CN109735315B - Environment-friendly delayed crosslinking profile control agent for oil extraction and preparation method and application thereof - Google Patents
Environment-friendly delayed crosslinking profile control agent for oil extraction and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of an environment-friendly delayed crosslinking profile control agent for oil extraction, which comprises the following steps: s1: synthesizing a salt-resistant polymer solution; s2: hydrolyzing the salt-resistant polymer solution to obtain a hydrolysate; s3: treating the hydrolysate to obtain salt-resistant polymer; s4: at normal temperature, adding the salt-resistant polymer, the phenolic compound, the aldehyde compound and the catalyst into deionized water, and stirring and mixing uniformly to obtain the environment-friendly delayed crosslinking profile control agent for oil recovery. Also relates to the environment-friendly delayed crosslinking profile control agent for oil extraction obtained by the preparation method and application thereof in oil extraction. The environment-friendly delayed crosslinking profile control agent for oil extraction has a plurality of excellent performances such as excellent thermal stability, plugging performance, high temperature resistance, tackifying performance, high mineralization resistance and the like, so that the environment-friendly delayed crosslinking profile control agent can be applied to oil extraction, can be used for realizing various profile control effects, and has good application prospect and production potential in the technical field of oil extraction.
Description
Technical Field
The invention relates to a profile control agent for improving the yield and recovery ratio of petroleum in the exploitation and development of an oil field, a preparation method and application thereof, in particular to an environment-friendly delayed crosslinking profile control agent for oil extraction, a preparation method and application thereof, belonging to the technical field of petroleum exploitation auxiliary agents.
Background
At present, old water-flooding oil fields in China generally enter a high-water-content or even ultra-high-water-content exploitation period, and long-term water-flooding scouring causes injected water to perform low-efficiency or ineffective circulation along a water flow dominant channel or a high-permeability strip, so that the water-flooding development effect and the overall benefit are seriously influenced, the yield is reduced, the benefit is reduced, and the influence on the environment is increasingly increased.
In order to solve the problem, people develop a deep liquid flow diversion and profile control technology, which is an important effective means for improving the development effect and the efficiency of water drive at home and abroad. The technology mainly utilizes a diverting chemical agent to block a water flow dominant channel at the deep part of an oil reservoir or reduce the seepage capability of the channel, thereby forming flow resistance, enlarging swept volume by profile control of subsequent injection, further improving water drive efficiency and improving water drive development effect.
So far, the research of the domestic deep liquid flow diversion and profile control technology mainly focuses on liquid flow diversion and profile control chemical agent systems, and the systems mainly comprise two main types of organogel and inorganic gel.
At present, most of organic gel profile control and flooding systems applied to oilfield development sites are polymer gel systems obtained by crosslinking organic chromium and high molecular compounds. But the organochromium crosslinking system is due to residual Cr6+Easily releases pungent odor with free formaldehyde and small molecular reactants (such as phenol and the like) which do not completely react in the system, can cause harm to the body of field constructors and serious pollution to the water environment.
With the more and more strict environmental protection requirements of the country on the field operation of the oil field in recent years, the research and development of low-toxicity and environment-friendly profile control agents for oil extraction, the improvement of plugging efficiency, the improvement of the extraction effect and the like are urgent needs at present.
The applicant has made a great deal of intensive research aimed at new profile control agents and has achieved numerous results, such as:
CN104927005A discloses a pre-crosslinked gel swelling particle alkali-resistant profile control agent, a preparation method and application thereof, wherein the preparation method of the profile control agent comprises the following steps: s1: preparing elastic particles with strong toughness; s2: oil-filling treatment of elastic particles with strong toughness; s3: premixing materials; s4: and carrying out polymerization reaction to obtain the pre-crosslinked gel swelling particle alkali-resistant profile control agent. The preparation method obtains the target product with the best effect through the synergistic effect of unique modification of raw materials, proper selection of components, unique steps and process parameters of the preparation method and the like, has excellent mechanical property, temperature resistance, mineralization resistance and alkali resistance, and has good application prospect and industrialization potential in the field of energy exploitation.
CN105368423A discloses a chrome-free composite resin gel profile control agent for oil extraction, which comprises, by weight, 5-9 parts of nano silicon dioxide modified cross-linked polymer, 0.1-0.16 part of stabilizer, 0.06-0.12 part of reinforcing agent, 0.15-0.22 part of organic sulfonate, 0.2-0.4 part of density regulator, 0.2-0.3 part of surfactant, 0.05-0.1 part of auxiliary agent, 0.1-0.2 part of thickener, 0.08-0.14 part of wetting agent and 30-40 parts of water, and the profile control agent has excellent mechanical property, temperature resistance, mineralization resistance, alkali resistance and the like.
CN106883357A discloses a pre-crosslinked gel slow-expansion microsphere profile control agent, which comprises, by weight, 2-4 parts of a polyacrylic acid grafting prepolymer, 18-23 parts of an acrylamide monomer, 0.5-1.5 parts of a hydrophobic monomer, 2.5-4 parts of a salt-resistant monomer, 0.25-1 part of a temperature-resistant tackifying monomer, 2-4 parts of sodium carbonate, 1.25-1.5 parts of a composite surfactant, 1.5-3 parts of modified kaolin powder, 0.025-0.05 part of a composite crosslinking agent, 0.05-0.1 part of an initiator and 60-75 parts of deionized water. The profile control agent has excellent high temperature resistance, high salt resistance, good tackifying performance, good plugging performance and the like, and has good application prospect and industrialization potential in the field of oil exploitation.
Apart from the applicant, other researchers have conducted a great deal of intensive research and have obtained a variety of profile control agents with different properties, methods for preparing them and methods for oil recovery using them, such as:
CN103265934A discloses a profile control agent for a water injection well, which is prepared from the following components in parts by weight based on 100 parts by weight: 3-4 parts of acrylamide, 3-5 parts of bentonite, 0.1-0.2 part of modified polypropylene fiber, 0.1-0.2 part of initiator, 0.1-0.3 part of cross-linking agent and the balance of water. The profile control agent has the characteristics of certain strength and adjustable gelling time, and also has the excellent characteristics of certain flushing resistance, prolonged effective period of profile control of a gel water injection well and forced steering of follow-up injected water to an oil layer with lower permeability, so that the water injection sweep efficiency and the crude oil recovery rate can be improved.
CN103194192A discloses an alkali-resistant time-lapse expansion particle profile control agent, which is prepared by the following steps: the method comprises the steps of initiating homopolymerization of an acrylamide aqueous solution by adding an initiator, introducing a modifying group into a main chain of a reactant, and finally drying, crushing and screening to prepare the particle profile control agent with the particle size of 20-70 meshes. By using alkali liquor, surfactant and anionic polyacrylamide solution with different proportions as carrier fluid, the particle profile control agent can slowly expand in the carrier fluid, so that the particle profile control agent can be injected into a stratum needing profile control and water plugging to realize the profile control function.
CN1036002325A discloses a delayed crosslinking gel profile control agent and a preparation method thereof, belonging to the technical field of oilfield chemistry. The gel profile control agent comprises the following components in mass concentration: 0.1-0.5% of partially hydrolyzed polyacrylamide, 0.1-1% of cyclodextrin/phenol inclusion compound, 0.1-0.5% of urotropine, 0.1-0.3% of citric acid, 0.01-0.1% of competitive inclusion agent carrying agent and water as solvent. Competitive inclusion agent is dissolved in the competitive inclusion agent carrying agent and is dispersed into a delayed crosslinking system to generate competitive inclusion on phenol, and the release speed of phenol is regulated and controlled by regulating and controlling the inclusion constant of the competitive inclusion agent and cyclodextrin and the molar ratio of the competitive inclusion agent to the phenol, so that the gelling time of the gel profile control agent is delayed, and deep profile control is selectively performed on high-permeability oil reservoirs, large pore canals, cracks and the like.
CN104479654A discloses a compound cationic polyacrylamide profile control agent, which comprises, by mass fraction, 0.2-0.8% of compound cationic polyacrylamide, 0.5-0.7% of phenolic crosslinking agent, and the balance of water; wherein, the compound cationic polyacrylamide comprises 3-12% of cationic polyacrylamide with molecular weight of 500-1500 ten thousand and 88-97% of nonionic polyacrylamide with molecular weight of 800-1200 ten thousand by mass fraction. The polymer for the profile control agent adopts cationic polyacrylamide, and the positive charge of the polymer and the negative charge of the reservoir rock are attracted, so that the viscous force between the polymer and the rock can be increased, the plugging strength is improved, and the period of validity of profile control is prolonged.
CN101362940A discloses a profile control agent for injection well. The profile control agent comprises the following components: polyacrylamide with molecular weight of 100-. After the profile control agent is adopted, the permeability of the high permeability layer reaches 40-60%, and the proportion of the profile control agent entering a target layer can be improved to more than 95% from 70% originally.
CN102153999A discloses a zwitterion gel profile control agent, which comprises the following components in percentage by mass: 0.1-0.3% of zwitterionic polymer, wherein the molecular weight of the zwitterionic polymer is more than 1500 ten thousand, the cationic degree is 5-10%, and the anionic degree is 5-20%; 0.1-0.3% of composite cross-linking agent, prepared by the following method, firstly, adding phenol and formaldehyde in an enamel reaction kettle with a stirrer according to the mass ratio of 1:1, heating to 60 ℃, then adding triethanolamine to react the phenol and the formaldehyde to generate a mixture of mono-hydroxymethyl phenol, di-hydroxymethyl phenol and tri-hydroxymethyl phenol for standby, wherein the amount of the added triethanolamine is 1-2% of the total weight of the phenol and the formaldehyde; secondly, adding 7-10% of sodium dichromate and 10-15% of thiourea into a reaction kettle with a stirrer according to the weight ratio of 1:1, adding 30-37% of hydrochloric acid and a mixture of sodium acetate and sodium malonate according to the weight ratio of 1:1, adding 1-2% of the total amount of the sodium dichromate and the thiourea into the mixture of the sodium acetate and the sodium malonate according to the weight ratio of 22.5:1, and reacting for 12 hours for later use; mixing the products obtained in the two steps according to the equal volume ratio, adding absolute ethyl alcohol with the total weight of 10-15% as a mutual solvent, and uniformly stirring to obtain the composite cross-linking agent; the balance of water.
CN103333671A discloses a profile control agent for oil fields; the sewage treatment system consists of oil field sewage containing hydrogen sulfide, polymer and sodium dichromate; the concentration of the sewage containing hydrogen sulfide in the oil field is 0.1-20mg/L, the addition amount of sodium dichromate is 30-50mg/L, and the addition amount of polymer is 1500 mg/L; when the oil field sewage contains 20-50mg/L hydrogen sulfide, carrying out oxygen exposure on the sewage, reducing the hydrogen sulfide content to be in the range of 0.1-20mg/L, and adding 30-50mg/L sodium dichromate and 1500mg/L polymer; the profile control agent solves the problem that the polymer is used as a main agent and cannot be prepared by utilizing the hydrogen sulfide-containing sewage, solves the problem that the gel cannot be formed by utilizing the hydrogen sulfide-containing sewage in the conventional profile control, reduces the use concentration of sodium dichromate, and does not need reducing agent components such as thiourea.
CN101531890A discloses a preparation method of a profile control agent for oil field deep temporary plugging, belonging to the technical field of oil exploitation. Firstly, weighing phenolic resin, organic chromium, glacial acetic acid, resorcinol and polyacrylamide according to mass percentage, then slowly adding the weighed polyacrylamide into the weighed water and stirring, and sequentially adding the weighed other delayed crosslinking agents and stirring. The profile control agent for the deep temporary plugging of the oil field, which is prepared by the method, has the advantages that different cross-linking agents are added, the gelling time of the profile control agent is controllable when the profile control agent is used, and the gelling time is 8-48 hours; the gelling strength is high, the gel is not easy to break, and the effective period is 1-2 years; the flow direction of the water injection water of the stratum can be effectively changed; has good adsorption and blocking effects on the stratum.
CN102086385A discloses a method for determining an organochromium crosslinked gel system based on a low-molecular high-concentration polymer, which comprises the following steps: selecting chromium acetate as a primary crosslinking agent; selecting 400 ten thousand of low molecular weight high concentration polymer as a profile control agent raw material; the concentration of 400 ten thousand of low molecular weight high concentration polymer is 0.6-0.8%; the polymerization ratio of the primary crosslinking agent is 25-35: 1; the strength after gelling is 190-200 mPas. The method has the advantages of strong selectivity, no permanent damage to the stratum, no influence on the implementation of later measures and simple construction process.
CN102174317A discloses a profile control agent suitable for three-component combination flooding. The profile control agent comprises the following components: polyacrylamide with the concentration of 2000mg/L, the molecular weight of the polyacrylamide is 1600-2000 ten thousand, and the degree of hydrolysis is 20-25 percent; an organic chromium crosslinking agent with a crosslinking ratio of 25:1 (W/W); thiourea as a stabilizer at a concentration of 800 mg/L; and the balance water; wherein the organic chromium crosslinking agent consists of chromium trichloride, sodium hydroxide and lactic acid according to the molar ratio of 1:3: 3. The profile control agent is adopted to increase the pressure of an injection well, reduce the relative water absorption proportion of a main water absorption layer and improve the oil layer utilization condition, thereby enlarging swept volume, effectively relieving the development contradiction, improving the utilization rate of chemical flooding, saving the fund and improving the recovery ratio.
CN103694977A discloses an anti-shear delayed crosslinking organic profile control agent. The profile control agent comprises the following components in volume molar concentration: 0.4 to 0.6 percent of anionic polyacrylamide with 800 ten thousand molecular weight, 0.1 to 0.2 percent of sodium dichromate, 0.4 to 0.6 percent of thiourea and 0.05 percent of sodium sulfite. The gel forming strength after stratum shearing meets the profile control requirement of a low-permeability fracture stratum, the gel forming time can be controlled by adjusting the concentration of the stabilizer, the requirements of oil reservoirs with different well intervals are met, and the recovery ratio is improved. The defects that the strength of the conventional profile control agent is greatly reduced after the conventional profile control agent is sheared by a near-wellbore area of a water well, the requirement of plugging cracks cannot be met, and the profile control requirement of a low-permeability crack stratum cannot be met are overcome.
As mentioned above, there are many profile control agents available in the field of oil exploration and development disclosed in the prior art, but there is still an urgent need for new profile control agents for the need for continued improvement of the profile control effect and the reality of the increasing complexity of the oil well geological conditions and the decreasing oil recovery.
Based on the consideration, the development of a profile control agent with excellent performance and a preparation method thereof are problems to be solved in the field of oil exploitation at present and are research hotspots and key points in the field at present, which have very important industrial values and scientific research meanings for technical progress of oil exploration and exploitation, and are the basis and the power of the completion of the invention.
Disclosure of Invention
In order to research and develop a novel profile control agent, the inventor of the invention has conducted intensive research, and aiming at various defects shown by the profile control agent in the production of the existing oil and gas wells, after a large amount of creative labor is paid, an environment-friendly delayed crosslinking profile control agent for oil extraction and a preparation method and application thereof are obtained, and the invention is further completed.
Specifically, the technical solution and contents of the present invention mainly relate to the following aspects.
In a first aspect, the invention relates to a preparation method of an environment-friendly delayed crosslinking profile control agent for oil recovery, which comprises the following steps:
s1: synthesizing a salt-resistant polymer solution;
s2: hydrolyzing the salt-resistant polymer solution to obtain a hydrolysate;
s3: treating the hydrolysate to obtain a salt-resistant polymer;
s4: and at normal temperature, adding the salt-resistant polymer, the phenolic compound, the aldehyde compound and the catalyst into deionized water, and stirring and mixing uniformly to obtain the environment-friendly delayed crosslinking profile control agent for oil recovery.
In the preparation method of the present invention, the step S1 specifically includes: according to parts by weight, adding 18-20 parts of acrylamide, 3-5 parts of 2-acrylamido-2-methylpropanesulfonic acid, 0.5-1 part of N, N-dimethyl-hexadecyl allyl ammonium chloride (also called hexadecyl dimethyl allyl ammonium chloride) and 0.05 part of sodium formate into 100 parts of deionized water at 10-12 ℃, fully and uniformly stirring, then slowly adding a ternary composite initiator, and reacting at constant temperature of 10-12 ℃ for 2-3 hours to obtain the salt-resistant polymer solution.
Wherein the ternary composite initiator is a mixture of 0.2-0.4 part of tetramethylethylenediamine, 0.05-0.1 part of ammonium persulfate and 0.025-0.05 part of sodium sulfite. Wherein 0.2 to 0.4 part, 0.05 to 0.1 part and 0.025 to 0.05 part are all parts by weight.
The inventors have found that the best technical result can be obtained by using a ternary complex initiator, which should be the result that the initiation properties of the three components are mutually coordinated and synergistic under the reaction conditions (the initiation efficiency and efficiency of each component are different in different reaction time stages, but the combination of the initiation effects is mutually promoted and synergistic).
In the preparation method of the present invention, the step S2 specifically includes:
adding sodium carbonate into the salt-resistant polymer solution at 40-50 ℃, wherein the adding amount of the sodium carbonate is such that the number average molecular weight of the salt-resistant polymer in the hydrolysate obtained after hydrolysis is 1500-1800 ten thousand, thereby obtaining the hydrolysate.
That is, the amount of sodium carbonate added is such that the number average molecular weight of the salt resistant polymer in the hydrolysate obtained after sufficient hydrolysis is 1500-1800 ten thousand,
the inventor finds that the addition amount of sodium carbonate is very important, which directly affects the profile control effect of the final product, and when the addition amount is such that the number average molecular weight of the salt-resistant polymer in the hydrolysate is 1500-1800 ten thousand, good technical effect can be obtained, and when the number average molecular weight of the salt-resistant polymer is 1600-1700 ten thousand, the best technical effect can be obtained, so the addition amount of sodium carbonate is most preferably such that the number average molecular weight of the salt-resistant polymer is 1600-1700 ten thousand.
Among them, the method for measuring the number average molecular weight is well known, and can be determined by, for example, gel chromatography, and will not be described in detail.
In the preparation method of the present invention, the step S3 specifically includes:
naturally cooling the hydrolysate to room temperature, pouring the hydrolysate into sufficient absolute ethyl alcohol, standing overnight to obtain a precipitate, filtering the precipitate, washing the precipitate with absolute ethyl alcohol and deionized water in sequence, and completely drying in vacuum to obtain the salt-resistant polymer.
In the preparation method of the present invention, the step S4 specifically includes:
at normal temperature, adding 0.3-0.5 part of the salt-resistant polymer, 0.2-0.4 part of phenolic compound, 0.1-0.25 part of aldehyde compound, 0.05-0.07 part of catalyst and optionally adding a proper amount of stabilizer into 100 parts of deionized water by weight, and then uniformly stirring and mixing to obtain the environment-friendly delayed crosslinking profile control agent for oil recovery.
Wherein the phenolic compound is any one of bisphenol A, cardanol or saligenin, and most preferably cardanol.
Wherein, the aldehyde compound is any one of glyoxal, glutaraldehyde or salicylaldehyde, and is most preferably glutaraldehyde.
Wherein the catalyst is ammonium sulfate or sodium citrate, and most preferably sodium citrate.
Wherein the stabilizer is thiourea or hydroquinone, and the addition amount thereof can be suitably selected, for example, the amount is usually 0.02 to 0.04 parts by weight relative to 0.3 to 0.5 parts by weight of the salt-resistant polymer in step S4.
In a second aspect, the invention relates to the environment-friendly delayed crosslinking profile control agent for oil recovery prepared by the preparation method.
In a third aspect, the invention relates to the use of the environmentally friendly delayed cross-linking profile control agent for oil recovery in oil recovery.
The environment-friendly delayed crosslinking profile control agent for oil extraction has a plurality of excellent performances such as excellent thermal stability, plugging performance, high temperature resistance, tackifying performance, high mineralization resistance and the like, so that the environment-friendly delayed crosslinking profile control agent can be applied to oil extraction, can be used for realizing various profile control effects, and has good application prospect and production potential in the technical field of oil extraction.
As described above, the present invention provides an environment-friendly delayed crosslinking profile control agent for oil recovery, which has various good properties and good industrial potential in the field of energy development by a preferred and unique preparation method of a plurality of technical characteristics thereof, and a preparation method and use thereof.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the use and purpose of these exemplary embodiments are merely to exemplify the present invention, and do not set forth any limitation on the actual scope of the present invention in any form, and the scope of the present invention is not limited thereto.
Example 1: preparation of environment-friendly delayed crosslinking profile control agent for oil extraction
S1: synthesizing a salt-resistant polymer solution, which specifically comprises the following steps:
adding 18 parts by weight of acrylamide, 5 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 0.5 part by weight of N, N-dimethyl-hexadecylallylammonium chloride and 0.05 part by weight of sodium formate into 100 parts by weight of deionized water at constant temperature of 10 ℃, fully and uniformly stirring, slowly adding a ternary composite initiator (a mixture of 0.2 part by weight of tetramethylethylenediamine, 0.1 part by weight of ammonium persulfate and 0.025 part by weight of sodium sulfite), and continuously reacting at constant temperature of 10 ℃ for 3 hours to obtain the salt-resistant polymer solution;
s2: hydrolyzing the salt-resistant polymer solution to obtain a hydrolysate, which specifically comprises the following steps:
adding a proper amount of sodium carbonate into the salt-resistant polymer solution at a constant temperature of 40 ℃ so that the number average molecular weight of the salt-resistant polymer in the hydrolyzed solution is 1600 +/-10 ten thousand (namely about 1600 ten thousand) to obtain the hydrolyzed solution;
s3: treating the hydrolysate to obtain the salt-resistant polymer, which specifically comprises the following steps:
naturally cooling the hydrolysate to room temperature, pouring the hydrolysate into sufficient absolute ethyl alcohol, standing overnight to obtain a precipitate, filtering the precipitate, washing the precipitate with absolute ethyl alcohol and deionized water in sequence, and completely drying the precipitate in vacuum to obtain the salt-resistant polymer;
s4: at normal temperature, adding the salt-resistant polymer, the phenolic compound, the aldehyde compound and the catalyst into deionized water, and stirring and mixing uniformly to obtain the environment-friendly delayed crosslinking profile control agent for oil recovery, which specifically comprises the following steps:
at normal temperature, adding 0.3 part of the salt-resistant polymer, 0.4 part of phenolic compound cardanol, 0.1 part of aldehyde compound glutaraldehyde, 0.07 part of catalyst sodium citrate and 0.04 part of thiourea into 100 parts of deionized water by weight, and then stirring and mixing uniformly to obtain the environment-friendly delayed crosslinking profile control agent for oil recovery, which is named as J1.
Example 2: preparation of environment-friendly delayed crosslinking profile control agent for oil extraction
S1: synthesizing a salt-resistant polymer solution, which specifically comprises the following steps:
adding 20 parts by weight of acrylamide, 3 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 1 part by weight of N, N-dimethyl-hexadecyl allyl ammonium chloride and 0.05 part by weight of sodium formate into 100 parts by weight of deionized water at the constant temperature of 12 ℃, fully and uniformly stirring, slowly adding a ternary composite initiator (a mixture of 0.4 part by weight of tetramethyl ethylenediamine, 0.05 part by weight of ammonium persulfate and 0.05 part by weight of sodium sulfite), and continuously reacting at the constant temperature of 12 ℃ for 2 hours to obtain the salt-resistant polymer solution;
s2: hydrolyzing the salt-resistant polymer solution to obtain a hydrolysate, which specifically comprises the following steps:
adding a proper amount of sodium carbonate into the salt-resistant polymer solution at a constant temperature of 50 ℃ so that the number average molecular weight of the salt-resistant polymer in the hydrolyzed solution is 1700 +/-10 thousands (namely about 1700 thousands) to obtain the hydrolyzed solution;
s3: treating the hydrolysate to obtain the salt-resistant polymer, which specifically comprises the following steps:
naturally cooling the hydrolysate to room temperature, pouring the hydrolysate into sufficient absolute ethyl alcohol, standing overnight to obtain a precipitate, filtering the precipitate, washing the precipitate with absolute ethyl alcohol and deionized water in sequence, and completely drying the precipitate in vacuum to obtain the salt-resistant polymer;
s4: at normal temperature, adding the salt-resistant polymer, the phenolic compound, the aldehyde compound and the catalyst into deionized water, and stirring and mixing uniformly to obtain the environment-friendly delayed crosslinking profile control agent for oil recovery, which specifically comprises the following steps:
at normal temperature, adding 0.5 part of the salt-resistant polymer, 0.2 part of phenolic compound cardanol, 0.25 part of aldehyde compound glutaraldehyde, 0.05 part of catalyst sodium citrate and 0.02 part of hydroquinone into 100 parts of deionized water in parts by weight, and then stirring and mixing uniformly to obtain the environment-friendly delayed crosslinking profile control agent for oil recovery, which is named as J2.
Example 3: preparation of environment-friendly delayed crosslinking profile control agent for oil extraction
S1: synthesizing a salt-resistant polymer solution, which specifically comprises the following steps:
adding 19 parts by weight of acrylamide, 4 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 0.75 part by weight of N, N-dimethyl-hexadecyl allyl ammonium chloride and 0.05 part by weight of sodium formate into 100 parts by weight of deionized water at the constant temperature of 11 ℃, fully and uniformly stirring, slowly adding a ternary composite initiator (a mixture of 0.3 part by weight of tetramethyl ethylenediamine, 0.075 part by weight of ammonium persulfate and 0.038 part by weight of sodium sulfite), and continuously reacting at the constant temperature of 11 ℃ for 2.5 hours to obtain the salt-resistant polymer solution;
s2: hydrolyzing the salt-resistant polymer solution to obtain a hydrolysate, which specifically comprises the following steps:
adding a proper amount of sodium carbonate into the salt-resistant polymer solution at a constant temperature of 45 ℃ so that the number average molecular weight of the salt-resistant polymer in the hydrolyzed hydrolysate is 1650 +/-10 ten thousand (namely about 1650 ten thousand) to obtain the hydrolyzed solution;
s3: treating the hydrolysate to obtain the salt-resistant polymer, which specifically comprises the following steps:
naturally cooling the hydrolysate to room temperature, pouring the hydrolysate into sufficient absolute ethyl alcohol, standing overnight to obtain a precipitate, filtering the precipitate, washing the precipitate with absolute ethyl alcohol and deionized water in sequence, and completely drying the precipitate in vacuum to obtain the salt-resistant polymer;
s4: at normal temperature, adding the salt-resistant polymer, the phenolic compound, the aldehyde compound and the catalyst into deionized water, and stirring and mixing uniformly to obtain the environment-friendly delayed crosslinking profile control agent for oil recovery, which specifically comprises the following steps:
at normal temperature, adding 0.4 part of the salt-resistant polymer, 0.3 part of phenolic compound cardanol, 0.175 part of aldehyde compound glutaraldehyde, 0.06 part of catalyst sodium citrate and 0.03 part of thiourea into 100 parts of deionized water in parts by weight, and then stirring and mixing uniformly to obtain the environment-friendly delayed crosslinking profile control agent for oil recovery, which is named as J3.
Examples 4 to 9: preparation of environment-friendly delayed crosslinking profile control agent for oil extraction
The procedures were carried out as in examples 4 to 9, except that one or two initiators were omitted, respectively, and the initiator used, the correspondence between examples, and the nomenclature of the obtained environmentally friendly delayed crosslinking profile control agent for oil recovery (abbreviated as "profile control agent") were as shown in the following table.
Where "-" indicates omitted and "+" indicates present.
Examples 10 to 13: preparation of environment-friendly delayed crosslinking profile control agent for oil extraction
Examples 10 to 13 were carried out in accordance with the methods of examples 1 to 3, respectively, except that the amount of sodium carbonate added was adjusted to change the number average molecular weight of the salt-resistant polymer in the hydrolyzed solution obtained after sufficient hydrolysis, and the amount of sodium carbonate used was such that the number average molecular weight of the salt-resistant polymer (as shown in the following table, actually, within a range of ± 10 ten thousand, the specific number average molecular weight in the following table is rounded), the correspondence between the examples, and the nomenclature of the obtained environmentally friendly delayed crosslinking profile control agent for oil recovery (abbreviated as "profile control agent") were as shown in the following table.
Examples 14 to 17: preparation of environment-friendly delayed crosslinking profile control agent for oil extraction
Example 14: example 14 was carried out in the same manner as in example 1 except that cardanol was replaced with bisphenol a, and the obtained eco-friendly delayed cross-linking profile control agent for oil recovery was named J14.
Example 15: example 15 was carried out in the same manner as in example 2 except that cardanol was replaced with saligenin, and the obtained eco-friendly delayed cross-linking profile control agent for oil recovery was named J15.
Example 16: example 16 was performed according to the method of example 3, except that glutaraldehyde was simply replaced with glyoxal, and the resulting eco-friendly delayed cross-linking profile control agent for oil recovery was named J16.
Example 17: example 17 was performed according to the method of example 1 except that only glutaraldehyde was replaced with salicylaldehyde, and the resulting eco-friendly delayed cross-linking profile control agent for oil recovery was named J17.
Examples 18 to 20: preparation of environment-friendly delayed crosslinking profile control agent for oil extraction
The procedures were otherwise unchanged except that only sodium citrate was replaced with ammonium sulfate, so that examples 18 to 20 were performed according to the methods of examples 1 to 3, respectively, and the resulting eco-friendly delayed cross-linking profile control agent for oil recovery was named J18, J19 and J20 in this order.
Performance testing
The environmental-friendly delayed crosslinking profile control agent for oil recovery obtained in the above examples was subjected to performance tests of different indexes, specifically as follows.
1. Investigation of thermal stability
The instantly prepared environment-friendly delayed crosslinking profile control agent for oil recovery is respectively filled into opaque glass bottles with blue caps, the volume of which is 100ml (80 ml is filled into each bottle), the bottle caps are screwed, the bottles are placed in a thermostat at 100 ℃, the apparent viscosity (hereinafter referred to as the initial apparent viscosity) of the gel in the initial gelling process after 24 hours is respectively measured, the temperature is continuously kept for 3 months, 6 months and 10 months, the gel viscosity retention rate is respectively measured, and the calculation formula is as follows:
gel viscosity retention (%) { (apparent viscosity after aging-initial apparent viscosity) ÷ initial apparent viscosity } × 100%.
The results are shown in Table 1 below.
TABLE 1
When the sample factor values of the respective groups are small, the average value is taken, for example, in the case of J1-J3, since the gel viscosity retention rates of J1, J2 and J3 are small, the average value is taken as the gel viscosity retention rate at different times (for example, the gel viscosity retention rate after 3 months is 95.2%, that is, 95.2% — J1+ J2+ J3) ÷ 3), and the values of the other groups are calculated in the same manner (the same is true in the other tables below). For "/" refers to the correspondence relationship when the difference between the two is large, for example, taking "J14/J15" as an example, the correspondence relationship of the gel viscosity retention rate at 3 months "89.8/85.7" means that the gel viscosity retention rate (%) of J14 after 3 months is 89.8%, the gel viscosity retention rate (%) of J15 after 3 months is 85.7%, and the same correspondence relationship is present in the rest cases (similar expressions in other tables below also have corresponding correspondence relationships), and description thereof is omitted.
Therefore, the environment-friendly delayed crosslinking profile control agent J1-J3 for oil recovery has excellent thermal stability, and still has gel viscosity retention rate of 84.8 percent after 10 months; when one initiator component is omitted, the difference of gel viscosity retention among the components is small and the overall reduction is not large, but when the two components are omitted, the gel viscosity retention is remarkably reduced (particularly when the tetramethylethylenediamine and the ammonium persulfate are omitted, the reduction is most remarkable, see J4-J6 and J7-J9); the addition amount of sodium carbonate influencing the number average molecular weight of the salt-resistant polymer also has a remarkable influence on the thermal stability, when the addition amount is such that the number average molecular weight of the salt-resistant polymer is 1700-ten thousand, the best gel viscosity retention rate can be obtained (see J1-J3), and the larger the deviation from 1600-1700-ten thousand is, the smaller the gel viscosity retention rate is (see J10-J11, J12-J13), which proves that the profile control agent has the best performances of decomposition resistance, fracture resistance and the like under the composite conditions of the stratum such as high temperature, high pressure, high salt and the like under the condition that the number average molecular weight is 1600-1700-ten thousand, thereby having the best plugging performance and long-term stability; cardanol is most effective for phenols (see J1-J3 and J14-J15), which should be due to its longest carbon chain compared to bisphenol A and saligenin, resulting in the strongest entanglement and intercalation during polymerization, with the best gel strength; glutaraldehyde is most effective for aldehydes (see J1-J3 and J16-J17); when the catalyst during polymerization is changed, the gel viscosity retention is reduced (see J18-J20).
2. Testing of plugging Performance
The specific steps of the test process are as follows: filling quartz sand with the particle size range of 60-120 meshes into sand filling pipes with the diameter of 2.5cm and the length of 60cm, measuring the permeability of each sand filling pipe at room temperature (namely the permeability before plugging), and then injecting the different environment-friendly delayed crosslinking profile control agents (relative to each cm of the sand filling pipes) for oil recovery, which are prepared by uniform pressure injection and stand for 15 days at room temperature2Sectional area, injection speed of 0.15 ml/min, pressure of 0.1MPa, injection time of 5 hours); after the injection is finished, the permeability of the sand-packed pipe is measured again by the same method, and the plugging rate of the different environment-friendly delayed cross-linking profile control agent for oil recovery (plugging rate (%) (permeability before plugging-permeability after plugging)/permeability before plugging × 100%) can be calculated according to the permeability before plugging and after plugging of the sand-packed pipe, and the specific results are shown in table 2 below:
TABLE 2
As can be seen from the above table: 1. the environment-friendly delayed crosslinking profile control agent for oil recovery has excellent blocking property (see J1-J3); 2. when one initiator component is omitted, the blocking rate is reduced somewhat (see J4-J6), but when both components are omitted, the reduction is further exacerbated (see J7-J9); 3. for the addition amount of sodium carbonate influencing the number average molecular weight of the salt-resistant polymer, when the addition amount is such that the number average molecular weight of the salt-resistant polymer is 1700-; 4. cardanol and glutaraldehyde also have the best blocking performance for phenolic compounds and aldehyde compounds; 5. when the catalyst is changed, the blocking performance is reduced to a certain extent, which proves that the selection of the catalyst can influence the crosslinking degree of the polymerization and the strength of the polymer, and further, the difference of the blocking performance is finally caused.
3. Study on high temperature resistance and tackifying performance
The study was performed as follows: putting the prepared different environment-friendly delayed crosslinking profile control agents for oil extraction into a high-pressure sealing tank, and then carrying out hot rolling treatment at the high temperature of 200 ℃ for 25 hours to obtain a modified profile control agent after high-temperature treatment; then, the high-pressure sealed tank was depressurized to normal pressure, the modified profile control agent after high-temperature treatment was naturally cooled to room temperature, and the change in apparent viscosity and the change in fluid loss before and after high-temperature (i.e., 200 ℃) treatment of each modified profile control agent were measured, thereby examining the high-temperature resistance and the viscosifying properties thereof, and the results are shown in table 3 below.
TABLE 3
It can be seen from this that: 1. the environment-friendly delayed crosslinking profile control agent J1-J3 for oil extraction has excellent high temperature resistance and tackifying effect: after high-temperature treatment, the viscosity is increased, and the filtration loss is reduced, so that the high-temperature-resistant; 2. when one initiator component is omitted, the high-temperature resistance and the tackifying performance are somewhat reduced (see J4-J6), but when both components are omitted, the reduction is further exacerbated (see J7-J9, particularly with a significant increase in the amount of filtration); 3. as for the addition amount of sodium carbonate which affects the number average molecular weight of the salt-resistant polymer, when the addition amount is such that the number average molecular weight of the salt-resistant polymer is 1700-ten thousand, the best high temperature resistance and tackifying performance can be obtained (see J1-J3), and the higher the deviation from 1600-1700-ten thousand is, the more remarkable the reduction of the high temperature resistance and tackifying performance is (see J10-J11, J12-J13); 4. cardanol and glutaraldehyde have the best high temperature resistance and tackifying properties for phenolic and aldehyde compounds (due to the significant polymerization effect of chain length); 5. when the catalyst is changed, the high temperature resistance and the tackifying performance are reduced to a certain extent, which proves that the selection of the catalyst can influence the crosslinking degree of polymerization and the strength of the polymer, and further finally causes the difference of the high temperature resistance and the tackifying performance.
4. Investigation of hypersalinity resistance
Step 1: firstly, preparing composite mineral salt water, wherein the mass percentage concentration of each component is as follows: 15% of NaCl, 6% of KCl and MgCl22% of CaCl2Is 1.5%, ZnCl2Is 1.5% and AlCl3Is 1%.
Step 2: then, the different environment-friendly delayed crosslinking profile control agents for oil recovery of the invention are added into the same volume of the composite mineral brine, fully stirred until the mixing is complete, and after standing for 20 days, the plugging performance is measured according to the same method of the test of the plugging performance 2, and the results are shown in the following table 4.
TABLE 4
Therefore, the environment-friendly delayed crosslinking profile control agent J1-J3 for oil recovery has good high mineralization resistance, and even under the high mineralization, the high plugging rate of the average value of 98.1 percent is still realized after 20 days. While changes or omissions of other components resulted in a decrease, even a significant decrease, in the plugging rate (e.g., a very significant decrease in J10-J11).
As described above, the present invention provides an environment-friendly delayed cross-linking profile control agent for oil recovery, a preparation method and use thereof, wherein the environment-friendly delayed cross-linking profile control agent for oil recovery has various good properties such as thermal stability, plugging property, high temperature resistance, tackifying property, hypersalinity resistance and the like by a preferable and unique preparation method of a plurality of technical characteristics thereof, and thus has good industrialization potential and popularization value in the field of energy development, particularly in the technical field of oil recovery.
It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should also be understood that various alterations, modifications and/or variations can be made to the present invention by those skilled in the art after reading the technical content of the present invention, and all such equivalents fall within the protective scope defined by the claims of the present application.
Claims (4)
1. A preparation method of a delayed crosslinking profile control agent for oil recovery comprises the following steps:
s1: synthesizing a salt-resistant polymer solution;
s2: hydrolyzing the salt-resistant polymer solution to obtain a hydrolysate;
s3: treating the hydrolysate to obtain a salt-resistant polymer;
s4: at normal temperature, adding the salt-resistant polymer, the phenolic compound, the aldehyde compound and the catalyst into deionized water, and stirring and mixing uniformly to obtain the delayed crosslinking profile control agent for oil recovery;
the step S1 specifically includes:
adding 18-20 parts by weight of acrylamide, 3-5 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 0.5-1 part by weight of N, N-dimethyl-hexadecyl allyl ammonium chloride and 0.05 part by weight of sodium formate into 100 parts by weight of deionized water at 10-12 ℃, fully and uniformly stirring, slowly adding a ternary composite initiator, and reacting at constant temperature of 10-12 ℃ for 2-3 hours to obtain the salt-resistant polymer solution;
the ternary composite initiator is a mixture of 0.2-0.4 part of tetramethylethylenediamine, 0.05-0.1 part of ammonium persulfate and 0.025-0.05 part of sodium sulfite, wherein 0.2-0.4 part, 0.05-0.1 part and 0.025-0.05 part are all parts by weight;
the step S2 specifically includes:
adding sodium carbonate into the salt-resistant polymer solution at 40-50 ℃, wherein the adding amount of the sodium carbonate is such that the number average molecular weight of the salt-resistant polymer in the hydrolysate obtained after hydrolysis is 1500-1800 ten thousand, thereby obtaining the hydrolysate;
the step S3 specifically includes:
naturally cooling the hydrolysate to room temperature, pouring the hydrolysate into sufficient absolute ethyl alcohol, standing overnight to obtain a precipitate, filtering the precipitate, washing the precipitate with absolute ethyl alcohol and deionized water in sequence, and completely drying the precipitate in vacuum to obtain the salt-resistant polymer;
the step S4 specifically includes:
at normal temperature, adding 0.3-0.5 part of the salt-resistant polymer, 0.2-0.4 part of phenolic compound, 0.1-0.25 part of aldehyde compound, 0.05-0.07 part of catalyst and optionally a proper amount of stabilizer into 100 parts of deionized water by weight, and then uniformly stirring and mixing to obtain the delayed crosslinking profile control agent for oil recovery;
the phenolic compound is cardanol;
the aldehyde compound is glutaraldehyde.
2. The method of claim 1, wherein: in step S2, the sodium carbonate is added in such an amount that the number average molecular weight of the salt-resistant polymer in the hydrolysate obtained after hydrolysis is 1600-1700 ten thousand.
3. A delayed crosslinking profile control agent for oil recovery prepared by the preparation method according to any one of claims 1 to 2.
4. Use of the delayed cross-linking profile control agent for oil recovery according to claim 3 in oil recovery.
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| CN112175595B (en) * | 2019-07-02 | 2022-12-27 | 中石化南京化工研究院有限公司 | Temperature-resistant and salt-resistant profile control water shutoff agent |
| CN113136195A (en) * | 2020-01-20 | 2021-07-20 | 中国海洋石油集团有限公司 | Oligomeric polyphenol resin cross-linking agent for improving recovery ratio of oil field and preparation method thereof |
| CN111139046A (en) * | 2020-02-26 | 2020-05-12 | 刘小龙 | Polymer gel composite plugging agent and preparation method thereof |
| CN114437289B (en) * | 2020-11-02 | 2023-06-30 | 中国石油天然气股份有限公司 | Self-crosslinking polymer, oilfield flooding agent and preparation method thereof |
| CN113372489B (en) * | 2021-08-12 | 2021-10-29 | 山东诺尔生物科技有限公司 | Temperature-sensitive delayed water shutoff agent and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1644872A (en) * | 2005-01-18 | 2005-07-27 | 胜利油田方圆科工贸有限责任公司化工分公司 | Air well single-way closing agent and its formulating method |
| CN107794025A (en) * | 2016-09-06 | 2018-03-13 | 中国石油化工股份有限公司 | Multiple crosslinking agent and its preparation method and application |
| CN108166960A (en) * | 2018-01-16 | 2018-06-15 | 中国石油天然气股份有限公司 | A kind of low-permeability oil deposit transfer drive technique step by step |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107794025A (en) * | 2016-09-06 | 2018-03-13 | 中国石油化工股份有限公司 | Multiple crosslinking agent and its preparation method and application |
| CN108166960A (en) * | 2018-01-16 | 2018-06-15 | 中国石油天然气股份有限公司 | A kind of low-permeability oil deposit transfer drive technique step by step |
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