CN111732943B - Fixed-point self-heat-release paraffin removal ball and preparation process thereof - Google Patents
Fixed-point self-heat-release paraffin removal ball and preparation process thereof Download PDFInfo
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- CN111732943B CN111732943B CN202010628713.8A CN202010628713A CN111732943B CN 111732943 B CN111732943 B CN 111732943B CN 202010628713 A CN202010628713 A CN 202010628713A CN 111732943 B CN111732943 B CN 111732943B
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- 239000012188 paraffin wax Substances 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 108010010803 Gelatin Proteins 0.000 claims abstract description 48
- 229920000159 gelatin Polymers 0.000 claims abstract description 48
- 239000008273 gelatin Substances 0.000 claims abstract description 48
- 235000019322 gelatine Nutrition 0.000 claims abstract description 48
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 48
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- 239000003377 acid catalyst Substances 0.000 claims abstract description 29
- 150000007524 organic acids Chemical class 0.000 claims abstract description 29
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000006184 cosolvent Substances 0.000 claims abstract description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 54
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 44
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 41
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 35
- 235000010288 sodium nitrite Nutrition 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 19
- 239000001632 sodium acetate Substances 0.000 claims description 19
- 235000017281 sodium acetate Nutrition 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 235000006408 oxalic acid Nutrition 0.000 claims description 18
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 18
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 18
- 235000019270 ammonium chloride Nutrition 0.000 claims description 17
- 239000001509 sodium citrate Substances 0.000 claims description 16
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 13
- 239000003086 colorant Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 239000004304 potassium nitrite Substances 0.000 claims description 4
- 235000010289 potassium nitrite Nutrition 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 2
- 239000001993 wax Substances 0.000 abstract description 47
- 239000003921 oil Substances 0.000 abstract description 42
- 235000019198 oils Nutrition 0.000 abstract description 40
- 239000010779 crude oil Substances 0.000 abstract description 22
- 235000019476 oil-water mixture Nutrition 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 238000011010 flushing procedure Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 10
- 239000008188 pellet Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 239000003129 oil well Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
-
- 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
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/16—Materials undergoing chemical reactions when used
- C09K5/18—Non-reversible chemical reactions
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B37/00—Methods or apparatus for cleaning boreholes or wells
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/08—Pipe-line systems for liquids or viscous products
- F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
- F17D1/18—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity by heating
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- Engineering & Computer Science (AREA)
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mining & Mineral Resources (AREA)
- Physics & Mathematics (AREA)
- Geology (AREA)
- Thermal Sciences (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Public Health (AREA)
- Water Supply & Treatment (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Lubricants (AREA)
Abstract
A fixed-point self-heat-release paraffin removal ball and a preparation process thereof comprise, by mass, 10-20 parts of gelatin, 10-20 parts of polyacrylamide, 50-60 parts of a heating agent, 3-5 parts of a retarder, 10-15 parts of an organic acid catalyst and 15-25 parts of a cosolvent. The paraffin removal system of the invention is characterized in that the paraffin removal substance and water in the oil pipe are subjected to chemical reaction, the generated heat is directly diffused to paraffin deposited in the oil pipe, and the heat dissipated to the stratum is very little, so that the heat loss caused by the wax removal of the hot oil well-flushing can be avoided, and the heat efficiency is very high. Because all substances in the paraffin removal ball formula are water-soluble, when the paraffin removal ball is dissolved in an oil-water mixture, the properties of the crude oil cannot be influenced, and the subsequent processing of the crude oil cannot be influenced.
Description
Technical Field
The invention belongs to the technical field of crude oil production, and relates to a fixed-point self-heat-release paraffin removal ball and a preparation process thereof.
Background
In the process of crude oil gathering and transportation, the oil temperature is reduced due to various reasons, when the oil temperature is reduced to the cloud point, wax crystals begin to be separated out and adsorbed on the pipe wall, the oil transportation pipe diameter is gradually reduced due to the irreversibility of wax precipitation and wax melting temperature, the wax precipitation of an external transportation pipeline is serious, the pressure of an external transportation pump is increased, the daily transportation capacity is reduced, and the crude oil production is directly restrained. Therefore, the wax deposition on the inner wall of the pipeline is removed, the normal production is ensured, and the output capacity is improved to an extent that the process is not slow. In order to remove the wax deposition in the pipeline, many methods are adopted, such as the utilization of wax-proofing agent, hot-washing wax-removing, microorganism wax-removing and preventing technology, mechanical wax-removing and chemical ball wax-removing, wherein the chemical ball wax-removing is adopted, so that the method is a good method which is simple, convenient, feasible and effective. However, the prior art has three defects; firstly, in the prior art, the paraffin removal ball is clamped in the running process of a pipeline, so that the flow resistance of crude oil is increased, even the pipeline is blocked, and the specific position of the paraffin removal ball cannot be determined for paraffin removal, so that the production is difficult; secondly, in order to remove wax deposition in the pipeline, people adopt a hot washing wax removal method, but the hot washing wax removal needs to be added with hot washing agent in batches, which wastes time and labor; thirdly, when wax is cleaned by hot washing, the thermal efficiency is low and the heat loss is serious.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a fixed-point self-heat-release paraffin removal ball and a preparation process thereof, wherein the paraffin removal ball is put in one time, so that batch input in hot-washing paraffin removal can be avoided, and manpower and material resources are saved; the paraffin removal ball has high thermal efficiency, and the generated heat is directly diffused to the paraffin deposited in the oil pipe, so that the heat dissipated to the stratum is very little, thereby avoiding the heat loss caused by the wax removal of the hot oil well-flushing and having high thermal efficiency.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a fixed-point self-heat-release paraffin removal ball comprises, by mass, 10-20 parts of gelatin, 10-20 parts of polyacrylamide, 50-60 parts of a heating agent, 3-5 parts of a retarder and 10-15 parts of an organic acid catalyst.
The invention has the further improvement that the heat generating agent comprises 25-30 parts of ammonium chloride and 25-30 parts of sodium nitrite by mass parts, or the heat generating agent comprises 25-30 parts of ammonium chloride and 25-30 parts of potassium nitrite by mass parts.
The invention has the further improvement that the retarder is one of sodium bicarbonate, sodium acetate, potassium carbonate and potassium bicarbonate; the organic acid catalyst is one of oxalic acid, citric acid and tartaric acid.
The invention is further improved in that the cosolvent is a mixture of sodium citrate and sodium bicarbonate; the paraffin removal ball also comprises a colorant, wherein the colorant accounts for 1 part when the gelatin accounts for 10-15 parts by weight.
The invention has the further improvement that the cosolvent comprises 5-10 parts of citric acid and 10-15 parts of sodium bicarbonate by mass.
The invention has the further improvement that the paraffin removal ball also comprises 15 to 25 portions of cosolvent according to the mass portion.
The invention has the further improvement that the paraffin removal ball comprises 10-20 parts of gelatin, 10-20 parts of polyacrylamide, 25-30 parts of ammonium chloride, 25-30 parts of sodium nitrite, 2-5 parts of sodium acetate, 10-15 parts of oxalic acid, 5-10 parts of sodium citrate and 10-15 parts of sodium bicarbonate.
A preparation process of a fixed-point self-heat-release paraffin removal ball comprises the following steps:
1) uniformly mixing 50-60 parts of a heating agent, 3-5 parts of a retarder and 10-15 parts of an organic acid catalyst in parts by weight, and performing compression molding to obtain a spherical object;
heating and melting 10-20 parts of gelatin, uniformly mixing with 10-20 parts of polyacrylamide, adding water, and stirring for 10-15min to obtain a mixture; the ratio of gelatin to water was (10-20) g: (10-15) mL;
2) and putting the spherical object into the mixture, wrapping the mixture on the surface of the small ball to form an outer layer, and extruding, cooling and molding by adopting a spherical mold with a circular groove to obtain the paraffin removal ball.
A further improvement of the invention is that the diameter of the ball is 35-38 mm.
A further development of the invention is that the outer layer has a thickness of 5 to 6 mm.
Compared with the prior art, the invention has the following beneficial effects:
1. the selected self-heat-release system has large heat release and high heat efficiency. The selected self-heat-release system is self-accelerating reaction, and compared with the existing hydrogen peroxide heat-release system and polyhydroxy aldehyde oxidation heat-release system, the heat-release system has large heat release. The paraffin removal system is characterized in that a paraffin removal substance and water in an oil pipe are subjected to chemical reaction, the generated heat is directly diffused to paraffin deposited in the oil pipe, and the heat dissipated to a stratum is very little, so that heat loss caused by the hot oil well washing and paraffin removal can be avoided, and the heat efficiency is very high.
2. High efficiency, energy saving and saving of electric energy and heat energy. The reaction is self-exothermic, so that the system does not need to be excited by other heat sources, and can be used independently without heating methods such as steam injection and the like.
3. Excellent environmental protection performance, and the chemical agent and the product thereof are safe, environment-friendly, nontoxic, tasteless and easy to treat. Because all substances in the paraffin removal ball formula are water-soluble, when the paraffin removal ball is dissolved in an oil-water mixture, the properties of the crude oil cannot be influenced, and the subsequent processing of the crude oil cannot be influenced.
Drawings
FIG. 1 is a graph showing the exothermic properties of the paraffin wax removal ball of example 1.
Figure 2 is the exothermic performance of the paraffin removal ball of example 2.
Figure 3 is the exothermic performance of the paraffin wax removal ball of example 3.
Figure 4 is the exothermic performance of the paraffin wax removal ball of example 4.
Figure 5 is the heat release performance of the paraffin removal ball of example 1 at different water flow pressures.
Figure 6 is the heat release performance of the paraffin removal ball of example 2 at different water flow pressures.
Figure 7 is the heat release performance of the paraffin removal ball of example 3 at different water flow pressures.
Figure 8 is the heat release performance of the paraffin removal ball of example 4 at different water flow pressures.
FIG. 9 is a schematic structural view of a fixed-point self-exothermic paraffin removal ball prepared in example 4.
Fig. 10 is a schematic view of an indoor simulation apparatus.
In the figure, 1-oil groove, 2-oil pump, 3-wax tube and 4-shell.
Detailed Description
In order to overcome the defects of the prior art, the invention provides a fixed-point self-heat-release paraffin removal ball formula and a preparation process thereof, and the paraffin removal ball is explained in several different aspects below.
The paraffin removal ball is a solid ball, and comprises, by weight, 10-20 parts of gelatin, 10-20 parts of polyacrylamide, 50-60 parts of a heating agent, 3-5 parts of a retarder, 10-15 parts of an organic acid catalyst and 15-25 parts of a cosolvent.
Preferably, the heat generating agent comprises 25-30 parts of ammonium chloride and 25-30 parts of nitrite by weight.
The nitrite is one of sodium nitrite and potassium nitrite. The nitrite is preferably sodium nitrite.
The cosolvent is a mixture of sodium citrate and sodium bicarbonate.
Preferably, the cosolvent comprises 5-10 parts of sodium citrate and 10-15 parts of sodium bicarbonate in parts by weight.
The organic acid catalyst is one of oxalic acid, citric acid and tartaric acid.
Preferably, the organic acid catalyst is oxalic acid.
The retarder is one of sodium bicarbonate, sodium acetate, potassium bicarbonate and potassium carbonate.
Preferably, the retarder is sodium acetate.
Preferably, the paraffin removal ball comprises, by weight, 10-20 parts of gelatin, 10-20 parts of polyacrylamide, 25-30 parts of ammonium chloride, 25-30 parts of sodium nitrite, 2-5 parts of sodium acetate, 10-15 parts of oxalic acid, 5-10 parts of sodium citrate and 10-15 parts of sodium bicarbonate.
The paraffin removal ball mainly comprises two parts:
1) for the outer layer of the paraffin removal ball, the component of the outer layer of the paraffin removal ball is polyacrylamide which is used as the main component of the outer shell of the paraffin removal ball, and gelatin is used as a forming auxiliary agent of the polyacrylamide, so that the paraffin removal ball is easy to form, the mechanical property of the paraffin removal ball is improved, and the paraffin removal ball can be dissolved and softened to a certain extent; the shell component of the paraffin removal ball is completely soluble in a water phase, does not pollute crude oil, and simultaneously, the polyacrylamide serving as the shell component is also a flocculation component added in oilfield sewage treatment. Preferably, the thickness of the outer layer of the paraffin removal ball is about 5-6 mm; the surface of the paraffin removal ball is provided with a hydraulic stress groove which is a circular groove, and the diameter of the hydraulic stress groove is preferably 6-10 mm; preferably, it has a depth of 3-5 mm; the hydraulic stress groove is used as a bearing point of the water flow pressure of the oil-water mixture when the oil pipeline is blocked with wax, and provides a water environment for the wax removing ball. The water of the oil-water mixture in the oil pipeline is used as the initiator of the reaction, so that the paraffin removal ball can quickly generate self-heating reaction after meeting water.
When the outer layer is cooled and not formed, the wax cleaning ball is pressed by a spherical mould with a groove, and the wax cleaning ball is used for providing a water environment.
2) For the inner part of the paraffin removal ball, the inner core is a solid ball body with the diameter of 35-38 mm;
the inner core of the paraffin removal ball comprises a heating agent, an organic acid catalyst, a retarder and a cosolvent;
the heating agent is a mixture of sodium nitrite and ammonium chloride, and has the main function that when the mixture of the sodium nitrite and the ammonium chloride contacts with water in crude oil, a large amount of heat is generated by spontaneous reaction, and the dissolution of oil wax on the wall of an oil pipeline is accelerated;
the wax removal ball organic acid catalyst is oxalic acid, and the main function of the catalyst is to control the heat generation of an initiation system;
the retarder is sodium acetate, and the retarder is mainly used for controlling the initiation time;
the cosolvent is sodium bicarbonate and sodium citrate, and has the main function of accelerating the dissolution rate of the paraffin removal ball;
preferably, the paraffin removal ball also comprises a colorant, and the colorant is a natural non-toxic water-soluble colorant and cannot pollute crude oil. As a wax removing ball coloring agent, the wax removing ball coloring agent mainly has the function of distinguishing wax removing balls with different heat release performances. When the gelatin is 10 to 15 parts by weight, the colorant is 1 part.
The gas generated by the reaction in the paraffin removal ball is inert gas nitrogen, so that the original pipeline cannot be corroded, and the generated gas flow can enhance the flowability of the crude oil. The exothermic agent does not pollute crude oil, and sodium chloride and water generated after the exothermic agent reacts can be completely dissolved in a water phase, and the exothermic agent does not pollute the crude oil.
2. The preparation process of the paraffin removal ball comprises the following steps:
1) according to the mass portion, 25-30 portions of ammonium chloride, 25-30 portions of sodium nitrite, 2-5 portions of sodium acetate, 10-15 portions of oxalic acid, 5-10 portions of sodium citrate and 10-15 portions of sodium bicarbonate are uniformly mixed, and are pressed and molded by a spherical mold with the diameter of 24-30mm to obtain the pellet.
2) Heating 10-20 parts of gelatin at a high temperature of 40-50 ℃ for melting, then uniformly mixing with 10-20 parts of polyacrylamide, adding 10-15mL of water, uniformly stirring while heating, wherein the stirring speed is 600r/min, and the stirring time is 10-15min, so that the gelatin becomes viscous and is in a certain flowing state, and thus a mixture is obtained.
3) Putting the prepared pellets into the mixture, wrapping the surfaces of the pellets with the mixture of gelatin and polyacrylamide to form an outer layer, cooling the outer layer to be in a semi-solidified state to facilitate the wrapping, extruding and cooling the outer layer to form the paraffin removal balls, wherein the thickness of the outer layer is 5-6mm, and the outer layer is formed by a spherical die with a diameter of 45-50mm and a circular groove.
The present invention will be described in further detail below with reference to different formulations for different high water cut and high oil cut crudes
When the oil pipeline meets the wax removal ball and meets water in the pipeline, the oil pipeline generates heat to cause local high temperature, so that wax deposited in the oil pipeline is quickly dissolved, and the fixed-point wax removal effect is further achieved. The paraffin removal ball can select a certain amount of paraffin removal balls to carry out fixed-point paraffin removal according to the length of a paraffin clamping pipe of an oil pipeline; the wax removal balls are put in one time, so that batch input in hot washing wax removal can be avoided, and manpower and material resources are saved; the paraffin removal ball has high thermal efficiency, and the generated heat is directly diffused to the paraffin deposited in the oil pipe, so that the heat dissipated to the stratum is very little, thereby avoiding the heat loss caused by the wax removal of the hot oil well-flushing and having high thermal efficiency.
The data for examples 1-4 are shown in Table 1.
Example 1
The invention provides a formula of a fixed-point self-heat-release paraffin removal ball for crude oil with water content of more than 80%, wherein the internal components comprise a heating agent, an organic acid catalyst and a retarder, the heating agent comprises ammonium chloride salt and sodium nitrite, the organic acid catalyst is oxalic acid, and the retarder is sodium acetate.
The preparation method of the paraffin removal ball comprises the following steps:
firstly, mixing ammonium chloride salt, sodium nitrite, oxalic acid and sodium acetate powder according to a formula in a table 1 to prepare pellets with the diameter of 35-38 mm.
Step two, heating and melting gelatin in a water bath at 40-50 ℃, uniformly mixing the gelatin with polyacrylamide, adding water, uniformly stirring, heating and stirring simultaneously, after the gelatin becomes viscous and is in a certain flowing state, stirring at the speed of 500r/min for 15min, wrapping the prepared pellets outside the pellets by using a mixture of the gelatin and the polyacrylamide to form an outer layer, wherein the thickness of the outer layer is 5-6 mm; the ratio of gelatin to water was 20 g: 15 mL;
and step three, extruding, cooling and molding the paraffin removal ball by adopting a spherical mold with a circular concave hole with the diameter of 45-50mm to obtain the paraffin removal ball.
Example 2
The invention provides a fixed-point self-heat-release paraffin removal ball formula for crude oil with the water content of more than 80%, wherein the formula contains a cosolvent, and the cosolvent is sodium bicarbonate and sodium citrate. The internal formula comprises that the heating agent comprises ammonium chloride salt and sodium nitrite, the organic acid catalyst is oxalic acid, and the retarder is sodium acetate.
The preparation method of the paraffin removal ball comprises the following steps:
step one, weighing a certain mass of medicine according to a certain proportion according to a formula in the table 1, and mixing ammonium chloride salt, sodium nitrite, oxalic acid and sodium acetate powder to prepare a small ball with the diameter of 35-38 mm.
Step two, heating and melting gelatin in a water bath at 40-50 ℃, uniformly mixing the gelatin with polyacrylamide, adding water, uniformly stirring, heating and stirring simultaneously, after the gelatin becomes viscous and is in a certain flowing state, stirring at the speed of 600r/min for 10min, and wrapping the prepared pellets with a mixture of the gelatin and the polyacrylamide to form an outer layer, wherein the thickness of the outer layer is 5-6 mm; the ratio of gelatin to water was 10 g: 10 mL;
and step three, extruding, cooling and molding by adopting a spherical mold with a diameter of 45-50mm and a circular groove.
Example 3
The invention provides a formula of a fixed-point self-heat-release paraffin removal ball for crude oil with an oil content of 70-75%, wherein the internal formula comprises a heat generating agent, an organic acid catalyst and a retarder, the heat generating agent comprises ammonium chloride salt and sodium nitrite, the organic acid catalyst is oxalic acid, and the retarder is sodium acetate.
The preparation method of the paraffin removal ball comprises the following steps:
Step one, weighing a certain mass of medicine according to a certain proportion according to a formula in the table 1, and mixing ammonium chloride salt, sodium nitrite, oxalic acid and sodium acetate powder to prepare a small ball with the diameter of 35-38 mm.
Step two, heating and melting gelatin in a water bath at 40-50 ℃, uniformly mixing the gelatin with polyacrylamide, adding water, uniformly stirring, heating and stirring simultaneously, after the gelatin becomes viscous and is in a certain flowing state, stirring at 550r/min for 12min, wrapping the prepared pellets outside the pellets by using a mixture of the gelatin and the polyacrylamide to form an outer layer, wherein the thickness of the outer layer is 5-6 mm; the ratio of gelatin to water was 18 g: 15 mL;
and step three, extruding, cooling and molding by adopting a spherical mold with a diameter of 45-50mm and a circular groove.
Example 4
The invention provides a formula of a fixed-point self-heat-release paraffin removal ball for crude oil with an oil content of 70-75%, wherein the formula contains a cosolvent, the cosolvent is sodium citrate and sodium bicarbonate, the internal formula comprises a heat generating agent, an organic acid catalyst and a retarder, the heat generating agent comprises ammonium chloride and sodium nitrite, the organic acid catalyst is oxalic acid, and the retarder is sodium acetate.
The preparation method of the paraffin removal ball comprises the following steps:
step one, weighing a certain mass of medicine according to a certain proportion according to a formula in the table 1, and mixing ammonium chloride salt, sodium nitrite, oxalic acid and sodium acetate powder to prepare a small ball with the diameter of 35-38 mm.
Step two, heating and melting gelatin in a water bath at 40-50 ℃, uniformly mixing the gelatin with polyacrylamide, adding water, uniformly stirring, heating and stirring simultaneously, after the gelatin becomes viscous and is in a certain flowing state, stirring at the speed of 520r/min for 13min, and wrapping the prepared pellets with a mixture of the gelatin and the polyacrylamide to form an outer layer, wherein the thickness of the outer layer is 5-6 mm; gelatin to water ratio 12 g: 10 mL;
and step three, extruding, cooling and molding by adopting a spherical mold with a diameter of 45-50mm and a circular groove.
TABLE 1 EXAMPLES 1-4 Paraffin ball processing parameter Table (parts by weight)
Referring to fig. 9, the inner core of the paraffin removal ball prepared in this example has a diameter of 37mm, the outer layer has a thickness of 5mm, and the surface of the paraffin removal ball has 32 hydraulic pressure bearing grooves, which are circular grooves, and have a diameter of 6mm and a depth of 3 mm.
Performance testing
Evaluation of mechanical properties: the mechanical strength of the paraffin removal ball is measured by a 10t testing machine, and the testing pressure is as follows: 1Mpa and 2Mpa (the pressure of an oil pipeline is 0.8Mpa to 1.6Mpa), whether the surface of the paraffin removal ball is complete or not is observed, and the results are shown in Table 2 and the results of the mechanical property test of the paraffin removal ball in Table 2
| Pressure of | Example 1 | Example 2 | Example 3 |
| 1Mpa | Qualified | Qualified | Qualified |
| 2Mpa | Qualified | Qualified | Qualified |
Evaluating the heat release performance of the paraffin removal ball under high water content and high oil content:
1. the present invention provides an indoor simulator, as shown in fig. 10, the device comprises an oil pump 2, a wax deposition pipe 3 and an oil groove 1 which are arranged in a shell 4. The outlet of the oil tank 1 is connected with one end of an oil well pump 2, the other end of the oil well pump 2 is connected with one end of a wax deposition pipe 3, and the other end of the wax deposition pipe 3 is connected with the inlet of the oil tank 1. The simulation device is used for unfolding and simulating the self-fixed-point paraffin removal process of the paraffin removal ball. The oil well pump is used for providing power, the wax deposition pipe is used for simulating the wax blockage phenomenon of an oil pipeline, and the oil drum is used for providing and recovering an oil-water mixture. The device forms a circulating system, an oil-water mixture is conveyed to a wax precipitation pipe from an oil drum by using an oil pump, a prepared paraffin removal ball is put into the oil drum, the paraffin removal condition of the oil-water mixture at the wax precipitation position of a pipeline is observed, and the oil-water mixture is recovered at the tail of the oil pipeline and returns to the oil drum again after passing through the wax precipitation pipe for use.
The method comprises the following steps:
(1) wax removal balls were prepared according to examples 1, 2, 3, and 4, and placed into wax tubes according to the wax removal ball formulation of example 1.
(2) And putting the paraffin removal ball into an oil drum to simulate the normal flowing condition of the paraffin removal ball in an oil pipeline, opening an oil well pump to adjust the flow velocity of the oil-water mixture to 0.3-0.5m/s, conveying the paraffin removal ball to a wax precipitation position of the pipeline under the flushing of the oil-water mixture, and performing fixed-point paraffin removal. Meanwhile, a stopwatch is started, and the exothermic dissolution time of the paraffin removal ball is recorded by the stopwatch.
(3) And monitoring the heat release amount of the paraffin removal ball in the paraffin precipitation pipe every 1-2min, and waiting for the paraffin removal ball to completely release heat so as to obtain the heat release performance evaluation of the paraffin removal ball.
(4) When the wax removal ball exotherm was complete, the experiment was stopped. The wax removing balls prepared in the remaining examples 2 to 4 were subjected to the same experiment as the wax removing ball a.
The results of the wax ball test are shown in fig. 1, 2, 3 and 4. As can be seen from the figures 1, 2, 3 and 4, the water content of the crude oil is high, and the heating value of the paraffin removal ball is high; the crude oil has high oil content and the wax removal ball has low heat release. If the cosolvent is added into the paraffin removal ball formula, the paraffin removal ball has high dissolution rate and quick heat release.
Evaluating the heat release performance of the paraffin removal ball under different water flow pressures:
the paraffin removal ball releases heat after reaching a paraffin tube clamping tube in crude oil with high water content for 10-20min, and releases heat after reaching the paraffin tube clamping tube in crude oil with high oil content for 20-30 min. The invention detects the heat release of the paraffin removal ball when the paraffin removal ball bears different water flow pressures, preferably, the water flow pressures are 0.05MPa, 0.10MPa and 0.20 MPa. As can be seen from fig. 5, 6, 7 and 8, the wax removing balls have different dissolving capacities under different water flow pressures, and the higher the water flow pressure is, the faster the wax removing balls are dissolved.
Example 5
A preparation process of a fixed-point self-heat-release paraffin removal ball comprises the following steps:
1) according to the mass parts, 25 parts of ammonium chloride, 30 parts of sodium nitrite, 3 parts of a retarder, 12 parts of an organic acid catalyst, 5 parts of sodium citrate and 15 parts of sodium bicarbonate are uniformly mixed and pressed to form a spherical object with the diameter of 35 mm;
wherein the retarder is sodium bicarbonate. The organic acid catalyst is oxalic acid.
2) And putting the spherical object into the mixture, wrapping the mixture on the surface of the small ball to form an outer layer with the thickness of 5mm, and extruding, cooling and molding by adopting a spherical mold with a circular groove to obtain the paraffin removal ball.
Example 6
A preparation process of a fixed-point self-heat-release paraffin removal ball comprises the following steps:
1) according to the mass parts, 30 parts of ammonium chloride, 27 parts of potassium nitrite, 4 parts of a retarder, 15 parts of an organic acid catalyst, 7 parts of sodium citrate and 10 parts of sodium bicarbonate are uniformly mixed and pressed to form a spherical object with the diameter of 36 mm;
heating and melting 15 parts of gelatin, uniformly mixing with 20 parts of polyacrylamide and 1 part of colorant, adding water, heating to 50 ℃, and stirring at 550r/min for 10-15min to obtain a mixture; gelatin to water ratio 15 g: 13 mL;
Wherein the retarder is sodium acetate. The organic acid catalyst is citric acid.
2) And putting the spherical object into the mixture, wrapping the mixture on the surface of the small ball to form an outer layer with the thickness of 5mm, and extruding, cooling and molding by adopting a spherical mold with a circular groove to obtain the paraffin removal ball.
Example 7
A preparation process of a fixed-point self-heat-release paraffin removal ball comprises the following steps:
1) according to the mass parts, 28 parts of ammonium chloride, 25 parts of sodium nitrite, 5 parts of a retarder, 10 parts of an organic acid catalyst, 10 parts of sodium citrate and 13 parts of sodium bicarbonate are uniformly mixed and pressed to form a spherical object with the diameter of 37 mm;
heating and melting 20 parts of gelatin, uniformly mixing with 10 parts of polyacrylamide, adding water, heating to 45 ℃, and stirring at 600r/min for 10-15min to obtain a mixture; the ratio of gelatin to water was 20 g: 15 mL;
2) and putting the spherical object into the mixture, wrapping the mixture on the surface of the small ball to form an outer layer with the thickness of 6mm, and extruding, cooling and molding by adopting a spherical mold with a circular groove to obtain the paraffin removal ball.
The retarder is potassium bicarbonate. The organic acid catalyst is tartaric acid.
Example 8
A preparation process of a fixed-point self-heat-release paraffin removal ball comprises the following steps:
1) According to the mass parts, 28 parts of ammonium chloride, 25 parts of sodium nitrite, 3 parts of a retarder, 14 parts of an organic acid catalyst, 8 parts of sodium citrate and 12 parts of sodium bicarbonate are uniformly mixed and pressed to form a spherical object with the diameter of 35 mm;
heating 12 parts of gelatin to melt, uniformly mixing with 18 parts of polyacrylamide, adding water, heating to 50 ℃, and stirring at 500r/min for 10-15min to obtain a mixture; gelatin to water ratio 12 g: 10 mL;
wherein the retarder is sodium acetate. The organic acid catalyst is tartaric acid.
2) And putting the spherical object into the mixture, wrapping the mixture on the surface of the small ball to form an outer layer with the thickness of 5mm, and extruding, cooling and molding by adopting a spherical mold with a circular groove to obtain the paraffin removal ball.
Example 9
A preparation process of a fixed-point self-heat-release paraffin removal ball comprises the following steps:
1) according to the mass parts, 28 parts of ammonium chloride, 25 parts of sodium nitrite, 5 parts of a retarder, 15 parts of an organic acid catalyst, 9 parts of sodium citrate and 11 parts of sodium bicarbonate are uniformly mixed and pressed to form a spherical object with the diameter of 38 mm;
heating and melting 17 parts of gelatin, uniformly mixing with 13 parts of polyacrylamide and 1 part of colorant, adding water, heating and stirring for 10-15min to obtain a mixture; the ratio of gelatin to water was 17 g: 11 mL;
Wherein the retarder is potassium carbonate. The organic acid catalyst is tartaric acid.
2) And putting the spherical object into the mixture, wrapping the mixture on the surface of the small ball to form an outer layer with the thickness of 6mm, and extruding, cooling and molding by adopting a spherical mold with a circular groove to obtain the paraffin removal ball.
Claims (8)
1. A fixed-point self-heat-release paraffin removal ball is characterized by comprising, by mass, 10-20 parts of gelatin, 10-20 parts of polyacrylamide, 50-60 parts of a heat generating agent, 3-5 parts of a retarder and 10-15 parts of an organic acid catalyst;
the heat generating agent comprises 25-30 parts of ammonium chloride and 25-30 parts of sodium nitrite by mass, or the heat generating agent comprises 25-30 parts of ammonium chloride and 25-30 parts of potassium nitrite by mass;
the retarder is one of sodium bicarbonate, sodium acetate, potassium carbonate and potassium bicarbonate; the organic acid catalyst is one of oxalic acid, citric acid and tartaric acid.
2. The fixed-point self-heat-release paraffin removal ball as claimed in claim 1, further comprising 15-25 parts by weight of a cosolvent.
3. The fixed-point self-exothermic paraffin removal ball according to claim 2, wherein the cosolvent is a mixture of sodium citrate and sodium bicarbonate; the paraffin removal ball also comprises a colorant, wherein the colorant accounts for 1 part when the gelatin accounts for 10-15 parts by weight.
4. The fixed-point self-exothermic paraffin removal ball according to claim 3, wherein the cosolvent comprises 5-10 parts by weight of sodium citrate and 10-15 parts by weight of sodium bicarbonate.
5. The fixed-point self-heat-release paraffin ball as claimed in claim 1, which comprises 10-20 parts of gelatin, 10-20 parts of polyacrylamide, 25-30 parts of ammonium chloride, 25-30 parts of sodium nitrite, 2-5 parts of sodium acetate, 10-15 parts of oxalic acid, 5-10 parts of citric acid and 10-15 parts of sodium bicarbonate.
6. A preparation process of a fixed-point self-heat-release paraffin removal ball is characterized by comprising the following steps:
1) uniformly mixing 50-60 parts of a heating agent, 3-5 parts of a retarder and 10-15 parts of an organic acid catalyst in parts by weight, and performing compression molding to obtain a spherical object;
heating and melting 10-20 parts of gelatin, uniformly mixing with 10-20 parts of polyacrylamide, adding water, and stirring for 10-15min to obtain a mixture; the ratio of gelatin to water was (10-20) g: (10-15) mL;
2) and putting the spherical object into the mixture, wrapping the mixture on the surface of the small ball to form an outer layer, and extruding, cooling and molding by adopting a spherical mold with a circular groove to obtain the paraffin removal ball.
7. The process for preparing a fixed-point self-exothermic paraffin removal ball according to claim 6, wherein the diameter of the ball is 35-38 mm.
8. The process for preparing a fixed-point self-exothermic paraffin removal ball according to claim 6, wherein the thickness of the outer layer is 5-6 mm.
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