CN105602543B - Acid fracturing temporary plugging agent and preparation method thereof - Google Patents
Acid fracturing temporary plugging agent and preparation method thereof Download PDFInfo
- Publication number
- CN105602543B CN105602543B CN201510696920.6A CN201510696920A CN105602543B CN 105602543 B CN105602543 B CN 105602543B CN 201510696920 A CN201510696920 A CN 201510696920A CN 105602543 B CN105602543 B CN 105602543B
- Authority
- CN
- China
- Prior art keywords
- copolymer
- temporary plugging
- plugging agent
- agent
- acid fracturing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/725—Compositions containing polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
Abstract
The invention relates to an acid fracturing temporary plugging agent and a preparation method thereof, belonging to the technical field of oilfield chemistry. The polyester/starch composite material is prepared by mixing 25-35% by mass of a polyester copolymer reinforcing agent, 40-50% by mass of a modified starch copolymer and 20-30% by mass of a cross-linked copolymer. The acid dissolution rate of the acid pressure temporary plugging agent reaches 100 percent, and the breakthrough pressure gradient reaches 30.4 MPa.m‑1The temporary plugging rate exceeds 99.5 percent, and the temporary plugging agent can effectively plug formation cracks and meet the field construction requirements of the repeated acid fracturing technology. The plugging agent realizes plugging of cracks with different widths by adjusting the particle size, has wider applicability, can not cause harm to the environment or human bodies, can be completely degraded after being injected into a stratum, is easy to flowback and does not pollute the stratum.
Description
Technical Field
The invention relates to an acid fracturing temporary plugging agent and a preparation method thereof, belongs to the technical field of oilfield chemistry, and particularly relates to an acid fracturing operation applied to a large-span reservoir stratum of a deep long well section of a high-sulfur-containing gas field.
Background
The single-well yield of the low-permeability oil-gas field is gradually reduced after primary fracturing transformation, and the potential of the stratum must be excavated by means of repeated fracturing or repeated acid fracturing technology, so that the single-well yield is improved. For oil and gas wells which are in the middle and high water-cut period or are repeatedly fractured through multiple same layers, oil and gas in the original fracture control area are nearly completely produced, so that manual steering fracturing and new fracture pressing are carried out, the fracture control area is expanded, and the oil and gas yield and the final recovery rate are improved. Therefore, the technical problem that in the repeated acid fracturing process, the original cracks and the high permeability layer are blocked by using the temporary plugging agent for multiple times, so that the new cracks are opened by fluid diversion pressure must be solved.
The application number 201110078492.2 discloses a temporary plugging agent for gas testing and production operation of a high-sulfur-content gas well, and particularly relates to a temporary plugging agent for guaranteeing operation construction safety and reservoir protection in the gas testing and production operation process of a high-sulfur-content gas well, which is formed by mixing a swelling material, a bridging material, a filling material and a suspending agent, wherein the temporary plugging agent is used for temporarily plugging a near-wellbore zone of a shot hole, so that the occurrence of complex conditions such as well leakage or overflow and the like caused by the lifting of a tubular column during the gas testing and production operation of the high-sulfur-content gas well can be effectively avoided, the temporary plugging agent is suitable for the formation temperature of 130 ℃, the acid dissolution rate is over 90 percent, the temporary plugging strength is greater than 10MPa, and the temporary plugging agent has the defects of low temporary plugging strength, poor plugging effect and difficult automatic degradation.
ZL201010130407.8 discloses a temporary plugging agent for medium-high temperature oil and gas reservoirs, which consists of acrylamide, N-methylene bisacrylamide, a polymerization inhibitor, a thickening agent, an initiator, a gel breaker and water, wherein the temporary plugging agent forms high-strength gel under the medium-high temperature stratum condition, breaks the gel within a specified time, and can adapt to the segmental, repeated and turning reconstruction of the Regutation of the Changjiu section of the medium-high temperature oil and gas reservoirs. However, the temporary plugging agent has more compound components, gel formed by crosslinking is not easy to completely break, the damage to the stratum is large, the site construction process is complex, and the application is not facilitated.
ZL 201310393381.X discloses a multi-component acid pressure temporary plugging agent and a preparation method thereof, wherein the multi-component acid pressure temporary plugging agent consists of 30-43% of a grafted starch copolymer, 25-35% of an acrylic acid-acrylamide cross-linked copolymer, 5-16% of a fibrous polyester copolymer reinforcing agent and 6-25% of an auxiliary agent, has high acid solubility, high temporary plugging rate and high temperature resistance through the comprehensive action of the components, and fully meets the efficiency and performance requirements of later development of a low-permeability oil well, but the temporary plugging agent has the defects of more components, complex preparation process, inconvenience for large-scale industrial production and the like.
Disclosure of Invention
The invention aims to overcome the defects of difficult self-degradation, low temporary plugging strength, complex preparation technology and the like of the temporary plugging agent in the prior art, and provides an acid fracturing temporary plugging agent.
Meanwhile, the preparation method of the acid fracturing temporary plugging agent is provided.
The invention is realized by the following technical scheme:
an acid fracturing temporary plugging agent comprises a polyester copolymer reinforcing agent shown as a structural general formula (1), a modified starch copolymer shown as a structural general formula (2) and a cross-linked copolymer shown as a structural general formula (3):
wherein x is y is z, and the molecular weight of the polyester copolymer reinforcing agent is 400-600 ten thousand;
wherein the molecular weight of the modified starch copolymer is 300-500 ten thousand;
wherein the molecular weight of the crosslinked copolymer is 130-170 ten thousand.
The preparation method of the acid fracturing temporary plugging agent is formed by mixing 25-35% by mass of a polyester copolymer reinforcing agent, 40-50% by mass of a modified starch copolymer and 20-30% by mass of a cross-linked copolymer, and specifically comprises the following steps:
(1) granulating the modified starch copolymer to form solid granules for later use;
(2) adding 25-35% of polyester copolymer reinforcing agent into 20-30% of cross-linked copolymer in a reaction kettle, stirring and mixing uniformly, and then adding 40-50% of modified starch copolymer prepared in the step (1) into the cross-linked copolymer, stirring and mixing uniformly to obtain the modified starch copolymer.
The polyester copolymer reinforcing agent is prepared by the following chemical reaction:
wherein m is 80%, n is 20%, x ═ y ═ z ═ m/3, and the molecular weight of the polymer is 400 to 600 ten thousand.
The modified starch copolymer is prepared by the following chemical reactions:
wherein m is 50%, x is 20%, y is 30%, and the molecular weight of the polymer is 300-500 ten thousand.
The invention has the beneficial effects that: the acid dissolution rate of the acid pressure temporary plugging agent reaches 100 percent, and the breakthrough pressure gradient reaches 30.4 MPa.m-1The temporary plugging rate exceeds 99.5 percent, and the temporary plugging agent can effectively plug formation cracks and meet the field construction requirements of the repeated acid fracturing technology. The plugging agent realizes plugging of cracks with different widths by adjusting the particle size, has wider applicability, can not cause harm to the environment or human bodies, can be completely degraded after being injected into a stratum, is easy to flowback and does not pollute the stratum.
Detailed Description
The present invention is further illustrated by the following specific examples.
Preparation example 1: preparation of polyester copolymer reinforcing agent
Accurately weighing 20g of dried beta-cyclodextrin, adding the beta-cyclodextrin into a reaction kettle, adding 100g of dimethyl sulfoxide, stirring and dissolving completely, then adding 5g of lactide, adding 0.1g of catalyst triethylamine after the lactide is dissolved, heating to 85 ℃ under the protection of nitrogen, reacting for 8 hours to obtain light yellow liquid, cooling, pouring the light yellow liquid into ice water to obtain precipitate, filtering, washing with ethyl acetate, filtering and drying to obtain a white polyester copolymer, wherein the reaction process comprises the following steps:
wherein m is 80% and n is 20%; the molecular weight of the polymer is 400-600 ten thousand.
Preparation example 2: preparation of modified starch copolymers
Uniformly mixing 20g of starch with water, stirring and gelatinizing for 1h at 70 ℃, cooling to room temperature, adding the gelatinized starch into a reaction kettle, sequentially adding 50g of acrylamide and 30g of methyl acrylate, stirring until the acrylamide and the methyl acrylate are completely dissolved, adjusting the pH value of a reaction solution to 11 by using a sodium hydroxide solution, introducing 30 minutes of nitrogen into the reaction kettle until oxygen is completely removed, adding 0.2g of initiator azodiisobutyl imidazoline hydrochloride, continuously stirring for 10min, heating to 60 ℃, and sealing for reaction for 2h to obtain a white viscous gelatinous modified starch copolymer, wherein the reaction process is as follows:
wherein m is 50%, x is 20%, and y is 30%; the molecular weight of the polymer is 300-500 ten thousand.
Example 1: preparation of temporary plugging agent
Based on the total weight of the mixture, uniformly mixing 35g of polyester copolymer reinforcing agent, 40g of modified starch copolymer and 25g of crosslinked copolymer in a physical mode in a reaction kettle to obtain an acid fracturing temporary plugging agent, wherein the acid fracturing temporary plugging agent contains the polyester copolymer reinforcing agent shown in a structural general formula (1), the modified starch copolymer shown in a structural general formula (2) and the crosslinked copolymer shown in a structural general formula (3):
wherein x is y is z, and the molecular weight of the polyester copolymer reinforcing agent is 400-600 ten thousand;
wherein the molecular weight of the modified starch copolymer is 300-500 ten thousand;
wherein the molecular weight of the crosslinked copolymer is 130-170 ten thousand.
The preparation method of the examples 2-7 is the same as that of the example 1, and the specific formula is shown in the table 1:
table 1 examples 2-7 temporary plugging agent formulations
The acid dissolution rate was evaluated for the acid fracturing temporary plugging agent prepared in example 1. The acid solubility evaluation method comprises the following steps: take 10cm3The temporary plugging agent sample is placed in a 15 Wt% hydrochloric acid solution, and the volume change of the hydrochloric acid solution is measured at regular time.
The measurement results of the acid solubility of the acid fracturing temporary plugging agent of the invention are shown in table 2:
TABLE 2 acid solubility of acid fracturing temporary plugging agent
The acid fracturing temporary plugging agent prepared in example 1 was evaluated for breakthrough pressure gradient and temporary plugging rate.
And 6 groups of rock cores are selected, and a rock core flowing experiment of the temporary plugging agent for acid fracturing is carried out indoors. The evaluation method is as follows: vacuumizing a rock core with the length of 8cm, and saturating the rock core with simulated formation water; forward measurement of water phase permeability K of rock core1(ii) a Splitting a rock core along the central axis to manufacture an artificial crack, then paving a layer of quartz sand in the crack, simulating the fractured crack and measuring the permeability K of the crack2(ii) a The temporary plugging agent sample is positively driven into the rock core and is placed for 12 hours at the temperature of 120 ℃, and the rock core breakthrough pressure gradient and the water phase permeability K are measured by positive displacement3。
The temporary plugging rate Z is calculated according to the following formula [1 ]:
Z＝(K2-K3)/K2×100％ [1]
the measurement results of the breakthrough pressure gradient and the temporary plugging rate of the acid fracturing temporary plugging agent of the invention are shown in table 3:
TABLE 3 breakthrough pressure gradient and temporary plugging rate of acid fracturing temporary plugging agent
The measurement data show that the acid solubility of the temporary plugging agent for acid fracturing reaches 100 percent, and the breakthrough pressure gradient reaches 30.4 MPa.m-1The temporary plugging rate exceeds 99.5 percent, and the temporary plugging agent can effectively plug formation cracks and meet the field construction requirements of the repeated acid fracturing technology.
Claims (4)
1. An acid fracturing temporary plugging agent is characterized in that: contains a polyester copolymer reinforcing agent shown as a structural general formula (1), a modified starch copolymer shown as a structural general formula (2) and a cross-linked copolymer shown as a structural general formula (3):
wherein x is y is z, and the molecular weight of the polyester copolymer reinforcing agent is 400-600 ten thousand;
wherein the molecular weight of the modified starch copolymer is 300-500 ten thousand;
wherein the molecular weight of the crosslinked copolymer is 130-170 ten thousand.
2. A preparation method of an acid fracturing temporary plugging agent is characterized by comprising the following steps: the polyester/starch composite material is prepared by mixing 25-35% by mass of a polyester copolymer reinforcing agent, 40-50% by mass of a modified starch copolymer and 20-30% by mass of a cross-linked copolymer, and specifically comprises the following steps:
(1) granulating the modified starch copolymer to form solid granules for later use;
(2) adding 25-35% of polyester copolymer reinforcing agent into 20-30% of cross-linked copolymer in a reaction kettle, stirring and mixing uniformly, and then adding 40-50% of modified starch copolymer prepared in the step (1) into the cross-linked copolymer, stirring and mixing uniformly to obtain the modified starch copolymer.
3. The method for preparing the acid fracturing temporary plugging agent according to claim 2, which is characterized by comprising the following steps: the polyester copolymer reinforcing agent is prepared by the following chemical reaction:
wherein m is 80%, n is 20%, x ═ y ═ z ═ m/3, and the molecular weight of the polymer is 400 to 600 ten thousand.
4. The method for preparing the acid fracturing temporary plugging agent according to claim 2, which is characterized by comprising the following steps: the modified starch copolymer is prepared by the following chemical reactions:
wherein m is 50%, x is 20%, y is 30%, and the molecular weight of the polymer is 300-500 ten thousand.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510696920.6A CN105602543B (en) | 2015-10-22 | 2015-10-22 | Acid fracturing temporary plugging agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510696920.6A CN105602543B (en) | 2015-10-22 | 2015-10-22 | Acid fracturing temporary plugging agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105602543A CN105602543A (en) | 2016-05-25 |
| CN105602543B true CN105602543B (en) | 2020-11-06 |
Family
ID=55982911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510696920.6A Active CN105602543B (en) | 2015-10-22 | 2015-10-22 | Acid fracturing temporary plugging agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105602543B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106833596B (en) * | 2016-12-21 | 2020-12-01 | 中国石油天然气股份有限公司 | Fracturing fluid capable of generating acid by itself and preparation method and application thereof |
| CN107245330B (en) * | 2017-07-05 | 2021-01-22 | 北京斯迪莱铂油气技术有限公司 | Composite temporary plugging agent and temporary plugging method for horizontal well repeated fracturing |
| CN108059952B (en) * | 2018-01-03 | 2020-05-08 | 中国石油天然气股份有限公司 | Degradable shielding protective agent and preparation method and application thereof |
| CN112431570B (en) * | 2020-11-06 | 2023-06-30 | 中国石油天然气股份有限公司 | Test method of temporary plugging agent for temporary plugging of acid fracturing |
| CN113956859B (en) * | 2021-10-25 | 2023-01-17 | 山东恒立重装新技术有限公司 | Temporary plugging ball and manufacturing method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101091796A (en) * | 2007-05-11 | 2007-12-26 | 宁波工程学院 | Method for synthesizing lactide copolymer grafted by beta cyclodextrin |
| CN102229692A (en) * | 2011-05-16 | 2011-11-02 | 西南石油大学 | Temperature and salt-resistant AM/ACD/AE copolymer and its preparation method |
| CN103409130A (en) * | 2013-09-02 | 2013-11-27 | 重庆科技学院 | Multi-component acid pressure temporary plugging additive and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7276466B2 (en) * | 2001-06-11 | 2007-10-02 | Halliburton Energy Services, Inc. | Compositions and methods for reducing the viscosity of a fluid |
| US8598092B2 (en) * | 2005-02-02 | 2013-12-03 | Halliburton Energy Services, Inc. | Methods of preparing degradable materials and methods of use in subterranean formations |
| US8114818B2 (en) * | 2008-01-16 | 2012-02-14 | Halliburton Energy Services, Inc. | Methods and compositions for altering the viscosity of treatment fluids used in subterranean operations |
-
2015
- 2015-10-22 CN CN201510696920.6A patent/CN105602543B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101091796A (en) * | 2007-05-11 | 2007-12-26 | 宁波工程学院 | Method for synthesizing lactide copolymer grafted by beta cyclodextrin |
| CN102229692A (en) * | 2011-05-16 | 2011-11-02 | 西南石油大学 | Temperature and salt-resistant AM/ACD/AE copolymer and its preparation method |
| CN103409130A (en) * | 2013-09-02 | 2013-11-27 | 重庆科技学院 | Multi-component acid pressure temporary plugging additive and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 环糊精_聚_DL_丙交酯_接枝共聚物的合成与表征;潘 彤;《高分子学报》;20060228;330-334 * |
| 环糊精对聚乳酸的改性研究;司娅萍;《中国优秀硕士论文全文数据库 工程科技I辑》;20070615;1-55 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105602543A (en) | 2016-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105602543B (en) | Acid fracturing temporary plugging agent and preparation method thereof | |
| CN107629774B (en) | It is a kind of temporarily to block up diversion agent and preparation method thereof | |
| CN109777387B (en) | Repeated fracturing temporary plugging agent and preparation method and application thereof | |
| CN108300439B (en) | Water-soluble temporary plugging agent for fracturing temporary plugging steering of oil and gas well and preparation method thereof | |
| CN110079286B (en) | Delayed crosslinking gel composition for plugging and preparation method thereof | |
| CN113185960B (en) | Temperature response type self-degradation temporary plugging agent, preparation method thereof and application thereof in shaft plugging | |
| CN111484578B (en) | Water-soluble AA-AM-NVP-NGD quadripolymer temporary plugging agent for fracturing and synthesis method thereof | |
| CN106317321B (en) | It is used to prepare the composition of underground crosslinking plural gel and crosslinking plural gel prepared therefrom | |
| CN104861953A (en) | Oil field fracture temporary plugging agent and preparation method thereof | |
| CN106883357A (en) | A kind of pre-crosslinked gel delays swollen microballoon profile control agent and its production and use | |
| CN106750345B (en) | A kind of synthetic method of the degradable diversion agent of slippery water pressure break | |
| CN111320974B (en) | Acidizing temporary plugging agent and preparation method and application thereof | |
| CN103725274A (en) | High-pressure-resistant controllable degradation chemical molding fluid bridge plug as well as preparation method and application thereof | |
| CN102562021A (en) | Quick gel breaking process for intermediate and low temperate oil gas well fracturing fluid | |
| CN109826590B (en) | Water plugging and fracturing method for high-water-content old well in low-permeability oil and gas field | |
| CN114716984B (en) | Cementing and plugging type wall fixing agent for water-based drilling fluid and preparation method and application thereof | |
| CN108728068A (en) | A kind of preparation method of the underground polymerization water shutoff agent of suitable high-temperature oil reservoir | |
| CN105238372A (en) | High-molecular gel plugging agent and preparation method thereof | |
| CN102911649B (en) | High strength is from degraded packer material and preparation method thereof | |
| CN112980407B (en) | Temperature-controllable gel plugging agent and preparation method and application thereof | |
| CN108300442A (en) | A kind of shale gas pressure break overcome high stress difference temporarily stall to diverting agent and preparation method thereof | |
| CN109652039B (en) | Green full-soluble high-strength intra-seam pressurizing agent and preparation method thereof | |
| CN111518532A (en) | Staged fracturing temporary plugging agent for horizontal well and preparation method thereof | |
| CN105567188B (en) | Auxiliary agent for improving the solidifying class sealing agent leak stopping performance of cyanogen and preparation method thereof, cyanogen coagulates class sealing agent | |
| CN116103027A (en) | Liquid bridge plug and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |