CN107794076B - Method and device for separating refined mixed aromatic hydrocarbon containing hydrogen sulfide - Google Patents
Method and device for separating refined mixed aromatic hydrocarbon containing hydrogen sulfide Download PDFInfo
- Publication number
- CN107794076B CN107794076B CN201711029745.0A CN201711029745A CN107794076B CN 107794076 B CN107794076 B CN 107794076B CN 201711029745 A CN201711029745 A CN 201711029745A CN 107794076 B CN107794076 B CN 107794076B
- Authority
- CN
- China
- Prior art keywords
- tower
- mixed
- aromatic hydrocarbon
- narrow
- fraction
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G7/00—Distillation of hydrocarbon oils
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the technical field of stripping desulfurization of hydrogenation products of ethylene pyrolysis fuel oil, in particular to a method and a device for separating refined mixed aromatic hydrocarbon containing hydrogen sulfide. The desulfurization rectifying tower provided by the invention has the advantages that the desulfurization effect is good, the equipment investment (a reflux pump and a tower top distillation line are reduced), the equipment occupation area and the production investment are reduced, and the narrow fraction separating tower provided by the invention can be used for obtaining the 1# narrow fraction, the 2# narrow fraction, the 3# narrow fraction and the 4# narrow fraction with narrower distillation range width by additionally arranging the narrow fraction separating tower, so that the equipment investment of a production device is small, the energy consumption is correspondingly reduced, the sewage discharge is reduced, the production effect is better, and the operation flexibility is strong.
Description
Technical Field
The invention relates to the technical field of ethylene pyrolysis fuel oil hydrogenation product treatment and desulfurization, in particular to a method and a device for separating refined mixed aromatic hydrocarbon containing hydrogen sulfide.
Background
At present, the quality standard of aromatic hydrocarbon products is developed towards ultra-low sulfur and clean. Separating ethylene cracking fuel oil to obtain light distillate, two-stage hydrogenation to obtain refined mixed aromatic hydrocarbon, and converting organic sulfur in the raw material into inorganic sulfur in the hydrogenation process. The conventional process flow at present has the following problems: organic sulfur contained in light component oil in ethylene pyrolysis fuel oil is converted into hydrogen sulfide in the hydrogenation process, so that sulfur content in refined mixed aromatic hydrocarbon is high; if the refined mixed aromatic hydrocarbon is directly subjected to rectification separation, the obtained multiple narrow-fraction solvent oil has higher sulfur content, and meanwhile, the conventional method for removing hydrogen sulfide is steam direct stripping to remove hydrogen sulfide gas. However, this method produces a large amount of sewage and avoids the situation of product water. If the prior art is adopted to further separate the refined mixed aromatic hydrocarbon to obtain solvent oil with multiple brands, the conventional process method is shown in fig. 1, and a set of rectifying tower systems 1 are respectively arranged after the mixed trimethylbenzene and the mixed tetramethylbenzene to continuously and finely separate the mixed trimethylbenzene and the mixed tetramethylbenzene, so that the number of production equipment, investment, energy consumption and the like are increased.
Disclosure of Invention
The invention provides a method and a device for separating refined mixed aromatic hydrocarbon containing hydrogen sulfide, which overcome the defects of the prior art, and can effectively solve the problems that the number of production equipment, investment, energy consumption and the like are increased due to the fact that the refined mixed aromatic hydrocarbon obtained by two-stage hydrogenation of conventional ethylene cracking fuel oil is directly distributed into each narrow fraction product after not being desulfurized, the high additional value utilization of the product is affected, and the prior art is adopted to further separate the refined mixed aromatic hydrocarbon to obtain multiple brands of narrow fractions.
One of the technical schemes of the invention is realized by the following measures: a method for separating refined mixed aromatic hydrocarbon containing hydrogen sulfide comprises the following steps: firstly, preheating refined mixed aromatic hydrocarbon containing hydrogen sulfide to 200-220 ℃, and then sending the mixed aromatic hydrocarbon into a desulfurization rectifying tower for desulfurization; second step, desulfurization stage: the method comprises the steps that refined mixed aromatic hydrocarbon containing hydrogen sulfide is heated by a tower bottom reboiler and then flows back into a desulfurization rectifying tower, hydrogen sulfide in the refined mixed aromatic hydrocarbon containing hydrogen sulfide after being heated by the tower bottom reboiler escapes, the mixture rises to the tower top, condensate after being condensed by a tower top condenser falls back into the desulfurization rectifying tower above a partition plate in the tower top of the desulfurization rectifying tower, no condensed hydrogen sulfide is discharged through a hydrogen sulfide gas discharge pipeline and falls back into condensate above the partition plate in the tower top of the desulfurization rectifying tower, the condensate is firstly discharged into a reflux tank through a material reflux discharge pipeline communicated with the upper part of the partition plate in the tower top of the desulfurization rectifying tower, then flows back into the desulfurization rectifying tower through a material reflux pipeline communicated with the lower part of the partition plate in the tower top of the desulfurization rectifying tower, the mixture continuously participates in a desulfurization stage of the refined mixed aromatic hydrocarbon containing hydrogen sulfide, and the operation pressure of the desulfurization rectifying tower in the desulfurization stage is 0.1MPa to 0.6MPa, the temperature is 130 ℃ to 160 ℃, and the temperature of the tower bottom in the tower bottom is 230 ℃ to 260 ℃; thirdly, when the content of hydrogen sulfide in the refined mixed aromatic hydrocarbon is lower than 10ppm, discharging the refined mixed aromatic hydrocarbon from a discharging pipeline of the refined mixed aromatic hydrocarbon, then feeding the refined mixed aromatic hydrocarbon into a mixed aromatic hydrocarbon separating tower for rectification separation of mixed xylene, mixed trimethylbenzene, mixed tetramethylbenzene and slurry oil, discharging the mixed xylene from the top of the mixed aromatic hydrocarbon separating tower, discharging the slurry oil from the bottom of the mixed aromatic hydrocarbon separating tower, and discharging the mixed trimethylbenzene and the mixed tetramethylbenzene from the side line of the tower body of the mixed aromatic hydrocarbon separating tower respectively, wherein the temperature of the top of the mixed aromatic hydrocarbon separating tower is 145-185 ℃, the pressure of the top of the mixed aromatic hydrocarbon separating tower is 0.08-0.1 MPa, the temperature of the bottom of the tower is 214-254 ℃, the pressure of the bottom of the tower is 0.11-0.13 MPa, and the reflux ratio is 3-7; fourth, when mixed trimethylbenzene is required to be further separated, the mixed trimethylbenzene is sent to a narrow-fraction separation tower to be subjected to rectification separation, mixed xylenes are discharged from the top of the narrow-fraction separation tower, 1# narrow fractions with the distillation range of 153-175 ℃ are extracted from the side line of the narrow-fraction separation tower, 2# narrow fractions with the distillation range of 174-199 ℃ are collected from the bottom of the narrow-fraction separation tower, when mixed tetramethylbenzene is required to be further separated, mixed tetramethylbenzene is sent to the narrow-fraction separation tower to be subjected to rectification separation, mixed trimethylbenzene is discharged from the top of the narrow-fraction separation tower after rectification separation, 3# narrow fractions with the distillation range of 161-191 ℃ are extracted from the side line of the narrow-fraction separation tower, 4# narrow fractions with the distillation range of 192-210 ℃ are collected from the bottom of the narrow-fraction separation tower, and in the step, the top temperature of the narrow-fraction separation tower is 160-200 ℃, the top pressure of 0.08-0.1 MPa, the bottom temperature of 190-230 ℃ and the bottom pressure of 0.11-0.13 MPa reflux ratio of 2-5.
The following are further optimizations and/or improvements to one of the above-described inventive solutions:
the mixed xylene is a fraction with a distillation range of not more than 160 ℃, the mixed trimethylbenzene is a fraction with a distillation range of 145 ℃ to 185 ℃, and the mixed tetramethylbenzene is a fraction with a distillation range of 155 ℃ to 205 ℃.
The desulfurization rectifying tower is a conventional plate type rectifying tower, a baffle plate similar to a Z shape is arranged in the top of the desulfurization rectifying tower, a shell-and-tube condenser is arranged on the outer side of the top of the tower and used as a top condenser, a hydrogen sulfide-rich gas condensing pipeline is communicated between the desulfurization rectifying tower below the baffle plate and a heat source inlet of the top condenser, a shell pass of the shell-and-tube condenser is communicated with the inside of the desulfurization rectifying tower above the baffle plate, a hydrogen sulfide gas discharging pipeline is communicated on the desulfurization rectifying tower above the baffle plate, a material backflow discharging pipeline is communicated on the desulfurization rectifying tower above the baffle plate at the lowest position of the baffle plate, a material backflow returning pipeline is communicated on the desulfurization rectifying tower below the baffle plate at the lowest position of the baffle plate, and the outlet end of the material backflow discharging pipeline and the inlet end of the material backflow returning pipeline are both communicated with the top of the backflow tank, wherein the top of the backflow tank is lower than the horizontal position at the lowest position of the baffle plate.
The mixed aromatic hydrocarbon separating tower is followed by a narrow fraction separating tower, the narrow fraction separating tower is a conventional plate type rectifying tower, 60 trays are arranged in the conventional plate type rectifying tower, and the position of the 40 th tray in the conventional plate type rectifying tower from bottom to top is the side line extraction position of the 1# narrow fraction and the 3# narrow fraction.
The method for separating the refined mixed aromatic hydrocarbon containing hydrogen sulfide is realized based on a desulfurization separation device for the refined mixed aromatic hydrocarbon containing hydrogen sulfide, the desulfurization separation device for the refined mixed aromatic hydrocarbon containing hydrogen sulfide comprises a desulfurization rectifying tower, a mixed aromatic hydrocarbon separation tower and a narrow fraction separation tower, wherein the middle part of the desulfurization rectifying tower is communicated with a feeding side line, the lower end of the desulfurization rectifying tower is communicated with a refined mixed aromatic hydrocarbon discharging pipeline, the bottom of the desulfurization rectifying tower is provided with a reboiler, a cold flow channel of the reboiler is communicated with the inside of the desulfurization rectifying tower, a hot flow channel of the reboiler is communicated with a steam pipeline, a feeding heat exchanger is connected in series with the feeding side line, and the hot flow channel of the feeding heat exchanger is communicated with the steam pipeline; the refined mixed aromatic hydrocarbon discharging pipeline is communicated with a material inlet of the mixed aromatic hydrocarbon separating tower, a 1# side line and a 2# side line are respectively communicated with a tower body of the mixed aromatic hydrocarbon separating tower, the 1# side line is communicated with the material inlet of the narrow-fraction separating tower through a mixed trimethylbenzene feeding pipe, the 2# side line is communicated with the material inlet of the narrow-fraction separating tower through a mixed tetramethylbenzene feeding pipe, a mixed xylene/mixed trimethylbenzene discharging pipeline is communicated with the tower top of the narrow-fraction separating tower, a 2#/4# narrow-fraction discharging pipeline is communicated with the tower bottom of the narrow-fraction separating tower, a 1#/3# narrow-fraction discharging side line is communicated with the tower body of the narrow-fraction separating tower, and control valves are respectively connected with the mixed trimethylbenzene feeding pipe and the mixed tetramethylbenzene feeding pipe in series.
The top of the mixed aromatic separation tower is communicated with a mixed xylene discharge pipeline, and the bottom of the mixed aromatic separation tower is communicated with an oil slurry discharge pipeline.
The second technical scheme of the invention is realized by the following measures: the device for desulfurizing and separating the refined mixed aromatic hydrocarbon containing hydrogen sulfide comprises a desulfurizing and rectifying tower, a mixed aromatic hydrocarbon separating tower and a narrow fraction separating tower, wherein the narrow fraction separating tower is connected behind the mixed aromatic hydrocarbon separating tower, the middle part of the desulfurizing and rectifying tower is communicated with a feeding side line, the lower end of the desulfurizing and rectifying tower is communicated with a discharging pipeline of the refined mixed aromatic hydrocarbon, the bottom of the desulfurizing and rectifying tower is provided with a reboiler, a cold flow channel of the reboiler is communicated with the inside of the desulfurizing and rectifying tower, a steam pipeline is communicated with a hot flow channel of the reboiler, a feeding heat exchanger is connected in series with the feeding side line, and a steam pipeline is communicated with a hot flow channel of the feeding heat exchanger; the refined mixed aromatic hydrocarbon discharging pipeline is communicated with a material inlet of the mixed aromatic hydrocarbon separating tower, a 1# side line and a 2# side line are respectively communicated with a tower body of the mixed aromatic hydrocarbon separating tower, the 1# side line is communicated with the material inlet of the narrow-fraction separating tower through a mixed trimethylbenzene feeding pipe, the 2# side line is communicated with the material inlet of the narrow-fraction separating tower through a mixed tetramethylbenzene feeding pipe, a mixed xylene/mixed trimethylbenzene discharging pipeline is communicated with the tower top of the narrow-fraction separating tower, a 2#/4# narrow-fraction discharging pipeline is communicated with the tower bottom of the narrow-fraction separating tower, a 1#/3# narrow-fraction discharging side line is communicated with the tower body of the narrow-fraction separating tower, and control valves are respectively connected with the mixed trimethylbenzene feeding pipe and the mixed tetramethylbenzene feeding pipe in series.
The following is a further optimization and/or improvement of the second technical scheme of the invention:
the desulfurization rectifying tower is a conventional plate type rectifying tower, a baffle plate similar to a Z shape is arranged in the top of the desulfurization rectifying tower, a shell-and-tube condenser is arranged on the outer side of the top of the tower and used as a top condenser, a hydrogen sulfide-rich gas condensing pipeline is communicated between the desulfurization rectifying tower below the baffle plate and a heat source inlet of the top condenser, a shell pass of the shell-and-tube condenser is communicated with the inside of the desulfurization rectifying tower above the baffle plate, a hydrogen sulfide gas discharging pipeline is communicated on the desulfurization rectifying tower above the baffle plate, a material backflow discharging pipeline is communicated on the desulfurization rectifying tower above the baffle plate at the lowest position of the baffle plate, a material backflow returning pipeline is communicated on the desulfurization rectifying tower below the baffle plate at the lowest position of the baffle plate, and the outlet end of the material backflow discharging pipeline and the inlet end of the material backflow returning pipeline are both communicated with the top of the backflow tank, wherein the top of the backflow tank is lower than the horizontal position at the lowest position of the baffle plate.
The narrow fraction separating tower is a conventional plate type rectifying tower, 60 trays are arranged in the conventional plate type rectifying tower, and the position of a 40 th tray in the conventional plate type rectifying tower from bottom to top is a side line extraction position of a 1# narrow fraction and a 3# narrow fraction; or/and the tower top of the mixed aromatic separation tower is communicated with a mixed xylene discharge pipeline, and the tower bottom of the mixed aromatic separation tower is communicated with an oil slurry discharge pipeline.
The invention obtains the desulfurizing rectifying tower suitable for the invention on the basis of improving the existing plate rectifying tower, adopts the desulfurizing rectifying tower to carry out desulfurization, has good desulfurizing effect, reduces equipment input amount (wherein a reflux pump and a tower top distillation line are reduced), reduces equipment occupied area and production input, obtains the narrow fraction separating tower suitable for the invention on the basis of improving the existing plate rectifying tower, can obtain the 1# narrow fraction, the 2# narrow fraction, the 3# narrow fraction and the 4# narrow fraction with narrower distillation range width by adopting one narrow fraction separating tower, has less equipment input amount of a production device, correspondingly reduces the energy consumption, reduces sewage discharge, has better production effect and strong operation flexibility.
Drawings
FIG. 1 is a block diagram of a prior art process for refining mixed aromatics.
FIG. 2 is a schematic diagram of the process flow of the present invention.
FIG. 3 is a schematic diagram of the structure of the inside of the top of the desulfurizing and rectifying tower in the present invention.
The codes in the drawings are respectively: 1 is a rectifying tower system, 2 is a desulfurization rectifying tower, 3 is a reboiler, 4 is a tower top condenser, 5 is a baffle, 6 is a hydrogen sulfide gas discharge pipeline, 7 is a material backflow discharge pipeline, 8 is a backflow tank, 9 is a material backflow return pipeline, 10 is a refined mixed aromatic hydrocarbon discharge pipeline, 11 is a mixed aromatic hydrocarbon separating tower, 12 is a narrow-fraction separating tower, 13 is a feeding side line, 14 is a steam pipeline, 15 is a feeding heat exchanger, 16 is a 1# side line, 17 is a 2# side line, 18 is a mixed trimethylbenzene feed pipe, 19 is a mixed tetramethylbenzene feed pipe, 20 is a mixed xylene/mixed trimethylbenzene discharge pipeline, 21 is a 2#/4# narrow-fraction discharge pipeline, 22 is a 1#/3# narrow-fraction discharge side line, 23 is a control valve, 24 is a mixed xylene discharge pipeline, 25 is an oil slurry discharge pipeline, and 26 is a hydrogen sulfide rich gas condensation pipeline.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments can be determined according to the technical scheme and practical situations of the present invention. The percentages in the invention are mass percentages unless otherwise specified.
The invention is further described below with reference to examples and figures:
example 1 as shown in fig. 2, the method for separating refined mixed aromatic hydrocarbon containing hydrogen sulfide is carried out according to the following steps: firstly, preheating refined mixed aromatic hydrocarbon containing hydrogen sulfide to 200-220 ℃, and then sending the mixed aromatic hydrocarbon into a desulfurization rectifying tower 2 for desulfurization; second step, desulfurization stage: the refined mixed aromatic hydrocarbon containing hydrogen sulfide flows back into the desulfurization rectifying tower 2 after being heated by the reboiler 3 at the bottom of the tower, hydrogen sulfide in the refined mixed aromatic hydrocarbon containing hydrogen sulfide flows out and rises to the top of the tower after being heated by the reboiler 3 at the bottom of the tower, condensed condensate after being condensed by the condenser 4 at the top of the tower falls back into the desulfurization rectifying tower 2 above the baffle plate 5 in the top of the desulfurization rectifying tower 2, hydrogen sulfide gas which is not condensed is discharged through the hydrogen sulfide gas discharge pipeline 6 and falls back into the condensate above the baffle plate 5 in the top of the desulfurization rectifying tower 2, the condensate is firstly discharged into the reflux tank 8 through the material reflux discharge pipeline 7 communicated with the upper part of the baffle plate 5 in the top of the desulfurization rectifying tower 2, and then flows back into the desulfurization rectifying tower 2 through the material reflux return pipeline 9 communicated with the lower part of the baffle plate 5 in the top of the desulfurization rectifying tower 2, the operation pressure of the desulfurization rectifying tower 2 is 0.1MPa to 0.6MPa, the temperature of the top of the tower is 130 ℃ to 160 ℃, and the temperature of the bottom of the tower is 230 ℃ to 260 ℃ in the stage of the desulfurization rectifying tower 2; thirdly, when the content of hydrogen sulfide in the refined mixed aromatic hydrocarbon is lower than 10ppm, the refined mixed aromatic hydrocarbon is discharged from a refined mixed aromatic hydrocarbon discharge pipeline 10 and enters a mixed aromatic hydrocarbon separation tower 11 to carry out rectification separation of mixed xylene, mixed trimethylbenzene, mixed tetramethylbenzene and slurry oil, after rectification separation, the mixed xylene is discharged from the top of the mixed aromatic hydrocarbon separation tower 11, the slurry oil is discharged from the bottom of the mixed aromatic hydrocarbon separation tower 11, the mixed trimethylbenzene and the mixed tetramethylbenzene are respectively discharged from the side line of the tower body of the mixed aromatic hydrocarbon separation tower 11, the temperature of the top of the mixed aromatic hydrocarbon separation tower 11 is 145-185 ℃, the pressure of the top of the tower is 0.08-0.1 MPa, the temperature of the bottom of the tower is 214-254 ℃, the pressure of the bottom of the tower is 0.11-0.13 MPa, and the reflux ratio is 3-7; fourth, when the mixed trimethylbenzene is required to be further separated, the mixed trimethylbenzene is sent to a narrow-fraction separation tower 12 to be subjected to rectification separation, mixed xylenes are discharged from the top of the narrow-fraction separation tower 12 after rectification separation, 1# narrow fraction with the distillation range of 153 ℃ to 175 ℃ is extracted from the side line of the narrow- fraction separation tower 12, 2# narrow fraction with the distillation range of 174 ℃ to 199 ℃ is collected from the bottom of the narrow-fraction separation tower 12, when the mixed tetramethylbenzene is required to be further separated, the mixed tetramethylbenzene is sent to the narrow-fraction separation tower 12 to be subjected to rectification separation, 3# narrow fraction with the distillation range of 161 ℃ to 191 ℃ is discharged from the top of the narrow-fraction separation tower 12 after rectification separation, 4# narrow fraction with the distillation range of 192 ℃ to 210 ℃ is collected from the bottom of the narrow-fraction separation tower 12, and in this step, the top temperature of the narrow-fraction separation tower 12 is 160 ℃ to 200 ℃ and the pressure of 0.08MPa to 0.1MPa, the bottom temperature of 190 ℃ to the pressure of 0.11MPa to 0.11MPa, and the reflux ratio of the bottom of the narrow-fraction is 2.11 MPa.
The sulfur content in the refined mixed aromatic hydrocarbon obtained after desulfurization by the method and the device is obviously reduced, the mixed aromatic hydrocarbon separation tower 11 is a conventional rectifying tower in the prior art, mixed xylene, mixed trimethylbenzene, mixed tetramethylbenzene and slurry oil are separated after the desulfurized refined mixed aromatic hydrocarbon is separated by the mixed aromatic hydrocarbon separation tower 11, the method and the device are the prior art, a narrow fraction separation tower 12 is additionally arranged after the mixed aromatic hydrocarbon separation tower 11, the mixed trimethylbenzene and the mixed tetramethylbenzene separated by the mixed aromatic hydrocarbon separation tower 11 are further subjected to precise rectifying separation, and the obtained 1# narrow fraction, 2# narrow fraction, 3# narrow fraction and 4# narrow fraction with narrower distillation range width can be respectively obtained, and the obtained 1# narrow fraction, 2# narrow fraction, 3# narrow fraction and 4# narrow fraction have the distillation range width of 20 ℃ to 30 ℃; the mixed trimethylbenzene and the mixed tetramethylbenzene separated by the mixed aromatic separation tower 11 can be selectively subjected to further precise rectification separation by the narrow-fraction separation tower 12 according to production requirements, and can also not enter the narrow-fraction separation tower 12 to be subjected to further precise rectification separation according to production requirements, so that the operation flexibility is high, the sulfur content in various narrow-fraction solvent oils obtained after the subsequent rectification separation is obviously reduced, the low-sulfur solvent oil capable of meeting market requirements is obtained, and the solvent oil can also meet new standards of national IV gasoline when being used as a gasoline blending component.
Example 2 as an optimization of the above example, according to actual needs, xylene was mixed as a fraction having a distillation range of not more than 160 ℃, trimethylbenzene was mixed as a fraction having a distillation range of 145 to 185 ℃, and tetramethylbenzene was mixed as a fraction having a distillation range of 155 to 205 ℃.
The invention obtains the narrow fraction separating tower 12 suitable for the invention on the basis of improving the existing plate type rectifying tower, and the 1# narrow fraction, the 2# narrow fraction, the 3# narrow fraction and the 4# narrow fraction with narrower distillation range width can be obtained by adopting one narrow fraction separating tower 12, so that the investment of production equipment is small, the energy consumption is correspondingly reduced, the sewage discharge is reduced, and the production effect is better.
In example 4, as shown in fig. 3, as an optimization of the above example, the desulfurizing rectifying tower 2 is a conventional plate rectifying tower, a baffle 5 similar to a zigzag shape is arranged in the top of the desulfurizing rectifying tower 2, a shell-and-tube condenser is arranged outside the top of the tower as the tower top condenser 4, a hydrogen sulfide-rich gas condensing pipeline 26 is communicated between the desulfurizing rectifying tower 2 below the baffle 5 and the heat source inlet of the tower top condenser 4, the shell side of the shell-and-tube condenser is communicated with the inside of the desulfurizing rectifying tower 2 above the baffle 5, a hydrogen sulfide gas discharging pipeline 6 is communicated with the desulfurizing rectifying tower 2 above the baffle 5, a material reflux discharging pipeline 7 is communicated with the desulfurizing rectifying tower 2 above the baffle 5 at the lowest position of the baffle 5, a material reflux return pipeline 9 is communicated with the desulfurizing rectifying tower 2 below the baffle 5, and the outlet end of the material reflux discharging pipeline 7 and the inlet end of the material reflux return pipeline 9 are both communicated with the top of the reflux tank 8, and the top of the reflux tank 8 is lower than the lowest position of the baffle 5. The baffle 5 in the top of the desulfurizing and rectifying tower 2 adopts a similar Z shape, when condensate condensed by the shell-and-tube condenser of the desulfurizing and rectifying tower 2 falls back to the baffle 5, the liquid flows downwards under the action of gravity, so that condensate can be ensured to be fully collected at the lowest position of the similar Z-shaped baffle 5, the condensate at the position is discharged into the reflux tank 8 through the material reflux discharge pipeline 7 and then flows back into the desulfurizing and rectifying tower 2 through the material reflux return pipeline 9, thus acid hydrogen sulfide above the baffle 5 can be effectively prevented from flowing back into the desulfurizing and rectifying tower 2, and the treatment burden in the desulfurizing and rectifying tower 2 is increased; the top of the reflux tank 8 is lower than the lowest horizontal position of the baffle plate 5, so that the arrangement of a reflux pump can be omitted, and the reflux can be carried out into the desulfurization rectifying tower 2 by means of the characteristic of liquid.
The invention obtains the desulfurization rectifying tower 2 suitable for the invention on the basis of improving the existing plate rectifying tower, and the desulfurization rectifying tower 2 is adopted for desulfurization, so that not only is the desulfurization effect good, but also the equipment input quantity (wherein a reflux pump and a tower top rectifying line are reduced) is reduced, and the equipment occupation area and the production input are reduced.
Example 5 as an optimization of the above example, the narrow cut separation column 12 was a conventional plate type rectifying column in which 60 trays were arranged, and the 40 th tray position from bottom to top in the conventional plate type rectifying column was the side draw position of the 1# narrow cut and the 3# narrow cut, according to actual needs.
Example 6 as shown in fig. 2, as an optimization of the above example, the top of the mixed aromatic separation column 11 is connected with a mixed xylene discharge line 24, and the bottom of the mixed aromatic separation column 11 is connected with an slurry oil discharge line 25.
The method for carrying out the separation of the purified mixed aromatic hydrocarbon by using the mixed aromatic hydrocarbon separation column 11 and the narrow fraction separation column 12 is specifically referred to as follows: the refined mixed aromatic hydrocarbon enters a mixed aromatic hydrocarbon separating tower 11 from a mixed aromatic hydrocarbon refining mixed aromatic hydrocarbon discharging pipeline 10 to carry out rectification separation on mixed xylene, mixed trimethylbenzene, mixed tetramethylbenzene and slurry oil, the separated mixed xylene is discharged through a mixed xylene discharging pipeline 24, the separated mixed trimethylbenzene is discharged through a 1# side line 16, the separated mixed tetramethylbenzene is discharged through a 2# side line 17, and the separated slurry oil is discharged through a slurry oil discharging pipeline 25; when the mixed trimethylbenzene is required to be further separated, a control valve 23 on a mixed tetramethylbenzene feeding pipe 19 is closed, the mixed trimethylbenzene is fed into a narrow fraction separation tower 12 through a 1# side line 16 and a mixed trimethylbenzene feeding pipe 18 for rectification separation, the separated mixed xylenes are collected through a mixed xylenes/mixed trimethylbenzene discharge pipeline 20, a 1# narrow fraction is collected through a 1#/3# narrow fraction discharge side line 22, and a 2# narrow fraction is collected through a 2#/4# narrow fraction discharge pipeline 21; when further separation of mixed tetramethylbenzene is required, a control valve 23 on a mixed tetramethylbenzene feed pipe 18 is closed, mixed tetramethylbenzene is fed into a narrow fraction separation tower 12 through a No. 2 side line 17 and a mixed tetramethylbenzene feed pipe 19 for rectification separation, separated mixed trimethylbenzene is collected through a mixed xylene/mixed trimethylbenzene discharge line 20, a No. 3 narrow fraction is collected through a No. 1/No. 3 narrow fraction discharge side line 22, and a No. 4 narrow fraction is collected through a No. 2/No. 4 narrow fraction discharge line 21.
The sulfur content in the various brands of narrow-fraction mixed aromatic hydrocarbon solvent oil obtained by separating the refined mixed aromatic hydrocarbon by the mixed aromatic hydrocarbon separating tower 11 and the narrow-fraction separating tower 12 is greatly reduced after the refining mixed aromatic hydrocarbon is transformed by the technology, the sulfur content in the mixed-fraction mixed aromatic hydrocarbon solvent oil is reduced from 300ppm before transformation to 10ppm after transformation, the mixed trimethylbenzene is reduced from 30ppm before transformation to less than or equal to 10ppm after transformation, the mixed tetramethylbenzene is reduced from 30ppm before transformation to less than or equal to 10ppm after transformation, and the sulfur content in the narrow-fraction solvent oil with various brands can be effectively reduced by adopting the technology.
It is known that the desulfurizing rectifying tower 2 suitable for the present invention is obtained on the basis of improving the existing plate rectifying tower, the desulfurizing rectifying tower 2 is adopted to perform desulfurization, so that not only is the desulfurizing effect good, but also the equipment input amount (wherein a reflux pump and a tower top rectifying line are reduced), the equipment occupation area and the production input are reduced, and the narrow fraction separating tower 12 suitable for the present invention is obtained on the basis of improving the existing plate rectifying tower, and the narrow fraction 1# narrow fraction, the narrow fraction 2# narrow fraction, the narrow fraction 3# and the narrow fraction 4# with narrower distillation range width can be obtained by adopting one narrow fraction separating tower 12, so that the equipment input amount of the production device is small, the energy consumption is correspondingly reduced, the sewage discharge is reduced, the production effect is better, and the operation flexibility is strong.
The technical characteristics form the embodiment of the invention, have stronger adaptability and implementation effect, and can increase or decrease unnecessary technical characteristics according to actual needs so as to meet the requirements of different situations.
Claims (7)
1. The method for separating the refined mixed aromatic hydrocarbon containing the hydrogen sulfide is characterized by comprising the following steps of: firstly, preheating refined mixed aromatic hydrocarbon containing hydrogen sulfide to 200-220 ℃, and then sending the mixed aromatic hydrocarbon into a desulfurization rectifying tower for desulfurization; second step, desulfurization stage: the method comprises the steps that refined mixed aromatic hydrocarbon containing hydrogen sulfide is heated by a tower bottom reboiler and then flows back into a desulfurization rectifying tower, hydrogen sulfide in the refined mixed aromatic hydrocarbon containing hydrogen sulfide after being heated by the tower bottom reboiler escapes, the mixture rises to the tower top, condensate after being condensed by a tower top condenser falls back into the desulfurization rectifying tower above a partition plate in the tower top of the desulfurization rectifying tower, no condensed hydrogen sulfide is discharged through a hydrogen sulfide gas discharge pipeline and falls back into condensate above the partition plate in the tower top of the desulfurization rectifying tower, the condensate is firstly discharged into a reflux tank through a material reflux discharge pipeline communicated with the upper part of the partition plate in the tower top of the desulfurization rectifying tower, then flows back into the desulfurization rectifying tower through a material reflux pipeline communicated with the lower part of the partition plate in the tower top of the desulfurization rectifying tower, the mixture continuously participates in a desulfurization stage of the refined mixed aromatic hydrocarbon containing hydrogen sulfide, and the operation pressure of the desulfurization rectifying tower in the desulfurization stage is 0.1MPa to 0.6MPa, the temperature is 130 ℃ to 160 ℃, and the temperature of the tower bottom in the tower bottom is 230 ℃ to 260 ℃; thirdly, when the content of hydrogen sulfide in the refined mixed aromatic hydrocarbon is lower than 10ppm, discharging the refined mixed aromatic hydrocarbon from a discharging pipeline of the refined mixed aromatic hydrocarbon, then feeding the refined mixed aromatic hydrocarbon into a mixed aromatic hydrocarbon separating tower for rectification separation of mixed xylene, mixed trimethylbenzene, mixed tetramethylbenzene and slurry oil, discharging the mixed xylene from the top of the mixed aromatic hydrocarbon separating tower, discharging the slurry oil from the bottom of the mixed aromatic hydrocarbon separating tower, and discharging the mixed trimethylbenzene and the mixed tetramethylbenzene from the side line of the tower body of the mixed aromatic hydrocarbon separating tower respectively, wherein the temperature of the top of the mixed aromatic hydrocarbon separating tower is 145-185 ℃, the pressure of the top of the mixed aromatic hydrocarbon separating tower is 0.08-0.1 MPa, the temperature of the bottom of the tower is 214-254 ℃, the pressure of the bottom of the tower is 0.11-0.13 MPa, and the reflux ratio is 3-7; fourth, when mixed trimethylbenzene is required to be further separated, the mixed trimethylbenzene is sent to a narrow-fraction separation tower to be subjected to rectification separation, mixed xylenes are discharged from the top of the narrow-fraction separation tower, 1# narrow fractions with the distillation range of 153-175 ℃ are extracted from the side line of the narrow-fraction separation tower, 2# narrow fractions with the distillation range of 174-199 ℃ are collected from the bottom of the narrow-fraction separation tower, when mixed tetramethylbenzene is required to be further separated, mixed tetramethylbenzene is sent to the narrow-fraction separation tower to be subjected to rectification separation, mixed trimethylbenzene is discharged from the top of the narrow-fraction separation tower after rectification separation, 3# narrow fractions with the distillation range of 161-191 ℃ are extracted from the side line of the narrow-fraction separation tower, 4# narrow fractions with the distillation range of 192-210 ℃ are collected from the bottom of the narrow-fraction separation tower, and in the step, the top temperature of the narrow-fraction separation tower is 160-200 ℃, the top pressure of 0.08-0.1 MPa, the bottom temperature of 190-230 ℃ and the bottom pressure of 0.11-0.13 MPa reflux ratio of 2-5.
2. The method for separating refined mixed aromatic hydrocarbon containing hydrogen sulfide according to claim 1, wherein mixed xylenes are fractions having a distillation range of not more than 160 ℃, mixed trimethylbenzene is a fraction having a distillation range of 145 ℃ to 185 ℃, and mixed tetramethylbenzene is a fraction having a distillation range of 155 ℃ to 205 ℃.
3. The method for separating hydrogen sulfide-containing refined mixed aromatic hydrocarbon according to claim 1 or 2, characterized in that the desulfurizing rectifying tower is a conventional plate rectifying tower, a baffle plate similar to a Z shape is arranged in the top of the desulfurizing rectifying tower, a shell-and-tube condenser is arranged outside the top of the tower to serve as a tower top condenser, a hydrogen sulfide-rich gas condensing pipeline is communicated between the desulfurizing rectifying tower below the baffle plate and a heat source inlet of the tower top condenser, a shell pass of the shell-and-tube condenser is communicated with the inside of the desulfurizing rectifying tower above the baffle plate, a hydrogen sulfide gas discharging pipeline is communicated with the desulfurizing rectifying tower above the baffle plate, a material reflux discharging pipeline is communicated with the desulfurizing rectifying tower above the baffle plate at the lowest position of the baffle plate, an outlet end of the material reflux discharging pipeline and an inlet end of the material reflux returning pipeline are both communicated with the top of a reflux tank, and the top of the reflux tank is lower than the horizontal position of the lowest position of the baffle plate.
4. The method for separating refined mixed aromatic hydrocarbon containing hydrogen sulfide according to claim 1 or 2, which is characterized in that a narrow fraction separating tower is connected behind the mixed aromatic hydrocarbon separating tower, the narrow fraction separating tower is a conventional plate type rectifying tower, 60 trays are arranged in the conventional plate type rectifying tower, and the position of the 40 th tray in the conventional plate type rectifying tower from bottom to top is a side line extraction position of a 1# narrow fraction and a 3# narrow fraction.
5. The method for separating refined mixed aromatic hydrocarbon containing hydrogen sulfide according to claim 3, wherein a narrow-fraction separating tower is connected behind the mixed aromatic hydrocarbon separating tower, the narrow-fraction separating tower is a conventional plate type rectifying tower, 60 trays are arranged in the conventional plate type rectifying tower, and the position of the 40 th tray in the conventional plate type rectifying tower from bottom to top is a side line extraction position of the 1# narrow fraction and the 3# narrow fraction.
6. The method for separating refined mixed aromatic hydrocarbon containing hydrogen sulfide according to claim 5, which is characterized in that the method for separating the refined mixed aromatic hydrocarbon containing hydrogen sulfide is realized based on a device for desulfurizing and separating the refined mixed aromatic hydrocarbon containing hydrogen sulfide, the device for desulfurizing and separating the refined mixed aromatic hydrocarbon containing hydrogen sulfide comprises a desulfurizing rectifying tower, a mixed aromatic hydrocarbon separating tower and a narrow fraction separating tower, the middle part of the desulfurizing rectifying tower is communicated with a feeding side line, the lower end of the desulfurizing rectifying tower is communicated with a refined mixed aromatic hydrocarbon discharging pipeline, the bottom of the desulfurizing rectifying tower is provided with a reboiler, a cold flow channel of the reboiler is communicated with the inside of the desulfurizing rectifying tower, a steam pipeline is communicated with a hot flow channel of the reboiler, a feeding heat exchanger is connected in series with the hot flow channel of the feeding heat exchanger; the refined mixed aromatic hydrocarbon discharging pipeline is communicated with a material inlet of the mixed aromatic hydrocarbon separating tower, a 1# side line and a 2# side line are respectively communicated with a tower body of the mixed aromatic hydrocarbon separating tower, the 1# side line is communicated with the material inlet of the narrow-fraction separating tower through a mixed trimethylbenzene feeding pipe, the 2# side line is communicated with the material inlet of the narrow-fraction separating tower through a mixed tetramethylbenzene feeding pipe, a mixed xylene/mixed trimethylbenzene discharging pipeline is communicated with the tower top of the narrow-fraction separating tower, a 2#/4# narrow-fraction discharging pipeline is communicated with the tower bottom of the narrow-fraction separating tower, a 1#/3# narrow-fraction discharging side line is communicated with the tower body of the narrow-fraction separating tower, and control valves are respectively connected with the mixed trimethylbenzene feeding pipe and the mixed tetramethylbenzene feeding pipe in series.
7. The method for separating refined mixed aromatic hydrocarbon containing hydrogen sulfide according to claim 6, wherein the top of the mixed aromatic hydrocarbon separating tower is connected with a mixed xylene discharge line, and the bottom of the mixed aromatic hydrocarbon separating tower is connected with an oil slurry discharge line.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711029745.0A CN107794076B (en) | 2017-10-27 | 2017-10-27 | Method and device for separating refined mixed aromatic hydrocarbon containing hydrogen sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711029745.0A CN107794076B (en) | 2017-10-27 | 2017-10-27 | Method and device for separating refined mixed aromatic hydrocarbon containing hydrogen sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107794076A CN107794076A (en) | 2018-03-13 |
| CN107794076B true CN107794076B (en) | 2023-06-23 |
Family
ID=61548468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711029745.0A Active CN107794076B (en) | 2017-10-27 | 2017-10-27 | Method and device for separating refined mixed aromatic hydrocarbon containing hydrogen sulfide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107794076B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111921218A (en) * | 2020-08-03 | 2020-11-13 | 章丘市胜隆化工有限公司 | Production equipment and production process of mixed aromatic hydrocarbon |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5573645A (en) * | 1995-06-29 | 1996-11-12 | Mobil Oil Corporation | Process and apparatus for the separation of aromatic hydrocarbons |
| CN101362672A (en) * | 2008-09-28 | 2009-02-11 | 黄健雄 | Apparatus and method for continuously preparing trimethyl benzene and tetramethylbenzene in single tower by heavy aromatic hydrocarbon one step method |
| CN207811679U (en) * | 2017-10-27 | 2018-09-04 | 新疆寰球工程公司 | Desulfurization separator for hydrogen sulfide containing refined BTX aromatics |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8754281B2 (en) * | 2010-08-25 | 2014-06-17 | Uop Llc | Energy conservation in heavy-hydrocarbon distillation |
| US20120271084A1 (en) * | 2011-04-22 | 2012-10-25 | Uop Llc | Recycle of transalkylation effluent fractions enriched in trimethylbenzene |
-
2017
- 2017-10-27 CN CN201711029745.0A patent/CN107794076B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5573645A (en) * | 1995-06-29 | 1996-11-12 | Mobil Oil Corporation | Process and apparatus for the separation of aromatic hydrocarbons |
| CN101362672A (en) * | 2008-09-28 | 2009-02-11 | 黄健雄 | Apparatus and method for continuously preparing trimethyl benzene and tetramethylbenzene in single tower by heavy aromatic hydrocarbon one step method |
| CN207811679U (en) * | 2017-10-27 | 2018-09-04 | 新疆寰球工程公司 | Desulfurization separator for hydrogen sulfide containing refined BTX aromatics |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107794076A (en) | 2018-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106477792A (en) | A kind of method and device for stripping process petrochemical industry sour water nothing side line single column negative pressure | |
| CN102234541B (en) | Energy-saving pyrolysis gasoline full-cut hydrogenation method and device | |
| CN107021590B (en) | Method for reducing harmful components in ammonia distillation wastewater through step-by-step separation based on high dry distillation of coal cakes | |
| CN102234540B (en) | Hydrogenation method and apparatus for center fractions of pyrolysis gasoline | |
| CN109762590B (en) | Fractionation system and fractionation method | |
| CN102309863B (en) | Reduced pressure distillation method and device | |
| CN103484159B (en) | Matching technology method for optimizing feeding of coal tar suspended bed hydrocracker | |
| CN107794076B (en) | Method and device for separating refined mixed aromatic hydrocarbon containing hydrogen sulfide | |
| CN208517188U (en) | A kind of Containing-Sulfur Wastewater Treatment System | |
| CN107177372B (en) | The suspended bed hydrogenation method and hydrogenation system of heavy oil feedstock | |
| CN102311771B (en) | Crude oil processing method | |
| RU2544994C1 (en) | Method and unit for oil preliminary distillation | |
| CN201686667U (en) | Cracking gasoline full-fraction hydrogenation device | |
| CN102443406B (en) | Crude oil distillation method | |
| CN102443407B (en) | Crude oil deep drawing process method | |
| CN207811679U (en) | Desulfurization separator for hydrogen sulfide containing refined BTX aromatics | |
| RU2546677C1 (en) | Method and installation of hydrocracking with obtaining motor fuels | |
| CN201686666U (en) | Middle-fraction hydrogenation device of cracked gasoline | |
| CN107267202B (en) | Method and device for stripping fractionation and negative pressure desorption of hydrogenated diesel refinery gas | |
| CN204385135U (en) | Full cut catalytic gasoline selective hydrodesulfurization device | |
| CN113604248A (en) | Mixed crude oil distillation device and method | |
| CN103351272B (en) | MTP (Methanol to Propylene) and catalytic cracking combined technology and integrated unit | |
| CN106554260B (en) | Methyl tert-butyl ether desulfurization process and device | |
| CN102443408B (en) | Pressure reduction distillation process method | |
| CN212174844U (en) | Furfural refining device supporting wide solvent-oil ratio operation conditions |
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 |