CN117447690A - Waterproof locking agent for oil field and synthesis method thereof - Google Patents
Waterproof locking agent for oil field and synthesis method thereof Download PDFInfo
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- CN117447690A CN117447690A CN202311390527.5A CN202311390527A CN117447690A CN 117447690 A CN117447690 A CN 117447690A CN 202311390527 A CN202311390527 A CN 202311390527A CN 117447690 A CN117447690 A CN 117447690A
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 51
- 238000010438 heat treatment Methods 0.000 claims abstract description 48
- 238000001816 cooling Methods 0.000 claims abstract description 24
- TTXIFFYPVGWLSE-UHFFFAOYSA-N 1-[bis(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1C(C=1C=CC(F)=CC=1)N1CCNCC1 TTXIFFYPVGWLSE-UHFFFAOYSA-N 0.000 claims abstract description 20
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 19
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 12
- 230000001105 regulatory effect Effects 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 238000010926 purge Methods 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims 4
- 239000011435 rock Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 26
- 235000019198 oils Nutrition 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 6
- 238000005553 drilling Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
- C08G65/3348—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing nitrogen in addition to sulfur
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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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
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Abstract
The invention belongs to the technical field of petrochemical industry, and particularly relates to a waterproof locking agent for an oil field and a synthesis method thereof. The synthesis method comprises the following steps: adding 1- [ bis- (4-fluorophenyl) methyl ] piperazine and a catalyst into a high-pressure reaction kettle, vacuumizing, slowly heating, vacuumizing again, slowly heating, stopping vacuumizing, introducing ethylene oxide, heating, performing heat preservation reaction, stopping the reaction when the pressure is reduced to 0, and cooling the system to below 40 ℃; adding sulfamic acid powder into the high-pressure reaction kettle, stirring, heating while preserving heat, reacting, cooling to below 40 ℃, and regulating pH value to obtain the waterproof locking agent. The waterproof locking agent has the characteristics of simple synthesis process, low surface and interface tension and good effect of changing the contact angle of rock.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to a waterproof locking agent for an oil field and a synthesis method thereof.
Background
The hypotonic reservoir generally has the characteristics of ultralow water saturation, high capillary pressure, small pore throat, ultra-thin throat, poor connectivity and the like, and is extremely easy to cause water lock damage of the reservoir due to invasion of external liquid phase in the drilling, completion and workover processes.
The main reason is that the external liquid phase invades into the reservoir, and liquid phase blockage can be formed in pore channels around the well wall, so that permeability near the well shaft is reduced, and the yield of the oil-gas well is reduced. In addition, when the external liquid phase invades into the hypotonic reservoir, and the water saturation of the near-wellbore zone is increased, the water saturation of the reservoir cannot be reduced to the original water saturation, so that the seepage resistance of the near-wellbore zone is increased, and the reservoir is seriously damaged by water lock. Research shows that the damage rate reaches 70-90%.
The addition of a water blocking agent to the external fluid to reduce surface tension or alter the wettability of the coal sample is the most effective method of reducing water blocking damage.
Therefore, only a proper low-permeability oil reservoir waterproof locking agent is developed to effectively improve the productivity of the low-permeability oil reservoir oil well, and the waterproof locking agent is generally composed of a surfactant and a mixed solvent, wherein the principle is that the surfactant is adsorbed on the surface of rock through adsorption after a certain time of reaction, so that a layer of molecular film with lower tension than water surface is formed, and the hydrophilic rock surface is reversed to be weakly hydrophilic or hydrophobic. Thereby reducing the water absorption of reservoir rock, reducing the constraint of capillary force and reducing the damage degree of water lock.
The conventional waterproof locking agents comprise OP-10, ABS, tween and other nonionic surfactants, but for oil and gas reservoirs with complex geological conditions such as low pores, low permeability and the like, the waterproof locking agents cannot effectively reduce the surface tension and oil-water interfacial tension of filtrate so as to improve the relative permeability of gas phase.
CN102618224a discloses a waterproof locking agent for drilling fluid, which relates to a waterproof locking agent for reducing liquid phase trap damage in the process of drilling operation of a low permeability hydrocarbon reservoir, and comprises: at least one surfactant that acts to reduce interfacial tension; at least one cosurfactant which reduces interfacial tension and solubilizes; at least one vegetable or mineral oil; the balance is water, and the waterproof locking agent is used in the drilling fluid for developing the low-permeability reservoir, so that the interfacial tension of the rock can be changed, the oil-gas flow resistance is reduced, the liquid phase trap damage in the process of implementing the drilling operation on the low-permeability hydrocarbon reservoir is reduced, and the purposes of protecting the reservoir and improving the yield are achieved. However, the waterproof locking agent of the invention generally has the defects of high surface tension, difficulty in making a reservoir achieve air humidity, high foaming rate and unsatisfactory waterproof locking effect, and cannot meet the field use requirement.
Disclosure of Invention
The invention provides a waterproof locking agent for an oil field and a synthesis method thereof aiming at the defects of the prior art. The waterproof locking agent has the characteristics of simple synthesis process, low surface tension and good effect of changing the contact angle of rock, and the concentration surface tension of 0.3wt% is as low as 22.8mN/m, and the interfacial tension is as low as 0.032mN/m.
The invention discloses a waterproof locking agent for an oil field, which has the following molecular structural formula:
wherein n is a natural number from 5 to 100.
The invention further discloses a synthesis method of the waterproof locking agent for the oil field, which comprises the following specific steps:
(1) Adding 1- [ bis- (4-fluorophenyl) methyl ] piperazine and a catalyst into a high-pressure reaction kettle, purging a pipeline and the reaction kettle for 2-3min by using nitrogen, vacuumizing, purging the pipeline and the reaction kettle for 2-3min by using nitrogen again, then slowly heating to 85-90 ℃, vacuumizing again, then slowly heating to 115-120 ℃, stopping vacuumizing, introducing ethylene oxide at a speed of 3-10ml/min, heating to 160-165 ℃ after the introduction is finished, performing heat preservation reaction, stopping the reaction when the pressure is reduced to 0, and cooling the system to below 40 ℃;
(2) Adding sulfamic acid powder into the high-pressure reaction kettle, heating while stirring, carrying out heat preservation reaction at 120-130 ℃ for 60-120min, cooling to below 40 ℃, adding 10wt% of ethanolamine, and regulating pH to 7-8 by using sodium hydroxide solution to obtain the product of the waterproof locking agent for the oil field.
In the present invention, preferably, the ethylene oxide and sulfamic acid are used in an amount of 5 to 100 mole parts, 1.5 to 3 mole parts, respectively, based on 1 mole part of 1- [ bis- (4-fluorophenyl) methyl ] piperazine; more preferably, the ethylene oxide and sulfamic acid are used in an amount of 20 to 100 mole parts and 2 to 3 mole parts, respectively, based on 1 mole part of 1- [ bis- (4-fluorophenyl) methyl ] piperazine.
In the present invention, preferably, the mass ratio of one of sodium hydroxide, potassium hydroxide and potassium carbonate of the catalyst in the step (1) to 1- [ bis- (4-fluorophenyl) methyl ] piperazine is 0.1-0.5:1.
in the present invention, preferably, the mass ratio of the 10wt% ethanolamine to the 1- [ bis- (4-fluorophenyl) methyl ] piperazine in the step (2) is 3 to 20:1.
the reaction equation of the waterproof locking agent for oil fields is as follows:
the invention relates to a waterproof locking agent molecule for an oil field, belonging to a composite special surfactant. Hydrophilic groups are piperazine, polyether and sulfuric acid groups, are nonionic and anionic compound surfactant groups, belong to soft linear structures, can penetrate deep into capillaries of rock, have adsorption effect with the surface of the rock, are easy to wet and spread on the surface of the rock, and can reduce capillary resistance and driving pressure of stratum fluid; the lipophilic groups are two fluorophenyl groups, and have strong hydrophobicity; hydrophilic groups penetrate into the rock, hydrophobic groups are arranged on the outer side of the hydrophilic groups, and the hydrophilic rock surface is reversed to be hydrophobic, so that the water absorption of reservoir rock is reduced, the binding of capillary force is reduced, and the damage degree of water lock is reduced; the ethanolamine belongs to low molecular alcohol organic matters and can play an auxiliary role of a waterproof lock.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The water-proof locking agent aqueous solution for oil fields has lower surface tension, the concentration of 0.3wt% has the lowest surface tension of 22.8mN/m and the lowest interfacial tension of 0.032mN/m;
(2) The contact angle of the rock surface treated by the waterproof locking agent for the oil field is increased to 99.4 degrees from 22.5 degrees, and the increase reaches more than 50 degrees.
Drawings
Fig. 1 is a graph of core flake-untreated (22.5 °) contact angle measurements;
fig. 2 is a graph of a core slice-comparative treatment (58.7 °) contact angle test;
fig. 3 is a graph of a core slice-comparative treatment (58.7 °) contact angle test;
fig. 4 is a graph of core flake-example 7 treatment (99.4 °) contact angle test.
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) Adding 0.06mol of 1- [ bis- (4-fluorophenyl) methyl ] piperazine and 8.64g of potassium carbonate into a high-pressure reaction kettle, purging a pipeline and the reaction kettle for 2min by using nitrogen, vacuumizing, purging the pipeline and the reaction kettle for 2min by using nitrogen again, then slowly heating to 85 ℃, vacuumizing again, then slowly heating to 115 ℃, stopping vacuumizing, introducing 0.3mol of ethylene oxide, introducing the mixture at a speed of 3ml/min, heating to 164 ℃ after the introduction is finished, preserving heat for reaction, stopping the reaction when the pressure is reduced to 0, and cooling the system to below 40 ℃;
(2) Adding 0.16mol of sulfamic acid powder into the high-pressure reaction kettle, heating while stirring, preserving heat at 120 ℃ for reaction for 85min, cooling to below 40 ℃, adding 51.84g of 10wt% ethanolamine, and regulating pH to 7-8 by using sodium hydroxide solution to obtain the waterproof locking agent for the oil field.
Example 2
(1) Adding 0.06mol of 1- [ bis- (4-fluorophenyl) methyl ] piperazine and 6.11g of potassium carbonate into a high-pressure reaction kettle, purging a pipeline and the reaction kettle for 2min by using nitrogen, vacuumizing, purging the pipeline and the reaction kettle for 3min by using nitrogen again, then slowly heating to 90 ℃ and vacuumizing again, then slowly heating to 120 ℃, stopping vacuumizing, introducing 0.6mol of ethylene oxide, introducing the ethylene oxide at a speed of 10ml/min, heating to 165 ℃ after the introduction, preserving heat for reaction, stopping the reaction when the pressure is reduced to 0, and cooling the system to below 40 ℃;
(2) Adding 0.12mol of sulfamic acid powder into the high-pressure reaction kettle, heating while stirring, preserving heat at 130 ℃ for 105min, cooling to below 40 ℃, adding 81.4g of 10wt% ethanolamine, and regulating pH to 7-8 by using sodium hydroxide solution to obtain the waterproof locking agent for the oil field.
Example 3
(1) Adding 0.06mol of 1- [ bis- (4-fluorophenyl) methyl ] piperazine and 5.26g of potassium carbonate into a high-pressure reaction kettle, purging a pipeline and the reaction kettle for 3min by using nitrogen, vacuumizing, purging the pipeline and the reaction kettle for 2min by using nitrogen again, then slowly heating to 90 ℃ and vacuumizing again, then slowly heating to 116 ℃, stopping vacuumizing, introducing 0.9mol of ethylene oxide, introducing the ethylene oxide at a speed of 5ml/min, heating to 160 ℃ after the introduction is finished, preserving heat for reaction, stopping the reaction when the pressure is reduced to 0, and cooling the system to below 40 ℃;
(2) Adding 0.1mol of sulfamic acid powder into the high-pressure reaction kettle, heating while stirring, preserving heat at 125 ℃ for 70min, cooling to below 40 ℃, adding 99.5g of 10wt% ethanolamine, and regulating pH to 7-8 with sodium hydroxide solution to obtain the waterproof locking agent for oil fields.
Example 4
(1) Adding 0.06mol of 1- [ bis- (4-fluorophenyl) methyl ] piperazine and 1.73g of sodium hydroxide into a high-pressure reaction kettle, purging a pipeline and the reaction kettle for 3min by using nitrogen, vacuumizing, purging the pipeline and the reaction kettle for 2min by using nitrogen again, then slowly heating to 86 ℃, vacuumizing again, then slowly heating to 118 ℃, stopping vacuumizing, introducing 1.2mol of ethylene oxide at a rate of 6ml/min, heating to 162 ℃ after the introduction is finished, preserving heat for reaction, stopping the reaction when the pressure is reduced to 0, and cooling the system to below 40 ℃;
(2) Adding 0.09mol of sulfamic acid powder into the high-pressure reaction kettle, heating while stirring, preserving heat at 122 ℃ for 75min, cooling to below 40 ℃, adding 136.64g of 10wt% ethanolamine, and regulating pH to 7-8 by using sodium hydroxide solution to obtain the waterproof locking agent for the oil field.
Example 5
(1) Adding 0.06mol of 1- [ bis- (4-fluorophenyl) methyl ] piperazine and 2.44g of sodium hydroxide into a high-pressure reaction kettle, purging a pipeline and the reaction kettle for 2min by using nitrogen, vacuumizing, purging the pipeline and the reaction kettle for 3min by using nitrogen again, then slowly heating to 87 ℃, vacuumizing again, then slowly heating to 115 ℃, stopping vacuumizing, introducing 2mol of ethylene oxide at a rate of 8ml/min, heating to 163 ℃ after the introduction, preserving heat for reaction, stopping the reaction when the pressure is reduced to 0, and cooling the system to below 40 ℃;
(2) Adding 0.12mol of sulfamic acid powder into the high-pressure reaction kettle, heating while stirring, preserving heat at 127 ℃ for 100min, cooling to below 40 ℃, adding 185.5g of 10wt% ethanolamine, and regulating pH to 7-8 with sodium hydroxide solution to obtain the waterproof locking agent for oil fields.
Example 6
(1) Adding 0.06mol of 1- [ bis- (4-fluorophenyl) methyl ] piperazine and 3.16g of sodium hydroxide into a high-pressure reaction kettle, purging a pipeline and the reaction kettle for 3min by using nitrogen, vacuumizing, purging the pipeline and the reaction kettle for 2min by using nitrogen again, then slowly heating to 88 ℃ and vacuumizing again, then slowly heating to 116 ℃, stopping vacuumizing, introducing 3mol of ethylene oxide at a rate of 7ml/min, heating to 161 ℃ after the introduction, preserving heat for reaction, stopping the reaction when the pressure is reduced to 0, and cooling the system to below 40 ℃;
(2) Adding 0.14mol of sulfamic acid powder into the high-pressure reaction kettle, heating while stirring, preserving heat at 128 ℃ for 80min, cooling to below 40 ℃, adding 241.37g of 10wt% ethanolamine, and regulating pH to 7-8 with sodium hydroxide solution to obtain the waterproof locking agent for oil fields.
Example 7
(1) Adding 0.06mol of 1- [ bis- (4-fluorophenyl) methyl ] piperazine and 4.28g of potassium hydroxide into a high-pressure reaction kettle, purging a pipeline and the reaction kettle for 2min by using nitrogen, vacuumizing, purging the pipeline and the reaction kettle for 3min by using nitrogen again, then slowly heating to 90 ℃ and vacuumizing again, then slowly heating to 117 ℃, stopping vacuumizing, introducing 4mol of ethylene oxide at a speed of 9ml/min, heating to 162 ℃ after the introduction, preserving heat for reaction, stopping the reaction when the pressure is reduced to 0, and cooling the system to below 40 ℃;
(2) Adding 0.15mol of sulfamic acid powder into the high-pressure reaction kettle, heating while stirring, preserving heat at 125 ℃ for 90min, cooling to below 40 ℃, adding 274.5g of 10wt% ethanolamine, and regulating pH to 7-8 with sodium hydroxide solution to obtain the waterproof locking agent for oil fields.
Example 8
(1) Adding 0.06mol of 1- [ bis- (4-fluorophenyl) methyl ] piperazine and 4.66g of potassium hydroxide into a high-pressure reaction kettle, purging a pipeline and the reaction kettle for 3min by using nitrogen, vacuumizing, purging the pipeline and the reaction kettle for 2min by using nitrogen again, then slowly heating to 86 ℃, vacuumizing again, then slowly heating to 119 ℃, stopping vacuumizing, introducing 5mol of ethylene oxide, introducing the ethylene oxide at a speed of 7ml/min, heating to 165 ℃ after the introduction, preserving heat for reaction, stopping the reaction when the pressure is reduced to 0, and cooling the system to below 40 ℃;
(2) Adding 0.17mol of sulfamic acid powder into the high-pressure reaction kettle, heating while stirring, keeping the temperature at 123 ℃ for reaction for 60min, cooling to below 40 ℃, adding 303.6g of 10wt% ethanolamine, and regulating the pH value to 7-8 by using a sodium hydroxide solution to obtain the waterproof locking agent for the oil field.
Example 9
(1) Adding 0.06mol of 1- [ bis- (4-fluorophenyl) methyl ] piperazine and 5.1g of potassium hydroxide into a high-pressure reaction kettle, purging a pipeline and the reaction kettle for 2min by using nitrogen, vacuumizing, purging the pipeline and the reaction kettle for 3min by using nitrogen again, then slowly heating to 87 ℃, vacuumizing again, then slowly heating to 116 ℃, stopping vacuumizing, introducing 6mol of ethylene oxide at a rate of 5ml/min, heating to 160 ℃ after the introduction, preserving heat for reaction, stopping the reaction when the pressure is reduced to 0, and cooling the system to below 40 ℃;
(2) Adding 0.18mol of sulfamic acid powder into the high-pressure reaction kettle, heating while stirring, preserving heat at 129 ℃ for 120min, cooling to below 40 ℃, adding 345.6g of 10wt% ethanolamine, and regulating pH to 7-8 by using sodium hydroxide solution to obtain the waterproof locking agent for the oil field.
Example 10 testing of surface tension
The waterproof locking agent for oil field (examples 1-9) of the invention (prepared into 0.3wt% solution) was used for measuring the surface tension at room temperature according to the method of GB/T5549-2010 "surface tension measurement by pull-up liquid film method", and the waterproof locking agent for male crown technology development Co., ltd. In Tianjin was used for comparative experiments,
the results are shown in Table 1.
As can be seen from table 1: the oilfield waterproof locking agent (examples 1-9) of the invention has a surface Zhang Lijun of less than 26.5mN/m and a minimum of 22.8mN/m (example 9) when used at a concentration of 0.3 wt%; the surface tension of the waterproof locking agent of the male crown technology development limited company of the Tianjin city of comparative example is 27.8mN/m, which is obviously higher than that of the invention.
Example 11 interfacial tension testing
The waterproof locking agent of the present invention (examples 1 to 9) was prepared as a 0.3wt% solution, and the interfacial tension of kerosene and the waterproof locking agent solution of the present invention was measured by the spin drop method at room temperature according to the method of SY/T5370-2018, surface and interfacial tension measurement method, and the results are shown in Table 1 using the waterproof locking agent of Tianjin Male crown scientific development Co., ltd.
As can be seen from table 1: the waterproof locking agent for oil fields (examples 1-9) has the interfacial tension of less than 0.1mN/m and the lowest reaching of 0.032mN/m (example 9) when the using concentration is 0.3 wt%; the interfacial tension of the waterproof locking agent of the comparative example Tianjin male crown technology development limited company is 1.12mN/m, which is obviously higher than that of the invention.
Example 12 contact angle test
The core piece is placed in the 0.3wt% waterproof locking agent (examples 1-9) solution for oil fields, placed in a closed container, placed in a baking oven at 150 ℃ for 24 hours, taken out, baked in the baking oven at 150 ℃ for 2 hours, cooled, tested for contact angle by distilled water, and subjected to a comparison experiment by using waterproof locking agent of Tianjin male crown technology development Co., ltd. With the result shown in Table 1 and the picture shown in FIG. 1.
TABLE 1 results of surface tension, interfacial tension, contact Angle test
As can be seen from fig. 1 and table 1: the waterproof locking agent for oil fields (examples 1-9) has a contact angle increase of more than 50 DEG when the using concentration is 0.3wt%, wherein the maximum increase reaches 76.9 DEG (example 7); the increase of the contact angle of the waterproof locking agent of the Sedrin male crown technology development limited company of comparative example is 36.2 degrees, and the increase is obviously lower than that of the invention.
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 (6)
1. The synthesis method of the waterproof locking agent for the oil field is characterized by comprising the following specific steps of:
(1) Adding 1- [ bis- (4-fluorophenyl) methyl ] piperazine and a catalyst into a high-pressure reaction kettle, purging a pipeline and the reaction kettle for 2-3min by using nitrogen, vacuumizing, purging the pipeline and the reaction kettle for 2-3min by using nitrogen again, then slowly heating to 85-90 ℃, vacuumizing again, then slowly heating to 115-120 ℃, stopping vacuumizing, introducing ethylene oxide at a speed of 3-10ml/min, heating to 160-165 ℃ after the introduction is finished, performing heat preservation reaction, stopping the reaction when the pressure is reduced to 0, and cooling the system to below 40 ℃;
(2) Adding sulfamic acid powder into the high-pressure reaction kettle, heating while stirring, carrying out heat preservation reaction at 120-130 ℃ for 60-120min, cooling to below 40 ℃, adding 10wt% of ethanolamine, and regulating pH to 7-8 by using sodium hydroxide solution to obtain the product of the waterproof locking agent for the oil field.
2. The method for synthesizing a waterproof lock agent for oil fields as claimed in claim 1, wherein the amounts of ethylene oxide and sulfamic acid are 5 to 100 mol parts and 1.5 to 3mol parts, respectively, based on 1mol part of 1- [ di- (4-fluorophenyl) methyl ] piperazine.
3. The method for synthesizing a waterproof lock agent for oil fields as claimed in claim 2, wherein the amounts of said ethylene oxide and sulfamic acid are 20 to 100 parts by mole and 2 to 3 parts by mole, respectively, based on 1 part by mole of 1- [ di- (4-fluorophenyl) methyl ] piperazine.
4. The method for synthesizing the waterproof locking agent for the oil field, as claimed in claim 1, wherein the mass ratio of one of sodium hydroxide, potassium hydroxide and potassium carbonate serving as the catalyst in the step (1) to 1- [ bis- (4-fluorophenyl) methyl ] piperazine is 0.1-0.5:1.
5. the method for synthesizing the waterproof locking agent for the oil field, as claimed in claim 1, wherein the mass ratio of the 10wt% ethanolamine to the 1- [ bis- (4-fluorophenyl) methyl ] piperazine in the step (2) is 3-20:1.
6. the waterproof locking agent for the oil field is characterized by comprising the following molecular structural formula:
wherein n is a natural number from 5 to 100.
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| CN202311390527.5A CN117447690A (en) | 2023-10-24 | 2023-10-24 | Waterproof locking agent for oil field and synthesis method thereof |
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| CN202311390527.5A CN117447690A (en) | 2023-10-24 | 2023-10-24 | Waterproof locking agent for oil field and synthesis method thereof |
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| CN117447690A true CN117447690A (en) | 2024-01-26 |
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