CN109749773B - Multi-stage extraction desulfurization method for hydrogenated gasoline - Google Patents
Multi-stage extraction desulfurization method for hydrogenated gasoline Download PDFInfo
- Publication number
- CN109749773B CN109749773B CN201910177734.XA CN201910177734A CN109749773B CN 109749773 B CN109749773 B CN 109749773B CN 201910177734 A CN201910177734 A CN 201910177734A CN 109749773 B CN109749773 B CN 109749773B
- Authority
- CN
- China
- Prior art keywords
- weight
- parts
- reaction kettle
- gasoline
- deionized water
- 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
Images
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a multistage extraction desulfurization method for hydrogenated gasoline, which belongs to the field of chemical industry, and comprises the steps of putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g after hydrotreating, 5-10 parts by weight of 1-heptyl pyridine triflate and 40-60 parts by weight of deionized water into a reaction kettle, and uniformly stirring to complete primary desulfurization; and adding 1-heptyl pyridine trifluoromethanesulfonate and deionized water repeatedly for the second two times, extracting for three times, and washing with water to obtain the gasoline with the sulfur content of less than 5 mu g/g. The invention has the beneficial effects that: 1-heptyl pyridine trifluoromethanesulfonate solution is used as an extracting agent, the gasoline subjected to hydrodesulfurization treatment is subjected to extraction desulfurization again, and the gasoline with the sulfur content of below 5 mu g/g is obtained after three times of extraction desulfurization, wherein the yield of the gasoline exceeds 65 percent, and the method has the characteristics of low sulfur content, high gasoline yield and the like.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a multistage extraction desulfurization method for hydrogenated gasoline.
Background
The sulfides in gasoline exist in the forms of hydrogen sulfide, mercaptan, thioether, thiophene and derivatives thereof, which not only cause poor oxidation stability, octane number reduction and corrosion of engine combustion systems, but also sulfur oxides generated after combustion are main pollutants in the atmosphere. With the stricter environmental regulations, the quality requirement of gasoline is higher and higher. From 1 month and 1 day in 2017, the motor gasoline meeting the national five standards (the sulfur content is reduced to below 10 mu g/g) is completely supplied nationwide, so the development and production of low-sulfur clean gasoline meeting the environmental protection requirements become an irreparable task for the oil refining industry.
At present, hydrodesulfurization is mainly adopted in industry to produce low-sulfur gasoline, although the method can meet the requirement of low sulfur of gasoline, the operation condition is harsh, the method needs to be carried out under the conditions of high temperature and high pressure, a high-efficiency catalyst is needed, a large amount of hydrogen is consumed, the investment and operation cost is high, and the production cost of the gasoline is greatly increased. In order to reduce the cost, many researchers have focused on non-hydrodesulfurization technologies such as extraction desulfurization, adsorption desulfurization, oxidative desulfurization, and ionic liquid desulfurization. The gasoline extraction desulfurization technology has the advantages of low octane value loss, no hydrogen consumption, mild operation conditions, low operation cost, capability of being combined with other desulfurization technologies, and the like, and becomes a hot point of domestic and foreign research in recent years.
Disclosure of Invention
In order to overcome the problems of harsh operating conditions, high-efficiency catalyst requirement, large hydrogen consumption, high investment and operating cost and the like in the production of low-sulfur gasoline by hydrodesulfurization in the prior art, the invention provides a multistage extraction desulfurization method for hydrogenated gasoline, which comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g, 5-10 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 40-60 parts by weight of deionized water into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 400-500 r/min, stopping stirring after 20-30 min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the middle lower layer of the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 10-15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 80-100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 5-7 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate solution and 30-50 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain third desulfurized gasoline;
step five: adding 30-50 parts by weight of deionized water into a reaction kettle, stirring and washing with water at a stirring speed of 600-800 r/min for 10-20 min, standing for 20-30 min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline with the sulfur content of below 5 mug/g.
Preferably, the 1-heptylpyridine trifluoromethanesulfonate is added in an amount of 10 parts by weight and the deionized water is added in an amount of 50 parts by weight in the first step.
Preferably, the stirring speed in the reaction kettle in the second step is 500r/min, and the stirring time is 20 min.
Preferably, the 1-heptyl pyridine trifluoromethanesulfonate is added in an amount of 15 parts by weight in the third step, and the deionized water is added in an amount of 100 parts by weight.
Preferably, the 1-heptyl pyridine trifluoromethanesulfonate is added in an amount of 5 parts by weight and the deionized water is added in an amount of 30 parts by weight in the fourth step.
Preferably, the deionized water is added in 50 parts by weight in the fifth step, the stirring speed is 800r/min, the stirring time is 20min, and the standing time is 30 min.
Preferably, the lower layer solvent discharged from the reaction kettle in the second step is distilled, NaOH solution is added to enable the pH value of the lower layer solvent to be 7-8, the obtained solution is used as a recycling extracting agent in the first step and the second step, and the liquid surface pressure of the solution is controlled to be 3 atmospheric pressures in the distillation process.
Compared with the prior art, the invention has the beneficial effects that:
(1) the 1-heptyl pyridine trifluoromethanesulfonate solution is used as an extracting agent, the gasoline subjected to hydrodesulfurization treatment is subjected to secondary extraction desulfurization treatment, and the gasoline with the sulfur content of below 5 mu g/g is obtained through three times of extraction desulfurization, wherein the gasoline yield exceeds 65 percent, and the method has the characteristics of low sulfur content, high gasoline yield and the like.
(2) The lower-layer solvent obtained in each extraction in the patent can be used as a recycling extractant for the first step and the second step after high-pressure distillation and pH value adjustment, so that the recycling of the extractant is realized, the consumption of 1-heptyl pyridine trifluoromethanesulfonate is greatly reduced, and the cost is reduced.
Drawings
FIG. 1 is a flow chart of a preferred process of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Fig. 1 shows a process flow of the extraction desulfurization process in the embodiment, wherein the hydrotreated gasoline is subjected to three-stage extraction and primary water washing to obtain low-sulfur gasoline, and the solvent after each extraction can be distilled and added with NaCl solution to obtain a recycled extractant for extraction in the first step and the second step, and the specific steps include:
the method comprises the following steps: for the first extraction, slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g, 5-10 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 40-60 parts by weight of deionized water into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 400-500 r/min, stopping stirring after 20-30 min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the middle lower layer of the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: extracting for the second time, adding 10-15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 80-100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: extracting for the third time, adding 5-7 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate solution and 30-50 parts by weight of deionized water into the reaction kettle, and repeating the step two to obtain desulfurized gasoline for the third time;
step five: and (2) washing, namely adding 30-50 parts by weight of deionized water into the reaction kettle, stirring and washing at the stirring speed of 600-800 r/min for 10-20 min, standing for 20-30 min to separate the liquid into an upper layer and a lower layer, and removing solvent residues on the lower layer to obtain the required gasoline with the sulfur content of below 5 mu g/g.
Preferably, the 1-heptylpyridine trifluoromethanesulfonate is added in an amount of 10 parts by weight and the deionized water is added in an amount of 50 parts by weight in the first step.
Preferably, the stirring speed in the reaction kettle in the second step is 500r/min, and the stirring time is 20 min.
Preferably, the 1-heptyl pyridine trifluoromethanesulfonate is added in an amount of 15 parts by weight in the third step, and the deionized water is added in an amount of 100 parts by weight.
Preferably, the 1-heptyl pyridine trifluoromethanesulfonate is added in an amount of 5 parts by weight and the deionized water is added in an amount of 30 parts by weight in the fourth step.
Preferably, the deionized water is added in 50 parts by weight in the fifth step, the stirring speed is 800r/min, the stirring time is 20min, and the standing time is 30 min.
Preferably, the lower layer solvent discharged from the reaction kettle in the second step is distilled, and NaOH solution is added to ensure that the pH value is 7-8, and the obtained solution is used as an extracting agent in the first step and the second step.
To specifically illustrate the technical effect of the desulfurization process employed in the present embodiment, further description will be made below by several pairs of comparative examples and examples.
The first embodiment is as follows:
the multistage extraction desulfurization method for hydrogenated gasoline in the embodiment comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g, 10 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 50 parts by weight of deionized water into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 5 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate solution and 30 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain third desulfurized gasoline;
step five: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Example two:
the multistage extraction desulfurization method for hydrogenated gasoline in the embodiment comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g, 5 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 40 parts by weight of deionized water into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed solution in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 60min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the middle-lower layer of the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 5 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate solution and 30 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain third desulfurized gasoline;
step five: and adding 30 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Example three:
the multistage extraction desulfurization method for hydrogenated gasoline in the embodiment comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g, 8 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 60 parts by weight of deionized water into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed solution in the reaction kettle at 25 ℃, controlling the stirring speed at 400r/min, stopping stirring after 24min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 45min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 10 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 80 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 5 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate solution and 50 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain third desulfurized gasoline;
step five: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Example four:
the multistage extraction desulfurization method for hydrogenated gasoline in the embodiment comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g, 10 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 50 parts by weight of deionized water into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed solution in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 25min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 7 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate solution and 50 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain third desulfurized gasoline;
step five: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 600r/min for 10min, standing for 25min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Example five:
the multistage extraction desulfurization method for hydrogenated gasoline in the embodiment comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g, 10 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 50 parts by weight of deionized water into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed solution in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 5 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate solution and 30 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain third desulfurized gasoline;
step five: and adding 30 parts by weight of deionized water into the reaction kettle, stirring and washing with water at the stirring speed of 700r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Comparative example one:
the multi-stage extraction desulfurization method for hydrogenated gasoline in the comparative example comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g and 100 parts by weight of N, N-dimethylformamide into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 100 parts by weight of N, N-dimethylformamide into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 100 parts by weight of N, N-dimethylformamide into the reaction kettle, and repeating the second step to obtain desulfurized gasoline for three times;
step five: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Comparative example two:
the multi-stage extraction desulfurization method for hydrogenated gasoline in the comparative example comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g and 100 parts by weight of acetonitrile into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 100 parts by weight of acetonitrile into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 100 parts by weight of acetonitrile into the reaction kettle, and repeating the second step to obtain third desulfurized gasoline;
step five: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Comparative example three:
the multi-stage extraction desulfurization method for hydrogenated gasoline in the comparative example comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g and 100 parts by weight of N-formylmorpholine into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 100 parts by weight of N-formylmorpholine into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 100 parts by weight of N-formylmorpholine into the reaction kettle, and repeating the second step to obtain third desulfurized gasoline;
step five: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Comparative example four:
the multi-stage extraction desulfurization method for hydrogenated gasoline in the comparative example comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g and 100 parts by weight of 1-n-butyl-3-methylimidazole trifluoromethanesulfonate which are subjected to hydrotreating into a reaction kettle;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 100 parts by weight of 1-n-butyl-3-methylimidazole trifluoromethanesulfonate into the reaction kettle, and repeating the step two to obtain secondary desulfurized gasoline;
step four: adding 100 parts by weight of 1-n-butyl-3-methylimidazole trifluoromethanesulfonate into the reaction kettle, and repeating the second step to obtain third desulfurized gasoline;
step five: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Comparative example five:
the multi-stage extraction desulfurization method for hydrogenated gasoline in the comparative example comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g and 100 parts by weight of 1-decyl-3-methylimidazolium bromide after hydrotreating into a reaction kettle;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 100 parts by weight of 1-decyl-3-methylimidazole bromine salt into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 100 parts by weight of 1-decyl-3-methylimidazole bromine salt into the reaction kettle, and repeating the second step to obtain tertiary desulfurized gasoline;
step five: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Comparative example six:
the multi-stage extraction desulfurization method for hydrogenated gasoline in the comparative example comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g and 100 parts by weight of N-butyl pyridine nitrate into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 100 parts by weight of N-butyl pyridine nitrate into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 100 parts by weight of N-butyl pyridine nitrate into the reaction kettle, and repeating the second step to obtain third desulfurized gasoline;
step five: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Comparative example seven:
the multi-stage extraction desulfurization method for hydrogenated gasoline in the comparative example comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g and 100 parts by weight of N-butylpyridinium tetrafluoroborate into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 100 parts by weight of N-butylpyridinium tetrafluoroborate into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 100 parts by weight of N-butylpyridinium tetrafluoroborate into the reaction kettle, and repeating the second step to obtain desulfurized gasoline for three times;
step five: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Comparative example eight:
the multistage extraction desulfurization method for hydrogenated gasoline in the embodiment comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g, 10 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 50 parts by weight of deionized water into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Comparative example nine:
the multistage extraction desulfurization method for hydrogenated gasoline in the embodiment comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g, 10 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 50 parts by weight of deionized water into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Comparative example ten:
the multistage extraction desulfurization method for hydrogenated gasoline in the embodiment comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g, 10 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 50 parts by weight of deionized water into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain third desulfurized gasoline;
step five: adding 5 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate solution and 30 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain four-time desulfurized gasoline;
step six: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Comparative example eleven:
the multistage extraction desulfurization method for hydrogenated gasoline in the embodiment comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g, 10 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 50 parts by weight of deionized water into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain third desulfurized gasoline;
step five: adding 15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain four-time desulfurized gasoline;
step six: adding 5 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate solution and 30 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain five times of desulfurized gasoline;
step seven: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Comparative example twelve:
the multistage extraction desulfurization method for hydrogenated gasoline in the embodiment comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g, 10 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 50 parts by weight of deionized water into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: and (3) adding 5 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate solution and 30 parts by weight of deionized water into the reaction kettle, and repeating the step two to obtain the required gasoline.
Comparative example thirteen:
the multi-stage extraction desulfurization method for hydrogenated gasoline in the comparative example comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g, 2 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 50 parts by weight of deionized water into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 5 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate solution and 30 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain third desulfurized gasoline;
step five: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Comparative example fourteen:
the multi-stage extraction desulfurization method for hydrogenated gasoline in the comparative example comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g, 4 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 50 parts by weight of deionized water into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 5 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate solution and 30 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain third desulfurized gasoline;
step five: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Comparative example fifteen:
the multi-stage extraction desulfurization method for hydrogenated gasoline in the comparative example comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g, 12 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 50 parts by weight of deionized water into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 5 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate solution and 30 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain third desulfurized gasoline;
step five: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
Comparative example sixteen:
the multi-stage extraction desulfurization method for hydrogenated gasoline in the comparative example comprises the following steps:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g, 15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 50 parts by weight of deionized water into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 500r/min, stopping stirring after 20min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the lower layer in the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 5 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate solution and 30 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain third desulfurized gasoline;
step five: and adding 50 parts by weight of deionized water into the reaction kettle, stirring and washing with water at a stirring speed of 800r/min for 20min, standing for 30min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline.
The five groups of examples and the sixteen groups of examples are used for carrying out sulfur content and yield tests on the gasoline obtained in proportion, and the results are as follows:
| sulfur content/. mu.g/g | Yield/% | |
| Example one | 4.5 | 68.2 |
| Example two | 4.7 | 67.1 |
| EXAMPLE III | 4.6 | 69.8 |
| Example four | 4.8 | 66.0 |
| EXAMPLE five | 5.0 | 65.8 |
| Comparative example 1 | 8.7 | 67.8 |
| Comparative example No. two | 9.2 | 67.4 |
| Comparative example No. three | 10.7 | 54.6 |
| Comparative example No. four | 12.6 | 68.1 |
| Comparative example five | 7.6 | 73.4 |
| Comparative example six | 11.7 | 70.5 |
| Comparative example seven | 8.8 | 64.8 |
| Comparative example eight | 17.4 | 93.4 |
| Comparative example No. nine | 8.4 | 83.1 |
| Comparative example ten | 4.5 | 56.4 |
| Comparative example eleven | 4.3 | 50.8 |
| Comparative example twelve | 5.7 | 60.3 |
| Comparative example thirteen | 12.6 | 63.4 |
| Comparative example fourteen | 6.5 | 68.9 |
| Comparative example fifteen | 5.4 | 68.3 |
| Comparative example sixteen | 7.8 | 57.4 |
The test result shows that the sulfur content of the gasoline obtained by the desulfurization process in the patent is below 5 mug/g, the yield exceeds 65%, and compared with the gasoline in a comparative example, the gasoline has the characteristics of low sulfur content, high gasoline yield and the like.
While the foregoing description shows and describes the preferred embodiments of the present invention, it is to be understood that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. The multistage extraction desulfurization method for hydrogenated gasoline is characterized by comprising the following steps of:
the method comprises the following steps: slowly putting 100 parts by weight of gasoline with the sulfur content of 25-30 mu g/g, 10 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 50 parts by weight of deionized water into a reaction kettle after hydrotreating;
step two: uniformly stirring, controlling the temperature of the mixed liquid in the reaction kettle at 25 ℃, controlling the stirring speed at 400-500 r/min, stopping stirring after 20-30 min, allowing the liquid in the reaction kettle to stand at 25 ℃ for 30-60 min under normal pressure environment to separate the liquid into an upper layer and a lower layer, and discharging the solvent at the middle lower layer of the reaction kettle to obtain the primary extraction desulfurized gasoline;
step three: adding 10-15 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate and 80-100 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain secondary desulfurized gasoline;
step four: adding 5-7 parts by weight of 1-heptyl pyridine trifluoromethanesulfonate solution and 30-50 parts by weight of deionized water into the reaction kettle, and repeating the second step to obtain third desulfurized gasoline;
step five: adding 30-50 parts by weight of deionized water into a reaction kettle, stirring and washing with water at a stirring speed of 600-800 r/min for 10-20 min, standing for 20-30 min to separate the liquid into an upper layer and a lower layer, and removing the solvent residue on the lower layer to obtain the required gasoline with the sulfur content of below 5 mug/g.
2. The method of claim 1, wherein the stirring speed in the reaction kettle in the second step is 500r/min, and the stirring time is 20 min.
3. The method of claim 1, wherein the 1-heptylpyridine trifluoromethanesulfonate is added in an amount of 15 parts by weight and the deionized water is added in an amount of 100 parts by weight in step three.
4. The method of claim 1, wherein the 1-heptylpyridine trifluoromethanesulfonate is added in an amount of 5 parts by weight and the deionized water is added in an amount of 30 parts by weight in step four.
5. The method for multi-stage extraction desulfurization of hydrogenated gasoline according to claim 1, wherein the amount of deionized water added in step five is 50 parts by weight, the stirring rate is 800r/min, the stirring time is 20min, and the standing time is 30 min.
6. The method for multi-stage extraction desulfurization of hydrogenated gasoline according to claim 1, wherein the lower solvent discharged from the reaction kettle in the second step is distilled and added with NaOH solution to adjust the pH value to 7-8, and the obtained solution is used as a recycling extractant in the first step and the second step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910177734.XA CN109749773B (en) | 2019-03-10 | 2019-03-10 | Multi-stage extraction desulfurization method for hydrogenated gasoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910177734.XA CN109749773B (en) | 2019-03-10 | 2019-03-10 | Multi-stage extraction desulfurization method for hydrogenated gasoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109749773A CN109749773A (en) | 2019-05-14 |
| CN109749773B true CN109749773B (en) | 2020-10-02 |
Family
ID=66407023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910177734.XA Active CN109749773B (en) | 2019-03-10 | 2019-03-10 | Multi-stage extraction desulfurization method for hydrogenated gasoline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109749773B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602348A (en) * | 2013-10-17 | 2014-02-26 | 上海交通大学 | Gasoline extraction-reduction desulphurization method |
| CN105733656A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | FCC gasoline oxidizing desulfurization method with composite acidic ionic liquid |
-
2019
- 2019-03-10 CN CN201910177734.XA patent/CN109749773B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602348A (en) * | 2013-10-17 | 2014-02-26 | 上海交通大学 | Gasoline extraction-reduction desulphurization method |
| CN105733656A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | FCC gasoline oxidizing desulfurization method with composite acidic ionic liquid |
Non-Patent Citations (1)
| Title |
|---|
| 离子液体的制备、表征以及在催化燃油脱硫中的应用;王亚楠;《中国优秀博士学位论文全文数据库》;20120115(第1期);第B016-24页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109749773A (en) | 2019-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101412928B (en) | Hydro-desulphurizing combined method | |
| CN105542849A (en) | Method for producing clean diesel oil and light aromatic hydrocarbons from inferior diesel oil | |
| CN103865577A (en) | Method for producing light arene product and clean fuel oil product from catalytic cracking diesel oil | |
| CN105296001A (en) | System for preparing aromatic hydrocarbons through hydrogenation catalytic reforming of coal tar and method | |
| CN102851073B (en) | Medium and low temperature combination processing method of coal tar | |
| CN1173012C (en) | Method of desulfurizing and dearomatizing diesel oil deeply | |
| CN109749773B (en) | Multi-stage extraction desulfurization method for hydrogenated gasoline | |
| CN103695032B (en) | A kind of method for modifying of heavy diesel | |
| CN100404646C (en) | Method for modifying poor-quality diesel-oil by cut fraction | |
| CN106701172A (en) | Hydrotreatment method for residual oil | |
| CN103361111A (en) | Catalyst sulfurization method of gasoline hydrotreating technique | |
| CN101412926B (en) | Hydro-upgrading combined method | |
| CN103059955B (en) | Method for producing clean gasoline from catalytic cracking gasoline | |
| CN103468311B (en) | A kind of method of producing low-sulphur oil | |
| CN102465014B (en) | Hydrocracking method for processing low-sulfur raw material | |
| CN105772113B (en) | A kind of additive for recovering activity of hydrocatalyst | |
| CN103740406A (en) | Extraction-hydrogenation combined process for producing low-sulfur-content gasoline | |
| CN101003747A (en) | Method for controlling concentration of sulfureted hydrogen in circulating hydrogen of hydrogenation unit | |
| CN103740405B (en) | Alkali cleaning-extraction-hydrogenation combined process for producing low-sulfur-content gasoline | |
| CN103740407B (en) | Alkali cleaning-extraction-washing-hydrogenation combined process for producing low-sulfur-content gasoline | |
| CN103059951B (en) | Catalytic cracking and catalytic gasoline hydrogenation combined technological method | |
| CN103695033B (en) | A kind of method improving cetane number of inferior diesel oil | |
| CN103087770A (en) | Clean gasoline production method through selective hydrogenation and desulfurization of catalytic gasoline | |
| CN103725323A (en) | Deodorization-extraction-washing-hydrogenation combined technology for producing low-sulfur gasoline | |
| CN111378503B (en) | Method for producing clean gasoline by catalytically cracking gasoline |
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 |