shaking the four-neck flask at random, and recording time T when no fluidity exists 2 And (3) the glue forming time is obtained, and meanwhile, the product liquid rubber plug temporary plugging agent is obtained.
Example 9: 1. preparation of delayed initiator
(1) Adding 50g of hollow ceramic microbeads into a beaker, adding 15wt% of potassium persulfate solution, soaking the hollow ceramic microbeads for more than 2 hours;
(2) Spreading the soaked hollow ceramic microbeads on a tray, and drying by an oven at 82 ℃;
(3) Placing the ceramic microbeads dried in the step (2) into an ethanol solution of 6wt% BR-116 type Mitsubishi acrylic resin to be soaked for 12min;
(4) And (3) taking out the ceramic microbeads in the step (3), drying in a 42 ℃ oven, crushing, and screening out the 100-150 mesh delayed initiator.
2. Preparation of base liquid
Purging the four-necked flask for 2min by nitrogen, sequentially adding 0.05mol of 2-allyloxymethyl-2-hydroxymethyl propane-1, 3-diol, 0.03mol of butenedioic acid, 0.03mol of 1-vinyl-2-pyrrolidone, 0.003mol of 2,4, 6-triallyloxy-1, 3, 5-triazine, 4.88g of fumed silica, 0.38g of disodium hydrogen phosphate and 840g of water, stirring and dissolving, ensuring that the silica is in a suspension state in the water, and regulating the pH value to 7-8 by using a sodium hydroxide solution to obtain a base solution;
3. synthesis of temporary plugging agent for liquid rubber plug
Heating the base liquid to 73 ℃ while stirring, adding 1.76g of the delay initiator in the step 1, starting timing, stopping stirring when the viscosity of the base liquid is observed to be increased, and recording the time T 1 Standing and observing, shaking the four-neck flask at random, and recording time T when no fluidity exists 2 And (3) the glue forming time is obtained, and meanwhile, the product liquid rubber plug temporary plugging agent is obtained.
Example 10: 1. preparation of delayed initiator
(1) Adding 50g of hollow ceramic microbeads into a beaker, adding 15wt% of potassium persulfate solution, soaking the hollow ceramic microbeads for more than 2 hours;
(2) Spreading the soaked hollow ceramic microbeads on a tray, and drying by using an oven at 83 ℃;
(3) Placing the ceramic microbeads dried in the step (2) into an ethanol solution of 6wt% BR-116 type Mitsubishi acrylic resin to be soaked for 13min;
(4) And (3) taking out the ceramic microbeads in the step (3), drying in a baking oven at 43 ℃, crushing, and screening out the 100-150-mesh delayed initiator.
2. Preparation of base liquid
Purging the four-necked flask for 3min by nitrogen, sequentially adding 0.05mol of 2-allyloxymethyl-2-hydroxymethyl propane-1, 3-diol, 0.02mol of butenedioic acid, 0.04mol of 1-vinyl-2-pyrrolidone, 0.004mol of 2,4, 6-triallyloxy-1, 3, 5-triazine, 6.41g of fumed silica, 0.44g of dipotassium hydrogen phosphate and 754g of water, stirring and dissolving, ensuring that the silica is in a suspension state in the water, and regulating the pH value to 7-8 by using a sodium hydroxide solution to obtain a base solution;
3. synthesis of temporary plugging agent for liquid rubber plug
Heating the base liquid to 74 ℃ while stirring, adding 0.88g of the delay initiator in the step 1, starting timing, stopping stirring when the viscosity of the base liquid is observed to be increased, and recording the time T 1 Standing and observing, shaking the four-neck flask at random, and recording time T when no fluidity exists 2 And (3) the glue forming time is obtained, and meanwhile, the product liquid rubber plug temporary plugging agent is obtained.
Example 11: 1. preparation of delayed initiator
(1) Adding 50g of hollow ceramic microbeads into a beaker, adding 15wt% of potassium persulfate solution, soaking the hollow ceramic microbeads for more than 2 hours;
(2) Spreading the soaked hollow ceramic microbeads on a tray, and drying by using an oven at 84 ℃;
(3) Placing the ceramic microbeads dried in the step (2) into an ethanol solution of 6wt% BR-116 type Mitsubishi acrylic resin, and soaking for 11min;
(4) And (3) taking out the ceramic microbeads in the step (3), drying in a baking oven at 41 ℃, crushing, and screening out the 100-150-mesh delayed initiator.
2. Preparation of base liquid
Purging the four-necked flask for 2min by nitrogen, sequentially adding 0.05mol of 2-allyloxymethyl-2-hydroxymethyl propane-1, 3-diol, 0.01mol of butenedioic acid, 0.05mol of 1-vinyl-2-pyrrolidone, 0.005mol of 2,4, 6-triallyloxy-1, 3, 5-triazine, 8.8g of fumed silica, 0.37g of sodium dihydrogen phosphate and 704g of water, stirring and dissolving, ensuring that the silica is in a suspension state in the water, and regulating the pH value to 7-8 by using a sodium hydroxide solution to obtain a base solution;
3. synthesis of temporary plugging agent for liquid rubber plug
Heating the base liquid to 75deg.C under stirring, adding 2.88g of the delayed initiator in step 1, starting timing, stopping stirring when the viscosity of the base liquid is observed to increase, and recording time T 1 Standing and observing, shaking the four-neck flask at random, and recording time T when no fluidity exists 2 And (3) the glue forming time is obtained, and meanwhile, the product liquid rubber plug temporary plugging agent is obtained.
Example 12: the only difference was that 0.003mol of 2,4, 6-triallyloxy-1, 3, 5-triazine was replaced by 0.004mol of 2,4, 6-triallyloxy-1, 3, 5-triazine.
Example 13: the only difference was that 0.003mol of 2,4, 6-triallyloxy-1, 3, 5-triazine was replaced by 0.005mol of 2,4, 6-triallyloxy-1, 3, 5-triazine.
Example 14: testing of gel time
The test process of the temporary plugging agent for the liquid rubber plug is shown in examples 1-13, and the test result is shown in Table 1.
As can be seen from table 1: the temporary plugging agent (examples 1-13) for the liquid rubber plug has controllable glue forming time and wide glue forming time range, and the glue forming time is between 62 and 260 minutes.
Example 15: determination of temporary blocking Rate and Permeability
Referring to Q/SH1020 2187-2018 general technical Condition for Water-soluble temporary blocking agent, the temporary blocking rate and permeability recovery rate are tested, and the test results of the temporary blocking rate and permeability recovery rate of the temporary blocking agent for the liquid rubber plug are shown in Table 1.
As can be seen from table 1:
(1) The temporary plugging rate of the liquid rubber plug temporary plugging agent (examples 1-13) is more than 98%, and the maximum rate is 99.1%;
(2) The permeability recovery rate of the temporary plugging agent (examples 1-13) of the liquid rubber plug is more than 97%, and the maximum recovery rate is 97.8%.
Example 16: test of blocking Strength
At 90℃the permeability of 0.314 μm was used 2 The artificial sealed core with the length of 6.5cm is extruded with the temporary plugging agent (examples 1-13) with the liquid rubber plug of the invention with the length of 1PV, the breakthrough pressure of the plugging agent is tested, the breakthrough pressure gradient is calculated, and the test result is shown in Table 1.
TABLE 1 test results of temporary blocking agent gel time, temporary blocking rate, permeability recovery rate, breakthrough pressure
，
As can be seen from table 1:
(1) The temporary plugging agent (examples 1-13) of the invention has a permeability of 0.314 μm at 90 DEG C 2 The breakthrough pressure of the artificial sealing core is more than 13MPa and reaches 15.8MPa at most (example 13);
(2) The temporary plugging agent (examples 1-13) of the invention has a permeability of 0.314 μm at 90 DEG C 2 The breakthrough pressure gradients of the artificial sealing core are all larger than 200MPa/m and reach 243MPa/m at most (example 13).
Meanwhile, as can be seen from examples 1 to 4, the concentration of potassium persulfate is an influencing factor of the gelling speed, and the higher the concentration of potassium persulfate, the faster the gelling speed; as can be seen from examples 1, 5, 6, and 7, the concentration of the resin is a factor influencing the gelling speed, and the higher the concentration of the resin, the slower the gelling speed; from examples 11 to 13, it can be seen that the concentration of the crosslinking agent is a factor affecting the gelling speed, the higher the concentration of the crosslinking agent, the faster the gelling speed; of the three factors of potassium persulfate, resin, and crosslinking agent, the resin concentration has the greatest effect on the gelling speed. The gel forming time of the invention is 62-260min, and the gel forming time range can be further widened by adjusting the amounts of potassium persulfate, resin and cross-linking agent.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (7)
1. The synthesis method of the temporary plugging agent for the liquid rubber plug with controllable glue forming speed is characterized by comprising the following specific steps of:
(1) Preparation of delayed initiator
(1) Adding hollow ceramic microbeads into a beaker, adding potassium persulfate solution, soaking the hollow ceramic microbeads for more than 2 hours;
(2) spreading the soaked hollow ceramic microbeads on a tray, and drying by using an oven at 80-85 ℃;
(3) soaking the hollow ceramic microbeads dried in the step (2) in an ethanol solution of BR-116 type Mitsubishi acrylic resin for 10-15min;
(4) taking out the hollow ceramic microbeads in the step (3), drying in a baking oven at 40-45 ℃, crushing, and screening out a 100-150-mesh delayed initiator;
(2) Preparation of base liquid
Purging the four-neck flask for 2-3min by nitrogen, sequentially adding 2-allyloxymethyl-2-hydroxymethyl propane-1, 3-diol, butenedioic acid, 1-vinyl-2-pyrrolidone, 2,4, 6-triallyloxy-1, 3, 5-triazine, fumed silica, buffer salt and water, stirring and dissolving, ensuring that the silica is in a suspension state in water, and regulating the pH value to 7-8 by using a sodium hydroxide solution to obtain a base solution;
the butenedioic acid, 1-vinyl-2-pyrrolidone, 2,4, 6-triallyloxy-1, 3, 5-triazine are used in an amount of 0.2 to 1 mole part, 0.02 to 0.1 mole part, respectively, based on 1 mole part of 2-allyloxymethyl-2-hydroxymethyl propane-1, 3-diol;
(3) Synthesis of temporary plugging agent for liquid rubber plug
Heating the base solution to 70-75 ℃ while stirring, adding a delay initiator, stopping stirring when the viscosity of the base solution is increased, then shaking the four-neck flask at random, and obtaining the product liquid rubber plug temporary plugging agent when no fluidity exists;
the mass ratio of the fumed silica, the buffer salt, the water and the 2-allyloxymethyl-2-hydroxymethyl propane-1, 3-diol in the step (2) is 0.2-1:0.03-0.05:80-100:1, a step of;
the buffer salt in the step (2) is one of sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate and dipotassium hydrogen phosphate.
2. The synthesis method of the temporary plugging agent for the liquid rubber plug with controllable glue forming speed, which is disclosed in claim 1, is characterized in that the particle size of the hollow ceramic microbeads in the step (1) is 800-900 meshes.
3. The method for synthesizing the temporary plugging agent for the liquid rubber plug with controllable gelling speed according to claim 1, wherein the concentration of the potassium persulfate solution in the step (1) is 10-%.
4. The synthesis method of the temporary plugging agent for the liquid rubber plug with controllable glue forming speed, which is characterized in that the concentration of the ethanol solution of the BR-116 type Mitsubishi acrylic resin in the step (1) is 4-%.
5. The synthesis method of the liquid rubber plug temporary plugging agent with controllable glue forming speed according to claim 1, wherein the mass ratio of the delay initiator to the 2-allyloxymethyl-2-hydroxymethyl propane-1, 3-diol in the step (3) is 0.1-0.5:1.
6. the liquid rubber plug temporary plugging agent prepared by the synthesis method according to any one of claims 1 to 5, wherein the molecular structural formula of the liquid rubber plug temporary plugging agent is as follows:
，
wherein:
a=300-3000；
b=5000-50000；
c=3000-30000；
d=3000-30000；
e=300-3000；
f=5000-50000；
g=3000-30000；
h=3000-30000；
i=300-3000；
j=5000-50000；
k=3000-30000；
l=3000-30000。
7. the controllable-gelling-speed liquid-rubber-plug temporary plugging agent according to claim 6, wherein the viscosity-average molecular weight of the liquid-rubber-plug temporary plugging agent is 20000000-40000000.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1207107A (en) * | 1996-02-06 | 1999-02-03 | Isp投资股份有限公司 | Polymerizable composition of vinylpyrrolidone and vinyl caprolactam |
| CN1714108A (en) * | 2002-11-20 | 2005-12-28 | Isp投资有限公司 | Process for making a vinyl amide polymer composition for skin and hair compositions |
| CN114920876A (en) * | 2022-05-25 | 2022-08-19 | 东营施普瑞石油工程技术有限公司 | Temporary plugging agent and preparation method thereof |
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| WO2014209485A1 (en) * | 2013-06-27 | 2014-12-31 | Isp Investments Inc. | A high-temperature high-pressure (hthp) stable synthetic polymer for water based oil-well servicing fluids |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1207107A (en) * | 1996-02-06 | 1999-02-03 | Isp投资股份有限公司 | Polymerizable composition of vinylpyrrolidone and vinyl caprolactam |
| CN1714108A (en) * | 2002-11-20 | 2005-12-28 | Isp投资有限公司 | Process for making a vinyl amide polymer composition for skin and hair compositions |
| CN114920876A (en) * | 2022-05-25 | 2022-08-19 | 东营施普瑞石油工程技术有限公司 | Temporary plugging agent and preparation method thereof |
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