CN114058357A - Preparation method and application of thickened oil viscosity reducer - Google Patents
Preparation method and application of thickened oil viscosity reducer Download PDFInfo
- Publication number
- CN114058357A CN114058357A CN202111492946.0A CN202111492946A CN114058357A CN 114058357 A CN114058357 A CN 114058357A CN 202111492946 A CN202111492946 A CN 202111492946A CN 114058357 A CN114058357 A CN 114058357A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- viscosity reducer
- thick oil
- oil
- porous carbon
- 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.)
- Granted
Links
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 23
- 230000009467 reduction Effects 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 239000003129 oil well Substances 0.000 claims description 4
- 238000004729 solvothermal method Methods 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004523 catalytic cracking Methods 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- -1 iron ions Chemical class 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000006073 displacement reaction Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 110
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 239000012265 solid product Substances 0.000 description 11
- 230000001603 reducing effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000295 fuel oil Substances 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000001476 alcoholic effect Effects 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical class Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical class [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical class [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical class [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/592—Compositions used in combination with generated heat, e.g. by steam injection
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
-
- 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
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
-
- 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
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/24—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
- E21B43/241—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection combined with solution mining of non-hydrocarbon minerals, e.g. solvent pyrolysis of oil shale
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Mining & Mineral Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Geochemistry & Mineralogy (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Lubricants (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a preparation method and application of a thick oil viscosity reducer, wherein the method comprises the following steps: (1) soaking porous carbon powder with a solution containing catalyst metal ions, adding a reducing agent to reduce the metal ions into metal simple substances, enriching and adsorbing the metal simple substances on the porous carbon powder, and separating the porous carbon powder to obtain a catalyst precursor for later use. (2) And carrying out hydrophilic modification treatment on the catalyst precursor, and then carrying out oleophylic modification treatment to obtain the modified catalyst. (3) And mixing the modified catalyst with water, and then carrying out ultrasonic dispersion to obtain an ultrasonic dispersion liquid, namely the thickened oil viscosity reducer. The viscosity reduction oil displacement agent enriches catalytic components on a porous carbon powder carrier, and has both hydrophilicity and lipophilicity, so that a catalyst can be fully contacted with thick oil, and the viscosity reduction effect on the thick oil is effectively improved.
Description
Technical Field
The invention relates to the technical field of thick oil viscosity reducers, in particular to a preparation method and application of a thick oil viscosity reducer.
Background
The heavy oil is low in light component content and high in asphaltene and colloid content, so that most of heavy oil has the characteristics of high viscosity and high density, the heavy oil exploitation industry is gradually promoted along with less and less light oil reserves, but the heavy oil is high in viscosity and low in fluidity and is difficult to exploit, and the heavy oil is difficult to stratify from an oil layer by adopting a conventional exploitation method, so that the heavy oil needs to be subjected to viscosity reduction before exploitation, for example, a heating method, a thin oil mixing method, a chemical agent viscosity reduction method and the like, and the heavy oil is converted into an emulsified state with water as an external phase from a water-in-oil emulsified state through viscosity reduction, so that the viscosity of the heavy oil is reduced. Among them, the heating method has been implemented due to its advantages of low cost, relatively simple process, etc. The process mainly reduces the viscosity of the thick oil by utilizing heat brought by high-temperature steam, but the reduction of the viscosity is reversible, and when the high-temperature steam is injected, the thick oil is gradually cooled, and the viscosity rises again to influence subsequent exploitation. In order to overcome the above problems, a catalyst is also added to irreversibly lower the viscosity of the thick oil when injecting steam into the oil well. Although the method overcomes the problem of re-increasing the viscosity of the thick oil, the viscosity reduction effect is not ideal, and the viscosity reduction efficiency of the whole process is low and needs to be further improved.
Disclosure of Invention
The viscosity-reducing oil displacement agent can reversibly reduce the viscosity of the thick oil and can effectively improve the viscosity-reducing effect on the thick oil. In order to realize the purpose, the invention discloses the following technical scheme:
in a first aspect of the invention, a preparation method of a thick oil viscosity reducer is disclosed, which comprises the following steps:
(1) soaking porous carbon powder with a solution containing catalyst metal ions, adding a reducing agent to reduce the metal ions into metal simple substances, enriching and adsorbing the metal simple substances on porous carbon, and separating the porous carbon to obtain a catalyst precursor for later use.
(2) And carrying out hydrophilic modification treatment on the catalyst precursor, and then carrying out oleophylic modification treatment to obtain the modified catalyst.
(3) And mixing the modified catalyst with water, and then carrying out ultrasonic dispersion to obtain an ultrasonic dispersion liquid, namely the thickened oil viscosity reducer.
Further, in the step (1), the catalyst metal ions include: at least one of iron ion, ferrous ion, copper ion, nickel ion, zinc ion, etc. The metal ions are reduced into nano metal simple substance particles by a reducing agent and are attached to the porous carbon.
Alternatively, the catalyst metal ion-containing solution includes a solution in which at least one of chloride, sulfate, nitrate, acetate, and the like of a metal ion is dissolved in water.
Preferably, in step (1), the solution containing the catalyst metal ions is a saturated solution at room temperature so as to provide sufficient catalyst metal ions.
Further, in the step (1), the reducing agent is any one of a sodium borohydride solution and a potassium borohydride solution. The amount of the reducing agent added may be such that the metal ions are sufficiently reduced.
Further, in the step (2), the catalyst precursor is mixed with liquid alcohol and then subjected to solvothermal reaction, so that a hydrophilic group is introduced into the catalyst precursor, and hydrophilic modification treatment of the catalyst precursor is realized.
Optionally, the temperature of the solvothermal reaction is 100-120 ℃, and the time is 20-40 min.
Optionally, the liquid alcohol comprises at least one of methanol, ethanol, propanol, butanol, and the like.
Further, in the step (2), the catalyst precursor subjected to hydrophilic modification treatment is mixed with a silane coupling agent solution, and then the mixture is heated to a set temperature and then is subjected to heat preservation, so that the modified catalyst is obtained.
Further, the silane coupling agent includes any one of vinyltriethoxysilane, vinyltrimethoxysilane, and the like.
Further, the heat preservation temperature is 50-65 ℃, and the time is 3-5 hours, so that a lipophilic group is grafted on the surface of the catalyst precursor, and the catalyst precursor has the characteristics of lipophilicity and hydrophilicity.
Further, in the step (3), the ratio of the modified catalyst to water is 1 g: 80-110 ml.
In a second aspect of the invention, the application of the thick oil viscosity reducer obtained by the preparation method of the thick oil viscosity reducer in petroleum engineering is disclosed.
Further, the thick oil viscosity reducer is used for reducing the viscosity of thick oil, and the using method comprises the following steps: injecting hot steam into the thickened oil recovery well to preheat the thickened oil, adding the thickened oil viscosity reducer, and sealing the oil well to perform a hydrothermal catalytic cracking reaction on the thickened oil.
Further, the addition amount of the thickened oil viscosity reducer is 0.6-1.5% of the mass of the thickened oil according to the mass of the modified catalyst in the thickened oil viscosity reducer.
Furthermore, the temperature of the preheating treatment is 130-170 ℃, and macromolecular substances such as colloid, asphalt and the like in the thick oil are cracked into micromolecular substances under the action of high temperature and a catalyst, so that the viscosity of the thick oil can be obviously reduced.
Compared with the prior art, the invention has the following beneficial effects:
(1) the thick oil viscosity reducer takes the porous carbon powder as a carrier, has huge surface area and good adsorption performance, can adsorb metal ions in the carrier, and has better capability of enriching catalytic active components compared with other carriers, so that more catalytic active components can be carried in thick oil, and the catalytic efficiency and the viscosity reduction effect are improved. In order to load the catalytic active component on the porous carbon, the invention adopts a method of chemically reducing the metal ions adsorbed on the porous carbon, and has the advantages that the metal ions can be converted into the metal simple substance to become the catalytic active component, and the metal simple substance is reduced by the metal ions, so the obtained metal simple substance is nano-scale particles, can play a nanometer effect in the catalytic process, and plays a role in promoting the cracking of the catalytic thick oil.
(2) The invention also carries out hydrophilic and oleophylic double modification treatment on the prepared catalyst, and hydrophilic and oleophylic groups are introduced on the surface of the catalyst simultaneously, so that the hydrophilic group can enable the catalyst to be uniformly dispersed in a water phase to form a dispersion liquid so as to be conveniently injected into an oil well. After the lipophilic group is introduced on the catalyst, the catalyst can migrate to the oil phase and be fused with the oil phase, so that the catalyst is fully contacted with the oil phase, and the viscosity reduction rate and the viscosity reduction effect are effectively improved.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. The invention will now be further illustrated by specific examples.
Example 1
1. A preparation method of the thick oil viscosity reducer comprises the following steps:
(1) taking 50g of porous carbon powder, adding the porous carbon powder into 200ml of saturated ferric chloride solution to infiltrate the porous carbon powder, stirring for 5min, adding an excessive sodium borohydride solution with the mass fraction of 20%, and filtering and separating out porous carbon in a reaction liquid to obtain a catalyst precursor for later use.
(2) Adding the catalyst precursor obtained in the step (1) and 300ml of absolute ethyl alcohol into a high-pressure reaction kettle, reacting for 25min at 115 ℃, and then filtering to separate a solid product.
(3) And (3) adding the solid product obtained in the step (2) into an alcoholic solution of vinyl triethoxysilane, and then preserving heat at 60 ℃ for 5 hours to obtain the modified catalyst.
(4) Mixing the modified catalyst in the step (3) with water according to the proportion of 1 g: mixing the components in a proportion of 90ml, and performing ultrasonic dispersion to disperse the modified catalyst in water to obtain the thick oil viscosity reducer.
2. A method for reducing viscosity of thick oil comprises the following steps:
(i) a sample of a thick oil having a viscosity of 36600 mPas at 50 ℃ was taken and heated to 80 ℃ for use.
(ii) Adding 200g of the preheated thickened oil sample and the thickened oil viscosity reducer of the embodiment into a high-pressure reaction kettle together, wherein the addition amount of the thickened oil viscosity reducer is 1.0% of the mass of the thickened oil based on the mass of the modified catalyst, reacting at 150 ℃ for 24 hours, opening the high-pressure reaction kettle, continuously heating to remove water in the thickened oil sample after reaction, measuring the viscosity of the obtained thickened oil sample at room temperature after the temperature of the reaction kettle is reduced, and calculating the viscosity reduction rate.
Example 2
1. A preparation method of the thick oil viscosity reducer comprises the following steps:
(1) taking 50g of porous carbon powder, adding the porous carbon powder into 200ml of saturated ferrous sulfate solution to infiltrate the porous carbon powder, stirring for 5min, adding an excessive sodium borohydride solution with the mass fraction of 20%, and filtering and separating out porous carbon in a reaction liquid to obtain a catalyst precursor for later use.
(2) Adding the catalyst precursor obtained in the step (1) and 300ml of propanol into a high-pressure reaction kettle, reacting for 40min at 100 ℃, and then filtering to separate a solid product.
(3) And (3) adding the solid product obtained in the step (2) into an alcoholic solution of vinyl trimethoxy silane, and then preserving the temperature for 3 hours at 65 ℃ to obtain the modified catalyst.
(4) Mixing the modified catalyst in the step (3) with water according to the proportion of 1 g: and mixing the components in a proportion of 80ml, and performing ultrasonic dispersion to disperse the modified catalyst in water to obtain the thick oil viscosity reducer.
2. A method for reducing viscosity of thick oil comprises the following steps:
(i) a sample of a thick oil having a viscosity of 36600 mPas at 50 ℃ was taken and heated to 80 ℃ for use.
(ii) Adding 200g of the preheated thickened oil sample and the thickened oil viscosity reducer of the embodiment into a high-pressure reaction kettle together, wherein the addition amount of the thickened oil viscosity reducer is 1.5% of the mass of the thickened oil based on the mass of the modified catalyst, reacting at 170 ℃ for 24 hours, opening the high-pressure reaction kettle, continuously heating to remove water in the thickened oil sample after reaction, measuring the viscosity of the obtained thickened oil sample at room temperature after the temperature of the reaction kettle is reduced, and calculating the viscosity reduction rate.
Example 3
1. A preparation method of the thick oil viscosity reducer comprises the following steps:
(1) taking 50g of porous carbon powder, adding the porous carbon powder into 100ml of saturated nickel nitrate solution and 100ml of saturated copper nitrate solution to infiltrate the porous carbon powder, stirring for 5min, adding excessive potassium borohydride solution with the mass fraction of 20%, and filtering and separating out porous carbon in reaction liquid to obtain a catalyst precursor for later use.
(2) Adding the catalyst precursor obtained in the step (1) and 300ml of methanol into a high-pressure reaction kettle, reacting for 20min at 120 ℃, and then filtering to separate a solid product.
(3) And (3) adding the solid product obtained in the step (2) into an alcoholic solution of vinyl trimethoxy silane, and then preserving the temperature for 4 hours at 50 ℃ to obtain the modified catalyst.
(4) Mixing the modified catalyst in the step (3) with water according to the proportion of 1 g: and mixing the components in a proportion of 110ml, and performing ultrasonic dispersion to disperse the modified catalyst in water to obtain the thick oil viscosity reducer.
2. A method for reducing viscosity of thick oil comprises the following steps:
(i) a sample of a thick oil having a viscosity of 36600 mPas at 50 ℃ was taken and heated to 80 ℃ for use.
(ii) Adding 200g of the preheated thickened oil sample and the thickened oil viscosity reducer of the embodiment into a high-pressure reaction kettle together, wherein the addition amount of the thickened oil viscosity reducer is 0.6% of the mass of the thickened oil based on the mass of the modified catalyst, reacting at 130 ℃ for 24 hours, opening the high-pressure reaction kettle, continuously heating to remove water in the thickened oil sample after reaction, measuring the viscosity of the obtained thickened oil sample at room temperature after the temperature of the reaction kettle is reduced, and calculating the viscosity reduction rate.
Example 4
1. A preparation method of the thick oil viscosity reducer comprises the following steps:
(1) taking 50g of porous carbon powder, adding the porous carbon powder into 200ml of saturated ferric acetate solution to infiltrate the porous carbon powder, stirring for 5min, adding an excessive sodium borohydride solution with the mass fraction of 20%, and filtering and separating out porous carbon in a reaction liquid to obtain a catalyst precursor for later use.
(2) Adding the catalyst precursor obtained in the step (1) and 300ml of butanol into a high-pressure reaction kettle, reacting for 35min at 110 ℃, and then filtering to separate a solid product.
(3) And (3) adding the solid product obtained in the step (2) into an alcoholic solution of vinyl trimethoxy silane, and then preserving the temperature for 3.5 hours at 55 ℃ to obtain the modified catalyst.
(4) Mixing the modified catalyst in the step (3) with water according to the proportion of 1 g: 105ml of the mixture is mixed and subjected to ultrasonic dispersion, so that the modified catalyst is dispersed in water, and the thick oil viscosity reducer is obtained.
2. A method for reducing viscosity of thick oil comprises the following steps:
(i) a sample of a thick oil having a viscosity of 36600 mPas at 50 ℃ was taken and heated to 80 ℃ for use.
(ii) Adding 200g of the preheated thickened oil sample and the thickened oil viscosity reducer of the embodiment into a high-pressure reaction kettle together, wherein the addition amount of the thickened oil viscosity reducer is 1.2% of the mass of the thickened oil based on the mass of the modified catalyst, reacting at 160 ℃ for 24 hours, opening the high-pressure reaction kettle, continuously heating to remove water in the thickened oil sample after reaction, measuring the viscosity of the obtained thickened oil sample at room temperature after the temperature of the reaction kettle is reduced, and calculating the viscosity reduction rate.
Example 5
1. A preparation method of the thick oil viscosity reducer comprises the following steps:
(1) taking 50g of porous carbon powder, adding the porous carbon powder into 200ml of saturated ferric chloride solution to infiltrate the porous carbon powder, stirring for 5min, adding an excessive sodium borohydride solution with the mass fraction of 20%, and filtering and separating out porous carbon in a reaction liquid to obtain a catalyst precursor for later use.
(2) And (2) adding the catalyst precursor obtained in the step (1) into an alcoholic solution of vinyl triethoxysilane, and then preserving heat at 60 ℃ for 5 hours to obtain the modified catalyst.
(3) Mixing the modified catalyst in the step (2) with water in an amount of 1 g: mixing the components in a proportion of 90ml, and performing ultrasonic dispersion to disperse the modified catalyst in water to obtain the thick oil viscosity reducer.
2. A method for reducing viscosity of thick oil comprises the following steps:
(i) a sample of a thick oil having a viscosity of 36600 mPas at 50 ℃ was taken and heated to 80 ℃ for use.
(ii) Adding 200g of the preheated thickened oil sample and the thickened oil viscosity reducer of the embodiment into a high-pressure reaction kettle together, wherein the addition amount of the thickened oil viscosity reducer is 1.0% of the mass of the thickened oil based on the mass of the modified catalyst, reacting at 150 ℃ for 24 hours, opening the high-pressure reaction kettle, continuously heating to remove water in the thickened oil sample after reaction, measuring the viscosity of the obtained thickened oil sample at room temperature after the temperature of the reaction kettle is reduced, and calculating the viscosity reduction rate.
Example 6
1. A preparation method of the thick oil viscosity reducer comprises the following steps:
(1) taking 50g of porous carbon powder, adding the porous carbon powder into 200ml of saturated ferric chloride solution to infiltrate the porous carbon powder, stirring for 5min, adding an excessive sodium borohydride solution with the mass fraction of 20%, and filtering and separating out porous carbon in a reaction liquid to obtain a catalyst precursor for later use.
(2) And (2) adding the catalyst precursor obtained in the step (1) and 300ml of absolute ethyl alcohol into a high-pressure reaction kettle, reacting for 25min at 115 ℃, and filtering to separate a solid product, thus obtaining the modified catalyst.
(3) Mixing the modified catalyst in the step (2) with water in an amount of 1 g: mixing the components in a proportion of 90ml, and performing ultrasonic dispersion to disperse the modified catalyst in water to obtain the thick oil viscosity reducer.
2. A method for reducing viscosity of thick oil comprises the following steps:
(i) a sample of a thick oil having a viscosity of 36600 mPas at 50 ℃ was taken and heated to 80 ℃ for use.
(ii) Adding 200g of the preheated thickened oil sample and the thickened oil viscosity reducer of the embodiment into a high-pressure reaction kettle together, wherein the addition amount of the thickened oil viscosity reducer is 1.0% of the mass of the thickened oil based on the mass of the modified catalyst, reacting at 150 ℃ for 24 hours, opening the high-pressure reaction kettle, continuously heating to remove water in the thickened oil sample after reaction, measuring the viscosity of the obtained thickened oil sample at room temperature after the temperature of the reaction kettle is reduced, and calculating the viscosity reduction rate.
Example 7
1. A preparation method of the thick oil viscosity reducer comprises the following steps:
(1) taking 50g of porous carbon powder, adding the porous carbon powder into 200ml of saturated ferric chloride solution to infiltrate the porous carbon powder, stirring for 5min, and filtering and separating out porous carbon in reaction liquid to obtain a catalyst precursor for later use.
(2) Adding the catalyst precursor obtained in the step (1) and 300ml of absolute ethyl alcohol into a high-pressure reaction kettle, reacting for 25min at 115 ℃, and then filtering to separate a solid product.
(3) And (3) adding the solid product obtained in the step (2) into an alcoholic solution of vinyl triethoxysilane, and then preserving heat at 60 ℃ for 5 hours to obtain the modified catalyst.
(4) Mixing the modified catalyst in the step (3) with water according to the proportion of 1 g: mixing the components in a proportion of 90ml, and performing ultrasonic dispersion to disperse the modified catalyst in water to obtain the thick oil viscosity reducer.
2. A method for reducing viscosity of thick oil comprises the following steps:
(i) a sample of a thick oil having a viscosity of 36600 mPas at 50 ℃ was taken and heated to 80 ℃ for use.
(ii) Adding 200g of the preheated thickened oil sample and the thickened oil viscosity reducer of the embodiment into a high-pressure reaction kettle together, wherein the addition amount of the thickened oil viscosity reducer is 1.0% of the mass of the thickened oil based on the mass of the modified catalyst, reacting at 150 ℃ for 24 hours, opening the high-pressure reaction kettle, continuously heating to remove water in the thickened oil sample after reaction, measuring the viscosity of the obtained thickened oil sample at room temperature after the temperature of the reaction kettle is reduced, and calculating the viscosity reduction rate.
As shown in table 1, the viscosity and viscosity reduction rate calculation results of the thick oil samples in the above examples are shown. It can be seen that the viscosity reducing effect of the viscosity reducer prepared in examples 1-4 on thick oil is obviously better than that of examples 5-7, wherein in example 5, no hydrophilic group is introduced into the catalyst, so that the catalyst is agglomerated in water to affect the dispersion effect of the catalyst in thick oil, and the catalytic effect and the catalytic efficiency are reduced. And in the embodiment 6, oleophilic groups are not introduced into the catalyst, and the layering phenomenon is caused due to the incompatibility of water and oil, so that the catalyst in water is difficult to effectively contact with the thick oil, the catalyst cannot fully play a role, and the viscosity reduction effect is not high and the viscosity reduction rate is slow. On the other hand, the reduction process of the metal ions on the porous carbon is not completed in example 7, and the metal ions are re-dissolved in water after the catalyst is added into water, so that the effective catalysis effect is difficult to achieve.
TABLE 1
Example number | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
Viscosity (Pa. s) | 2060 | 1142 | 2492 | 1859 | 12916 | 22823 | 33943 |
Viscosity reduction Rate (%) | 94.37 | 96.88 | 93.19 | 94.92 | 64.71 | 37.64 | 7.26 |
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the thick oil viscosity reducer is characterized by comprising the following steps:
(1) soaking porous carbon powder with a solution containing catalyst metal ions, adding a reducing agent to reduce the metal ions into metal simple substances, enriching and adsorbing the metal simple substances on the porous carbon powder, and separating the porous carbon powder to obtain a catalyst precursor for later use;
(2) carrying out hydrophilic modification treatment on the catalyst precursor, and then carrying out oleophylic modification treatment to obtain a modified catalyst;
(3) and mixing the modified catalyst with water, and then carrying out ultrasonic dispersion to obtain an ultrasonic dispersion liquid, namely the thickened oil viscosity reducer.
2. The method for preparing the thick oil viscosity reducer according to claim 1, wherein in the step (1), the catalyst metal ions comprise: at least one of iron ions, ferrous ions, copper ions, nickel ions and zinc ions;
preferably, the solution containing the catalyst metal ions comprises a solution formed by dissolving at least one of chloride, sulfate, nitrate and acetate of the metal ions in water;
preferably, the solution containing the catalyst metal ion is a saturated solution at room temperature.
3. The method for preparing the thick oil viscosity reducer according to claim 1, wherein in the step (1), the reducing agent is any one of a sodium borohydride solution and a potassium borohydride solution.
4. The method for preparing a viscosity reducer for thick oil according to claim 1, wherein in step (2), the catalyst precursor is mixed with liquid alcohol and then subjected to a solvothermal reaction;
preferably, the temperature of the solvothermal reaction is 100-120 ℃, and the time is 20-40 min;
preferably, the liquid alcohol comprises at least one of methanol, ethanol, propanol, butanol.
5. The preparation method of the thick oil viscosity reducer according to claim 1, wherein in the step (2), the catalyst precursor subjected to hydrophilic modification treatment is mixed with a silane coupling agent solution, and then heated to a set temperature, and then subjected to heat preservation to obtain a modified catalyst;
preferably, the silane coupling agent includes any one of vinyltriethoxysilane and vinyltrimethoxysilane.
6. The method for preparing the viscosity reducer for thickened oil according to any one of claims 1 to 5, wherein the temperature is 50 to 65 ℃ for 3 to 5 hours.
7. The method for preparing the thick oil viscosity reducer according to any one of claims 1 to 5, wherein in the step (3), the ratio of the modified catalyst to water is 1 g: 80-110 ml.
8. Use of the viscosity reducer for thick oil obtained by the method for preparing the viscosity reducer for thick oil according to any one of claims 1 to 7 in petroleum engineering.
9. The use of claim 8, wherein the thick oil viscosity reducer is used for viscosity reduction of thick oil, and the use method comprises the following steps: injecting hot steam into the thickened oil recovery well to preheat the thickened oil, adding the thickened oil viscosity reducer, and sealing the oil well to perform a hydrothermal catalytic cracking reaction on the thickened oil.
10. The application of claim 9, wherein the addition amount of the thick oil viscosity reducer is 0.6-1.5% of the mass of thick oil calculated according to the mass of the modified catalyst in the thick oil viscosity reducer; preferably, the temperature of the preheating treatment is 130-170 ℃.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111492946.0A CN114058357B (en) | 2021-12-08 | 2021-12-08 | Preparation method and application of thickened oil viscosity reducer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111492946.0A CN114058357B (en) | 2021-12-08 | 2021-12-08 | Preparation method and application of thickened oil viscosity reducer |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114058357A true CN114058357A (en) | 2022-02-18 |
CN114058357B CN114058357B (en) | 2023-01-17 |
Family
ID=80229194
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111492946.0A Active CN114058357B (en) | 2021-12-08 | 2021-12-08 | Preparation method and application of thickened oil viscosity reducer |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114058357B (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115011323A (en) * | 2022-07-19 | 2022-09-06 | 胜利油田方圆化工有限公司 | Viscosity reducer for hydrothermal cracking of heavy oil and preparation method and application thereof |
CN115142830A (en) * | 2022-08-11 | 2022-10-04 | 安东石油技术(集团)有限公司 | Yield and efficiency increasing method for fracturing and reforming heavy oil reservoir |
CN115651627A (en) * | 2022-12-27 | 2023-01-31 | 胜利油田方圆化工有限公司 | Preparation process and application of modified polymer oil displacement agent for petroleum exploitation |
CN115948155A (en) * | 2023-03-13 | 2023-04-11 | 胜利油田方圆化工有限公司 | Preparation process and application of viscosity-reducing oil displacement agent for oil exploitation |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103421483A (en) * | 2012-05-17 | 2013-12-04 | 中国石油化工股份有限公司 | Nano catalytic viscosity reducer for thickened oil aqua-thermolysis and preparation method thereof |
CN105290419A (en) * | 2015-11-04 | 2016-02-03 | 郑州大学 | Fishbone-shaped core-shell structure nanometer nickel-copper alloy powder and preparation method thereof |
CN105507862A (en) * | 2015-12-04 | 2016-04-20 | 中国石油天然气股份有限公司 | Injecting method of underground modifying and viscosity-reducing nano catalyst for thickened oil |
CN109929526A (en) * | 2017-12-19 | 2019-06-25 | 常州耐强传动机械有限公司 | Heatproof emulsified viscous oil visbreaking agent |
CN110743552A (en) * | 2019-11-07 | 2020-02-04 | 西安石油大学 | Clay loaded zero-valent metal heavy oil hydrothermal cracking catalyst and its preparation method |
CN113231097A (en) * | 2021-05-11 | 2021-08-10 | 山东科技大学 | Thermal cracking catalyst and preparation method thereof |
CN113403055A (en) * | 2021-08-18 | 2021-09-17 | 北京石大瑞伽石油技术开发有限公司 | Water-soluble polymer degradation agent and preparation and application thereof |
CN113441154A (en) * | 2021-05-10 | 2021-09-28 | 宁波锋成先进能源材料研究院有限公司 | Thick oil modification nickel-based catalyst and preparation method and application thereof |
-
2021
- 2021-12-08 CN CN202111492946.0A patent/CN114058357B/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103421483A (en) * | 2012-05-17 | 2013-12-04 | 中国石油化工股份有限公司 | Nano catalytic viscosity reducer for thickened oil aqua-thermolysis and preparation method thereof |
CN105290419A (en) * | 2015-11-04 | 2016-02-03 | 郑州大学 | Fishbone-shaped core-shell structure nanometer nickel-copper alloy powder and preparation method thereof |
CN105507862A (en) * | 2015-12-04 | 2016-04-20 | 中国石油天然气股份有限公司 | Injecting method of underground modifying and viscosity-reducing nano catalyst for thickened oil |
CN109929526A (en) * | 2017-12-19 | 2019-06-25 | 常州耐强传动机械有限公司 | Heatproof emulsified viscous oil visbreaking agent |
CN110743552A (en) * | 2019-11-07 | 2020-02-04 | 西安石油大学 | Clay loaded zero-valent metal heavy oil hydrothermal cracking catalyst and its preparation method |
CN113441154A (en) * | 2021-05-10 | 2021-09-28 | 宁波锋成先进能源材料研究院有限公司 | Thick oil modification nickel-based catalyst and preparation method and application thereof |
CN113231097A (en) * | 2021-05-11 | 2021-08-10 | 山东科技大学 | Thermal cracking catalyst and preparation method thereof |
CN113403055A (en) * | 2021-08-18 | 2021-09-17 | 北京石大瑞伽石油技术开发有限公司 | Water-soluble polymer degradation agent and preparation and application thereof |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115011323A (en) * | 2022-07-19 | 2022-09-06 | 胜利油田方圆化工有限公司 | Viscosity reducer for hydrothermal cracking of heavy oil and preparation method and application thereof |
CN115142830A (en) * | 2022-08-11 | 2022-10-04 | 安东石油技术(集团)有限公司 | Yield and efficiency increasing method for fracturing and reforming heavy oil reservoir |
CN115651627A (en) * | 2022-12-27 | 2023-01-31 | 胜利油田方圆化工有限公司 | Preparation process and application of modified polymer oil displacement agent for petroleum exploitation |
CN115651627B (en) * | 2022-12-27 | 2023-03-10 | 胜利油田方圆化工有限公司 | Preparation process and application of modified polymer oil-displacing agent for oil exploitation |
CN115948155A (en) * | 2023-03-13 | 2023-04-11 | 胜利油田方圆化工有限公司 | Preparation process and application of viscosity-reducing oil displacement agent for oil exploitation |
CN115948155B (en) * | 2023-03-13 | 2023-05-12 | 胜利油田方圆化工有限公司 | Preparation process and application of viscosity-reducing oil displacement agent for petroleum exploitation |
Also Published As
Publication number | Publication date |
---|---|
CN114058357B (en) | 2023-01-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN114058357B (en) | Preparation method and application of thickened oil viscosity reducer | |
CN100391601C (en) | Catalyst for downhole catalytic reforming of viscous crude | |
CN105478120A (en) | Preparation method for red mud-based iron-series catalyst and application of red mud-based iron-series catalyst in hydrogen production through cracking of methane | |
CN102049179A (en) | Method for preparing supported iron oxide series desulfurizing agent | |
WO2011034327A2 (en) | Absorbent containing chitosan for treating water and method for manufacturing same | |
Long et al. | Adsorption of ammonia on activated carbon from aqueous solutions | |
CN110201637B (en) | Preparation method of adsorbent for removing organic sulfide in natural gas | |
CN112320797B (en) | Preparation method of activated carbon for desulfurization of tar hydrogenation product | |
CN115011323B (en) | Viscosity reducer for aquathermolysis of thick oil and preparation method and application thereof | |
CN114988393A (en) | Preparation method of sulfur-nitrogen doped hierarchical porous carbon adsorption material | |
CN107081137B (en) | Lignin graft bentonite loads nano zero valence iron composite material and preparation method | |
CN101323794B (en) | Spherical active carbon fuel oil adsorption desulfurizing agent and preparation thereof | |
CN110589822A (en) | Method for preparing activated carbon from plastic waste and application of activated carbon | |
CN105126747A (en) | Preparation method of copper-containing mesoporous adsorbent for gasoline desulfurization | |
CN103394324B (en) | Load-type dearsenic agent and preparation method | |
CN107460021B (en) | Preparation method of low-temperature graphene-based nano borate composite material | |
CN110145282A (en) | A kind of method of loaded catalyst assisted microwave synthesis production of heavy oil reservoir | |
CN114058358A (en) | Preparation method and application of viscosity-reducing oil displacement agent for thick oil | |
CN115651627B (en) | Preparation process and application of modified polymer oil-displacing agent for oil exploitation | |
CN103480408B (en) | A kind of diesel oil distillate oil hydrogenation catalysts containing rare earth and Synthesis and applications thereof | |
CN111804328B (en) | Preparation method of catalyst for catalyzing viscosity reduction of thickened oil | |
CN111574986A (en) | Preparation method of hydrothermal cracking catalytic viscosity reducer | |
CN110743552A (en) | Clay loaded zero-valent metal heavy oil hydrothermal cracking catalyst and its preparation method | |
CN112044392A (en) | Preparation method of magnesium modified nano silicon dioxide hollow sphere | |
CN110437818B (en) | Gel breaking activator suitable for reservoir fracturing at 20-50 ℃ and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | 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 |