CN104588038A - Regeneration method for deactivated heavy oil hydrogenation catalyst - Google Patents
Regeneration method for deactivated heavy oil hydrogenation catalyst Download PDFInfo
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- CN104588038A CN104588038A CN201310532049.7A CN201310532049A CN104588038A CN 104588038 A CN104588038 A CN 104588038A CN 201310532049 A CN201310532049 A CN 201310532049A CN 104588038 A CN104588038 A CN 104588038A
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Abstract
The invention discloses a regeneration method for a deactivated heavy oil hydrogenation catalyst. The method comprises the following steps: placing the deactivated heavy oil hydrogenation catalyst in a supercritical fluid system reactor; preparing a mixed liquid from an organic solvent, a dispersing agent and organic acid and carrying out treatment on the heavy oil hydrogenation catalyst in the presence of supercritical fluid CO2; and then carrying out hydrothermal treatment so as to obtain the regenerated catalyst. The method overcomes the problem of generation of a large amount of pollution during regeneration of the deactivated catalyst, enables the mechanical properties and hydrogenation activity of the catalyst to be perfectly recovered and is easy to implement.
Description
Technical field
The present invention relates to a kind of renovation process of inactivation hydrogenation catalyst, the method is specially adapted to the regeneration of inactivation heavy oil hydrogenating treatment catalyst.
Background technology
Day by day become at crude oil be heavily deteriorated, under the ever-increasing situation of ultra-clean demand for fuel, hydrogen addition technology is more and more attractive.Hydrogenation catalyst in use, covers because strong adsorbent makes that activated centre is poisoning, active site is deposited thing (coke and metal), catalyst aperture reduces/blocks and the factor such as active phase sintering causes and loses its original activity.Inactivation hydrogenation catalyst mostly is black, and surface is containing materials such as oil, colloids, and catalyst itself is containing metal values such as Co, Ni, Mo, V, W, Fe.Inactivation hydrogenation catalyst can be used by the method for regeneration, reduces directly discharge to the pollution of environment and the waste of resource.
The regeneration of hydrogenation catalyst refers to that catalyst activity and selectivity after using drops to a certain degree, make the even a kind of operating process that is restored of mechanical strength of its activity and selectivity by suitable process, it be extending catalyst service life, reduce a kind of important means of production cost.The renovation process of conventional decaying catalyst mainly contains oxidizing process and solvent method two kinds.Oxidizing process ignition temperature is high, easily destroys the structure of catalyst or changes the chemical composition of catalyst.Solvent method adopts the solvable Jiao of solvent under certain operating conditions on catalyst-solvent, and solvent load is comparatively large and reclaim comparatively difficulty.
Supercritical fluid refers to the fluid being in more than critical-temperature and critical pressure.It has the character of gas and liquid concurrently, and both had liquid has larger solubility feature to solute, have again the characteristic that gas easily spreads and moves, its mass transfer rate is much higher than liquid phase process.Therefore, supercritical fluid is applied in fields such as extraction, separation, particulate preparation and chemical reactions.
At present, treatment with supercritical fluid decaying catalyst main purpose is adopted to be the organic substance that removing catalyst surface deposits.CN1762600A discloses a kind of method of reproducing catalyst by supercritical fluid.The method be by the catalyst of inactivation in unsaturation organic compound hydrogenation reaction in one of two extraction kettles of parallel connection with CO
2or CO
2-cosolvent contacts continuously, utilizes CO
2extraction takes regenerated catalyst.The method is thought under overcritical situation, CO
2and cosolvent noble metal catalyst causes the organic impurities of catalysqt deactivation to have good dissolubility to being adsorbed on and can not having harmful effect to catalyst carrier.But for heavy oil or residual oil inactivated hydrotreating catalyst, the carbon deposit more due to its surface deposition and W metal, V, Fe etc., adopt this supercritical process that the activity of heavy oil or catalyst for hydrotreatment of residual oil can not be made very well to be recovered.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of renovation process of inactivation heavy oil hydrogenating treatment catalyst.The method is the problem that when not only solving decaying catalyst regeneration, institute produces a large amount of pollution, and the mechanical performance of catalyst and hydrogenation activity are well recovered, and technology is easily implemented.
The renovation process of inactivation heavy oil hydrogenating treatment catalyst of the present invention, comprising:
(1) inactivation heavy oil hydrogenating treatment catalyst is placed in supercritical fluid system response device;
(2) mixed liquor is made with organic solvent, dispersant and organic acid; Described organic acid is one or more in acetic acid, citric acid, oxalic acid, tartaric acid, and addition is 0.1 ~ 5g/mL organic solvent, preferably 0.5 ~ 4g/mL organic solvent;
(3) in supercritical fluid system response device, temperature is 40 ~ 100 DEG C, and pressure is 8 ~ 25MPa, passes into liquid CO in reactor
2and mixed liquor prepared by above-mentioned steps (2), heavy oil hydrogenating treatment catalyst is processed;
(4) catalyst after the process of step (3) gained carries out hydrothermal treatment consists in hydrothermal treatment device, after hydrothermal treatment consists, obtains the catalyst after regenerating; Wherein said hydrothermal conditions is as follows: temperature is 400 DEG C ~ 600 DEG C, and processing pressure is 0.15 ~ 0.35MPa, and the processing time is 1 ~ 8h.
Inactivation heavy oil hydrogenating treatment catalyst, particularly catalyst for heavy oil hydrogenation demetal, Hydrobon catalyst or hydrogenation conversion catalyst in step (1).
Organic solvent described in step (2) is selected from ketones solvent, as one or more in acetone, butanone.Described dispersant is one or more in polyethylene glycol, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polypropylene amine, and addition is 0.5 ~ 5g/mL organic solvent, preferably 1 ~ 3 g/mL organic solvent.The molecular weight of described dispersant is 200 ~ 2000.Described organic acid is one or more in acetic acid, citric acid, oxalic acid, tartaric acid, and addition is 0.1 ~ 5g/mL organic solvent, preferably 0.5 ~ 4g/mL organic solvent.
Reaction temperature described in step (3) preferably 40 ~ 90 DEG C, pressure is 9 ~ 15MPa preferably.Liquid CO
2flow be 5 ~ 80mL/min, preferably 10 ~ 50mL/min, the flow of step (2) mixed liquor is 10 ~ 100 mL/min, preferably 10 ~ 50mL/min.Extraction time comprehensively determines according to catalyst inactivation, decaying catalyst treating capacity and operating condition.
The method of regeneration of deactivated heavy oil hydrogenating treatment catalyst provided by the invention, adopts CO
2supercritical fluids system, and at dispersant, under the existence of the mixed liquor of organic acid and organic solvent, inactivation heavy oil hydrogenating treatment catalyst is processed, not only effectively can remove residual heavy oil and the part carbon deposit on decaying catalyst surface, simultaneously can also when catalyst strength keeps substantially, the further W metal improving deposition, V, again the dispersion of Fe and active metal, and in follow-up hydrothermal treatment step further activating catalyst, not only avoid the loss of active metal, but also while the activity of active metal is recovered, take full advantage of again the metal of deposition.In addition, follow-up hydrothermal treatment process, can also reduce coke content and the sulfur content of catalyst surface, and improve catalyst pore structure.The inventive method can make the mechanical strength of catalyst revert to fresh dose more than 80%, hydrogenation activity reverts to fresh dose more than 70%.
Detailed description of the invention
State technical characteristic of the present invention further below by embodiment, but be not limited to embodiment.Wt% is mass fraction.
Embodiment 1
Measure the HDS catalyst A-N(wherein MoO of certain volume
3: 13wt%, NiO:2.3wt%, alumina content is 82.7wt%), drawing off after residual hydrogenation equipment running and obtaining catalyst A-S(carbon content is 22.48%, sulfur content is 4.86%), its weight is 10g, is positioned in the basketry of Multifunction super critical fluid system.Adopt PEG400 as organic dispersing agent, citric acid, as weak acid, is dissolved in the acetone solvent of 1L, and wherein the addition of PEG400 is 500g, and the addition of citric acid is 500g, is configured to mixed liquor.If consumption not can by this proportional arrangement.
Temperature in Multifunction super critical fluid system response device is set as 90 DEG C, and pressure setting is 10MPa, passes into liquid CO in reactor
2and the mixed liquor of above-mentioned preparation, decaying catalyst is processed, until when the liquid phase put into is near colorless, stops supercritical processing apparatus.The catalyst in basketry is taken out after cooling.Wherein CO
2flow be 20mL/min, the flow of mixed liquor is 20mL/min.
By the catalyst after overcritical device process, be placed in hydrothermal treatment device and carry out hydrothermal treatment consists, treatment temperature is 550 DEG C, processing pressure 0.23MPa, processing time 4h, the catalyst A-1 after hydrothermal treatment consists.With this condition repeatedly, sample is saved bit by bit.
Embodiment 2
Other condition is with embodiment 1, and just the addition of citric acid is 1000g, and hydrothermal treatment consists temperature is 600 DEG C, and process obtains catalyst A-2.With this condition repeatedly, sample is saved bit by bit.
Embodiment 3
Measure the HDM catalyst B-N(wherein MoO of certain volume
3: 5wt%, NiO:1.0 wt%, alumina content is 95wt%), drawing off after residual hydrogenation equipment running and obtaining catalyst B-S(carbon content is 9.50%, sulfur content is 12.93%), its weight is 15g, is positioned in the basketry of Multifunction super critical fluid system.Adopt Macrogol 200 as organic dispersing agent, glacial acetic acid as weak acid, in the acetone joining 1L and butanone (volume ratio 1:1), wherein the addition of Macrogol 200 is 100g, the addition of glacial acetic acid is 3500g, is configured to mixed liquor, if consumption not can by this proportional arrangement.
Temperature in Multifunction super critical fluid system response device is set as 120 DEG C, and pressure setting is 13MPa, passes into liquid CO in reactor
2and the mixed liquor of above-mentioned preparation, decaying catalyst is processed, until when the liquid phase put into is near colorless, stops supercritical processing apparatus.The catalyst in basketry is taken out after cooling.Wherein CO
2flow be 10mL/min, the flow of mixed solvent is 30mL/min.
By the catalyst after overcritical device process, be placed in hydrothermal treatment device and carry out hydrothermal treatment consists, treatment temperature is 500 DEG C, processing pressure 0.30MPa, processing time 6h, the catalyst B-1 after hydrothermal treatment consists.With this condition repeatedly, sample is saved bit by bit.
Embodiment 4
Other condition is with embodiment 3, and just increase citric acid 500g, first supercritical processing temperature changes 100 DEG C into, and hydrothermal treatment consists temperature is 450 DEG C, and process obtains catalyst B-2.With this condition repeatedly, sample is saved bit by bit.
Comparative example 1
Measure the HDS catalyst A-N of certain volume, draw off after residual hydrogenation equipment running and obtain catalyst A-S, its weight is 10g, is positioned in the basketry of Multifunction super critical fluid system.Temperature in Multifunction super critical fluid system response device is set as 90 DEG C, and pressure setting is 10MPa, passes into liquid CO in reactor
2and organic solvent-acetone, decaying catalyst is processed, until when the liquid phase put into is near colorless, stops supercritical processing apparatus.Catalyst A-the R1 in basketry is taken out after cooling.Wherein CO
2flow be 20mL/min, the flow of acetone is 20mL/min.With this condition repeatedly, sample is saved bit by bit.
Comparative example 2
Measure the HDS catalyst A-N of certain volume, draw off after residual hydrogenation equipment running and obtain catalyst A-S, its weight is 10g, is positioned in the basketry of Multifunction super critical fluid system.Temperature in Multifunction super critical fluid system response device is set as 90 DEG C, and pressure setting is 10MPa, passes into liquid CO in reactor
2and organic solvent-acetone, decaying catalyst is processed, until when the liquid phase put into is near colorless, stops supercritical processing apparatus.The catalyst in basketry is taken out after cooling.Wherein CO
2flow be 20mL/min, the flow of acetone is 20mL/min.
By the catalyst after overcritical device process, be placed in hydrothermal treatment device and carry out hydrothermal treatment consists, treatment temperature is 550 DEG C, processing pressure 0.23MPa, processing time 4h, the catalyst A-R2 after hydrothermal treatment consists.With this condition repeatedly, sample is saved bit by bit.
Comparative example 3
Measure the HDS catalyst A-N of certain volume, draw off after residual hydrogenation equipment running and obtain catalyst A-S, its weight is 10g, is positioned in the basketry of Multifunction super critical fluid system.Adopt citric acid as weak acid, be dissolved in the acetone solvent of 1L, wherein the addition of citric acid is 500g, is configured to mixed liquor.If consumption not can by this proportional arrangement.
Temperature in Multifunction super critical fluid system response device is set as 90 DEG C, and pressure setting is 10MPa, passes into liquid CO in reactor
2and the mixed liquor of above-mentioned preparation, decaying catalyst is processed, until when the liquid phase put into is near colorless, stops supercritical processing apparatus.Catalyst A-the R3 in basketry is taken out after cooling.Wherein CO
2flow be 20mL/min, the flow of mixed liquor is 20mL/min.With this condition repeatedly, sample is saved bit by bit.
Comparative example 4
Measure the HDM catalyst B-N of certain volume, draw off after residual hydrogenation equipment running and obtain catalyst B-S, its weight is 15g, is positioned in the basketry of Multifunction super critical fluid system.
Temperature in Multifunction super critical fluid system response device is set as 120 DEG C, and pressure setting is 13MPa, passes into liquid CO in reactor
2and mixed liquor prepared by acetone and butanone (volume ratio 1:1), decaying catalyst is processed, until when the liquid phase put into is near colorless, stops supercritical processing apparatus.Catalyst B-the R2 in basketry is taken out after cooling.Wherein CO
2flow be 10mL/min, the flow of mixed solvent is 30mL/min.With this condition repeatedly, sample is saved bit by bit.
Above-mentioned fresh catalyst and the catalyst after regeneration are analyzed, and carry out activity rating in batch autoclave, raw materials used oil nature is in table 1, and appreciation condition is in table 2, and the physico-chemical property of catalyst is in table 3, and evaluation result is in table 4.
Table 1 feedstock oil character
Table 2 process conditions
Table 3 catalyst property
Table 3 continues
Table 4 evaluation result
| Project | A-N | A-1 | A-2 | Comparative example A-R1 | Comparative example A-R2 | Comparative example A-R3 |
| Relatively de-(Ni+V) rate | 100 | 80 | 84 | 52 | 65 | 61 |
| Relative desulfurization degree | 100 | 83 | 89 | 58 | 70 | 65 |
| Relatively de-carbon yield | 100 | 79 | 83 | 53 | 66 | 62 |
Continued 4
| Project | B-N | B-1 | B-2 | Comparative example B-R1 |
| Relatively de-(Ni+V) rate | 100 | 73 | 79 | 50 |
| Relative desulfurization degree | 100 | 80 | 85 | 55 |
| Relatively de-carbon yield | 100 | 75 | 80 | 50 |
Data as can be seen from table 3 and table 4: adopt regeneration methods of the invention, specific area and pore volume recover better, C and S is effectively removed, and intensity reduces seldom, and active metallic content is higher, and activation recovering is higher.
Claims (9)
1. a renovation process for inactivation heavy oil hydrogenating treatment catalyst, comprising:
(1) inactivation heavy oil hydrogenating treatment catalyst is placed in supercritical fluid system response device;
(2) mixed liquor is made with organic solvent, dispersant and organic acid; Described organic acid is one or more in acetic acid, citric acid, oxalic acid, tartaric acid, and addition is 0.1 ~ 5g/mL organic solvent;
(3) in supercritical fluid system response device, temperature is 40 ~ 100 DEG C, and pressure is 8 ~ 25MPa, passes into liquid CO in reactor
2and mixed liquor prepared by above-mentioned steps (2), heavy oil hydrogenating treatment catalyst is processed;
(4) catalyst after the process of step (3) gained carries out hydrothermal treatment consists in hydrothermal treatment device, after hydrothermal treatment consists, obtains the catalyst after regenerating; Wherein said hydrothermal conditions is as follows: temperature is 400 DEG C ~ 600 DEG C, and processing pressure is 0.15 ~ 0.35MPa, and the processing time is 1 ~ 8h.
2. in accordance with the method for claim 1, it is characterized in that in step (1), heavy oil hydrogenating treatment catalyst is catalyst for heavy oil hydrogenation demetal, Hydrobon catalyst or hydrogenation conversion catalyst.
3. in accordance with the method for claim 1, it is characterized in that one or more that the organic solvent described in step (2) is selected from acetone, butanone.
4., according to the method described in claim 1 or 3, it is characterized in that the dispersant described in step (2) is one or more in polyethylene glycol, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polypropylene amine, addition is 0.5 ~ 5g/mL organic solvent.
5. in accordance with the method for claim 4, it is characterized in that the molecular weight of dispersant described in step (2) is 200 ~ 2000.
6. in accordance with the method for claim 1, it is characterized in that the dispersant addition described in step (2) is 1 ~ 3g/mL organic solvent.
7. in accordance with the method for claim 1, it is characterized in that described organic acid addition is 0.5 ~ 4g/mL organic solvent.
8. in accordance with the method for claim 1, it is characterized in that the reaction temperature described in step (3) is 40 ~ 90 DEG C, pressure is 9 ~ 15MPa.
9. in accordance with the method for claim 1, it is characterized in that in step (3), liquid CO
2flow be 5 ~ 80mL/min, the flow of step (2) gained mixed liquor is 10 ~ 100 mL/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113019470A (en) * | 2021-03-18 | 2021-06-25 | 上海大学材料基因组工程(萍乡)研究院 | Method for activating transition metal catalyst |
| CN114425393A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method of catalyst |
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| US20030144129A1 (en) * | 2002-01-29 | 2003-07-31 | Clark Janet Renee | Supported catalyst regeneration |
| CN1762600A (en) * | 2004-10-22 | 2006-04-26 | 中国石油化工股份有限公司 | A kind of method of reproducing catalyst by supercritical fluid |
| CN1762601A (en) * | 2004-10-22 | 2006-04-26 | 中国石油化工股份有限公司 | A kind of process of reproducing catalyst by supercritical fluid |
| CN101024185A (en) * | 2007-03-16 | 2007-08-29 | 扬子石油化工股份有限公司 | Method for reactivating palledium/carbon catalyst |
| CN102382676A (en) * | 2010-08-25 | 2012-03-21 | 中国石油化工股份有限公司 | Alkylation method |
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2013
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Patent Citations (6)
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| CN1230467A (en) * | 1998-03-30 | 1999-10-06 | 中国科学院山西煤炭化学研究所 | In-situ regeneration process of Fisher-Tropsch synthesis catalyst |
| US20030144129A1 (en) * | 2002-01-29 | 2003-07-31 | Clark Janet Renee | Supported catalyst regeneration |
| CN1762600A (en) * | 2004-10-22 | 2006-04-26 | 中国石油化工股份有限公司 | A kind of method of reproducing catalyst by supercritical fluid |
| CN1762601A (en) * | 2004-10-22 | 2006-04-26 | 中国石油化工股份有限公司 | A kind of process of reproducing catalyst by supercritical fluid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114425393A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method of catalyst |
| CN113019470A (en) * | 2021-03-18 | 2021-06-25 | 上海大学材料基因组工程(萍乡)研究院 | Method for activating transition metal catalyst |
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