CN114854448A - Recovery device of liquefied gas in reforming hydrogen production - Google Patents
Recovery device of liquefied gas in reforming hydrogen production Download PDFInfo
- Publication number
- CN114854448A CN114854448A CN202110147400.5A CN202110147400A CN114854448A CN 114854448 A CN114854448 A CN 114854448A CN 202110147400 A CN202110147400 A CN 202110147400A CN 114854448 A CN114854448 A CN 114854448A
- Authority
- CN
- China
- Prior art keywords
- stage
- liquid
- outlet
- absorption
- inlet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007789 gas Substances 0.000 title claims abstract description 148
- 239000001257 hydrogen Substances 0.000 title claims abstract description 134
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 134
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 59
- 238000002407 reforming Methods 0.000 title claims abstract description 30
- 238000011084 recovery Methods 0.000 title abstract description 33
- 238000010521 absorption reaction Methods 0.000 claims abstract description 93
- 238000000926 separation method Methods 0.000 claims abstract description 79
- 239000007788 liquid Substances 0.000 claims description 123
- 238000001816 cooling Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000007791 liquid phase Substances 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 49
- 239000000047 product Substances 0.000 description 31
- 238000007906 compression Methods 0.000 description 15
- 230000006835 compression Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 239000006096 absorbing agent Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000001833 catalytic reforming Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005057 refrigeration Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
- C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
- C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
-
- 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
- C10G35/00—Reforming naphtha
- C10G35/24—Controlling or regulating of reforming operations
-
- 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
- C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
- C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
- C10G70/043—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes by fractional condensation
-
- 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
- C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
- C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
- C10G70/06—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes by gas-liquid contact
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The application discloses liquefied gas's recovery unit in hydrogen is produced in reforming belongs to the petroleum processing field. The device carries out n times of extraction on reformate in the reformed hydrogen production through n pressurizing liquid-separating devices connected in series to obtain the reformed hydrogen production after extraction and n groups of mixed liquid phases; performing substance separation on the n groups of mixed liquid phases through a product separation device to obtain separated liquefied gas and separated reformed oil; reversely contacting the extracted reformed hydrogen with the separated reformed oil through an absorption device to obtain contacted reformed oil; and recovering the separated liquefied gas and the liquefied gas absorbed in the contacted reformed oil, wherein n is a positive integer. The device can simplify the flow of recovering liquefied gas from reforming hydrogen production, and improve the recovery efficiency of the liquefied gas.
Description
Technical Field
The application relates to the field of petroleum processing, in particular to a recovery device for liquefied gas in hydrogen production by reforming.
Background
The catalytic reforming is a petroleum processing technology, which takes naphtha as a raw material to refine reformed oil through catalytic reforming, and simultaneously produces hydrogen as a byproduct, namely reformed hydrogen.
The reformed hydrogen contains petroleum gas, and the liquefied gas can be industrially recovered from the reformed hydrogen through compression and cooling methods. Illustratively, the reformed hydrogen is pressurized for the first time, the reformed hydrogen after the first pressurization is cooled by an air cooler and then is mixed with the reformed oil from the bottom of the NO. 2 contact tank, the mixed reformate (including reformate and reformed hydrogen) is further cooled and then enters a No. 1 re-contact tank, the method comprises the steps of performing gas-liquid balance in a No. 1 re-contact tank, outputting reformed oil absorbing liquefied gas from the tank bottom of the No. 1 re-contact tank, performing secondary compression on reformed hydrogen produced at the tank top of the No. 1 re-contact tank according to the delivery pressure requirement, mixing the reformed hydrogen produced after the secondary compression with the reformed oil produced from the bottom of a reformate separation tank again, cooling the re-mixed reformate by a cooler, then feeding the cooled reformate into a No. 2 re-contact tank for gas-liquid balance, outputting the reformed hydrogen produced from the tank top of the No. 2 re-contact tank, and delivering the reformed oil at the tank bottom to the No. 1 re-contact tank.
The liquefied gas in the reformed hydrogen production needs to be in mixed contact with the reformed oil for multiple times in the recovery process of the liquefied gas to perform contact absorption on the liquefied gas in the reformed hydrogen production, and the whole process is complex, high in energy consumption and poor in absorption effect.
Disclosure of Invention
The embodiment of the application provides a recovery unit of liquefied gas in hydrogen is produced in reforming can simplify the flow of retrieving liquefied gas in the hydrogen is produced in the reforming, improves the recovery efficiency of liquefied gas. The technical scheme is as follows:
according to one aspect of the application, a recovery device for liquefied gas in reforming hydrogen production is provided, and the device comprises an absorption device, a product separation device and n pressurized liquid separation devices;
an i-level gas inlet for reforming to produce hydrogen is arranged on the ith pressurizing liquid separation device in the n pressurizing liquid separation devices; the i-stage gas outlet of the ith pressurizing and liquid separating device is connected with the i + 1-stage gas inlet of the (i + 1) th pressurizing and liquid separating device; the n-stage gas outlet of the nth pressurizing liquid-separating device in the n pressurizing liquid-separating devices is connected with the gas inlet of the absorption device; the absorption device is provided with a purified gas outlet for reforming to produce hydrogen;
the liquid outlet of each of the n pressurized liquid separation devices is connected with the liquid inlet of the product separation device, or is connected with the liquid inlets of other downstream devices; the reformate outlet of the product separation device is connected with the absorption liquid inlet of the absorption device; the absorption device is provided with an absorption liquid outlet for recovering the reformed oil; wherein i is a positive integer, n is a positive integer greater than 1, and i +1 is less than or equal to n.
According to another aspect of the application, a recovery device of liquefied gas in hydrogen production by reforming is provided, and the device comprises 1 absorption device, 1 product separation device, 1 pressurized liquid separation device and 1 intercooler;
the pressurizing and liquid-separating device comprises a primary booster, a primary air cooler, a primary water cooler and a primary liquid-separating tank; the absorption device comprises a secondary supercharger, a tower top heat exchanger, a tower bottom heat exchanger and an absorption tower;
the first-stage booster is provided with a first-stage gas inlet for reforming to produce hydrogen, a boosting outlet of the first-stage booster is connected with an air cooling inlet of a first-stage air cooler, an air cooling outlet of the first-stage air cooler is connected with a water cooling inlet of a first-stage water cooler, a water cooling outlet of the first-stage water cooler is connected with a liquid separating inlet of a first-stage liquid separating tank, a first-stage gas outlet arranged on the top of the first-stage liquid separating tank is connected with a second-stage gas inlet on the second-stage booster, a liquid outlet arranged on the bottom of the first-stage liquid separating tank is connected with a liquid inlet of a product separating device, or is connected with liquid inlets of other downstream devices;
a pressurizing outlet of the secondary supercharger is connected with a first heat exchange inlet of the tower bottom heat exchanger, a first heat exchange outlet of the tower bottom heat exchanger is connected with a first heat exchange inlet of the tower top heat exchanger, a first heat exchange outlet of the tower top heat exchanger is connected with a gas inlet arranged at the lower part of the tower body of the absorption tower, a reformed oil outlet in the product separation device is connected with an absorption liquid inlet arranged at the upper part of the tower body of the absorption tower through an intercooler, a tower bottom liquid outlet of the absorption tower is connected with a second heat exchange inlet of the tower bottom heat exchanger, and a tower top gas outlet of the absorption tower is connected with a second heat exchange inlet of the tower top heat exchanger;
an absorption liquid outlet of the reformed oil is arranged on the tower bottom heat exchanger, and a purified gas outlet of the reformed hydrogen is arranged on the tower top heat exchanger.
The beneficial effects brought by the technical scheme provided by the embodiment of the application at least comprise:
the recovery device for liquefied gas in reformed hydrogen production carries out forward compression on the reformed hydrogen production through the pressurization liquid separation device, liquefies a mixed liquid phase from the reformed hydrogen production, and then separates liquefied gas and reformed oil from the mixed liquid phase through the product separation device, so that the liquefied gas is rapidly separated from the reformed hydrogen production; and then the reformed hydrogen separated by the pressure liquid separation device and the reformed oil separated by the product separation device are in reverse contact, and the liquefied gas is absorbed again from the separated reformed hydrogen, namely the liquefied gas in the secondary separation reformed hydrogen production is combined with the absorption mode of the reformed oil, so that the liquefied gas can be rapidly recovered, the liquefied gas in the reformed hydrogen production is not required to be absorbed by the reformed oil for multiple times, the flow of recovering the liquefied gas from the reformed hydrogen production is simplified, the recovery efficiency of the liquefied gas and the reformed oil is improved, and the yield of the liquefied gas and the reformed oil and the purification effect of the reformed hydrogen production are also improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic structural diagram illustrating a recovery device for reforming liquefied gas in hydrogen production according to an exemplary embodiment of the present application;
FIG. 2 is a schematic diagram showing the structure of a recovery device for reforming liquefied gas in hydrogen production according to another exemplary embodiment of the present application;
fig. 3 shows a schematic structural diagram of a conventional recovery device for reforming liquefied gas in hydrogen production according to an exemplary embodiment of the present application.
Detailed Description
To make the objects, technical solutions and advantages of the present application more clear, the following detailed description of the embodiments of the present application will be made with reference to the accompanying drawings.
Reference will first be made to several terms referred to in this application:
catalytic reforming, which is an important oil refining process for producing high-octane gasoline and light aromatics (benzene, toluene and xylene) by taking naphtha as a raw material and simultaneously producing hydrogen as a byproduct; the oil refined by catalytic reforming is reformed oil, and the hydrogen gas by-produced is reformed hydrogen.
Naphtha refers to light oil for chemical raw materials produced by processing crude oil or other raw materials.
Liquefied petroleum gas, also called liquefied gas, is a colorless volatile liquid product obtained by pressurizing, cooling and liquefying gases (such as petroleum gas) generated and recovered in the refining process of oil refining. The main components are propane, butane, propylene and butylene.
Fig. 1 shows a schematic structural diagram of a recovery device for reforming liquefied gas in hydrogen production provided by an exemplary embodiment of the present application, and the recovery device comprises an absorption device 120, a product separation device 140, and n pressurized liquid separation devices 160;
an i-level gas inlet for reforming to produce hydrogen is arranged on the ith pressurizing and liquid-separating device 160 in the n pressurizing and liquid-separating devices 160; the i-stage gas outlet of the ith pressurizing and liquid-separating device 160 is connected with the i + 1-stage gas inlet of the (i + 1) th pressurizing and liquid-separating device 160; the n-stage gas outlet of the nth pressurized liquid separation device 160 in the n pressurized liquid separation devices 160 is connected with the gas inlet of the absorption device 120; the absorption device 120 is provided with a purified gas outlet for reforming to produce hydrogen;
the liquid outlet of each pressurized liquid separation device 160 in the n pressurized liquid separation devices 160 is connected with the liquid inlet of the product separation device 140, or is connected with the liquid inlets of other downstream devices; the reformate outlet of the product separation device 140 is connected to the absorption liquid inlet of the absorption device 120; the absorption device 120 is provided with an absorption liquid outlet for recovering the reformate; wherein i is a positive integer, n is a positive integer greater than 1, and i +1 is less than or equal to n.
In some embodiments, the ith pressurized liquid separation device 160 includes an i-stage booster 162, an i-stage cooler 164, and an i-stage liquid separation tank 166;
the i-stage gas inlet of the ith pressurizing and separating device 160 in the n pressurizing and separating devices 160 is arranged on an i-stage supercharger 162, the pressurizing outlet of the i-stage supercharger 162 is connected with the cooling inlet of an i-stage cooler 164, the cooling outlet of the i-stage cooler 164 is connected with the separating inlet of an i-stage liquid separating tank 166, and the i-stage gas outlet arranged on the top of the i-stage liquid separating tank 166 is connected with the i + 1-stage gas inlet; a liquid outlet provided on the bottom of the i-fraction liquid tank 166 is connected to a liquid inlet of the product separation device 140, or to a liquid inlet of another downstream device. The liquid outlet provided at the bottom of the i-fraction liquid tank 166 is the liquid outlet of the pressurized liquid separation device 160.
In some embodiments, the i-stage cooler 164 includes at least one of an air cooler, a water cooler, and a heat exchanger.
In some embodiments, the absorber apparatus 120 includes an n +1 stage booster 122, a bottoms heat exchanger 124, an overhead heat exchanger 126, and an absorber 128;
a gas inlet of the absorption device 120 is arranged on an n + 1-stage supercharger 122, a supercharging outlet of the n + 1-stage supercharger 122 is connected with a first heat exchange inlet of a tower bottom heat exchanger 124, a first heat exchange outlet of the tower bottom heat exchanger 124 is connected with a first heat exchange inlet of a tower top heat exchanger 126, a first heat exchange outlet of the tower top heat exchanger 126 is connected with a gas inlet arranged at the lower part of a tower body of an absorption tower 128, a reformate outlet is connected with an absorption liquid inlet arranged at the upper part of the tower body of the absorption tower 128, a tower bottom liquid outlet of the absorption tower 128 is connected with a second heat exchange inlet of the tower bottom heat exchanger 124, an tower top gas outlet of the absorption tower 128 is connected with a second heat exchange inlet of the tower top heat exchanger 126, an absorption liquid outlet is arranged on the tower bottom heat exchanger 124, and a purified gas outlet is arranged on the tower top heat exchanger 126.
In some embodiments, the reformate outlet is connected to the absorption liquid inlet via an intercooler 180; the intercooler 180 is configured to cool the reformate output from the reformate outlet to a temperature range of 0 to 40 degrees celsius, where the temperature range includes 0 degrees celsius and 40 degrees celsius.
In some embodiments, the absorber 128 is a tray column or a packed column.
In some embodiments, the gas pressure at the purified gas outlet is within the range of the gas pressure of the hydrogen pipe network.
Describing the process of recovering liquefied gas in reformed hydrogen production by using the recovery device, firstly, the reformed hydrogen production enters the recovery device from a primary gas inlet of a primary pressurizing liquid-separating device 160, and the reformed hydrogen production firstly passes through a primary supercharger 162 to obtain pressurized reformed hydrogen production; the pressurized reformed hydrogen enters a primary cooler 164 for cooling to obtain cooled reformed hydrogen; the cooled reformed hydrogen is sent into a first-stage liquid separation tank 166 for liquid separation treatment, a 1 st group of mixed liquid phase flows out from the bottom of the first-stage liquid separation tank 166, and first-stage reformed hydrogen flows out from the top of the first-stage liquid separation tank 166; the 1 st mixed liquid phase flows into the product separation device 140 for substance separation, the first-stage reformed hydrogen gas enters the second-stage booster 162, then the compression, cooling and liquid separation processes of the reformed hydrogen gas in the first-stage pressurized liquid separation device 160 are repeated in the remaining n-1 pressurized liquid separation devices 160, the 1 st mixed liquid phase flows out from each pressurized liquid separation device 160 and enters the product separation device 140, the i-stage reformed hydrogen gas flowing out from the i-stage liquid tank 166 of the i-stage pressurized liquid separation device 160 enters the i + 1-stage booster 162 of the i + 1-stage pressurized liquid separation device 160, and the n-stage reformed hydrogen gas flowing out from the n-stage liquid tank 166 of the n-stage pressurized liquid separation device 160 (i.e., the extracted reformed hydrogen gas) flows into the absorption device 120.
The n groups of mixed liquid phases contain reformate oil and liquefied gas; the n groups of mixed liquid phases sequentially enter the product separation device 140 for substance separation, liquefied gas and reformed oil are separated from the mixed liquid phase, and the separated liquefied gas and the separated reformed oil flow out from the product separation device 140. The separated reformate flowing out of the product separator 140 is cooled by the intercooler 180 and then enters the absorber 120, and the separated reformate is used as an absorption liquid for the liquefied gas in the extracted reformed hydrogen production.
The extracted reformed hydrogen enters the absorption device 120 from the gas inlet of the n + 1-stage supercharger 122, after the compression treatment of the n + 1-stage supercharger 122, the pressurized reformed hydrogen is obtained, the pressurized reformed hydrogen enters the tower bottom heat exchanger 124 at the bottom of the absorption tower, then enters the tower top heat exchanger 126 at the top of the absorption tower after passing through the tower bottom heat exchanger 124, the pressurized reformed hydrogen is cooled through two heat exchanges, the cooled reformed hydrogen enters the absorption tower from the gas inlet arranged at the lower part of the tower body of the absorption tower 128, the separated reformed product oil enters the absorption tower 128 from the absorption liquid inlet arranged at the upper part of the tower body of the absorption tower 128, the cooled reformed hydrogen flows upwards from the lower part of the absorption tower 128, the separated reformed product oil flows downwards from the upper part of the absorption tower 128, and the extracted reformed hydrogen and the separated reformed product oil are in reverse contact, so that the separated reformed oil fully absorbs the liquefied gas from the extracted reformed hydrogen.
The liquefied gas and the reformed oil are separately recovered, and illustratively, the separated reformed oil is subjected to material separation, the liquefied gas and the reformed oil are separated, the liquefied gas is stored in a storage device of the liquefied gas, and the reformed oil is stored in a storage device of the reformed oil; alternatively, the separated reformate may be directly recovered.
The hydrogen pipe network is a hydrogen transmission network, the absorption device absorbs liquefied gas in the extracted reformed hydrogen production to obtain purified reformed hydrogen production, and the purified reformed hydrogen production is input into the hydrogen pipe network according to a specified gas pressure value range.
Illustratively, the series of levels, i, … …, n, represents a gas pressure level, wherein the level is in positive correlation with the gas pressure, for example, the gas pressure of i +1 is greater than that of i.
For example, the cooler 164 may be a combination of coolers, for example, the cooler 164 is formed by combining an air cooler and a water cooler in series, when cooling the pressurized reformed hydrogen, the air cooler first cools the pressurized reformed hydrogen, the primarily cooled reformed hydrogen then enters the water cooler, the water cooler secondarily cools the primarily cooled reformed hydrogen, and finally the secondarily cooled reformed hydrogen enters the liquid separation tank.
Illustratively, the intercooler 180 may be a refrigeration system. When the pressure of the absorption tower is fixed, the lower the temperature of the reformed product oil entering the absorption tower 128 is, the better the absorption effect on liquefied gas in the reformed product hydrogen is, and the higher the purification degree of the reformed product hydrogen is, the temperature of the refrigeration system may be set according to the negative correlation between the purification degree of the reformed product hydrogen and the temperature of the reformed product oil, for example, the lower the temperature of the refrigeration system is set when the purification degree requirement of the reformed product hydrogen is higher. Illustratively, the freezing system is provided in a temperature range of 0 to 40 degrees celsius.
Illustratively, the gas inlet of the absorption tower 128 is disposed at a position near the bottom of the tower, and the absorption liquid inlet of the absorption tower 128 is disposed at a position near the top of the tower.
The specified pressure value range refers to the gas pressure value range of the hydrogen pipe network, that is, the gas pressure value of the purified gas outlet belongs to the gas pressure value range of the hydrogen pipe network. For example, the adjustment of the gas pressure may be a compression adjustment. Optionally, the value range of the gas pressure of the hydrogen pipe network is greater than or equal to 1Mpa and less than or equal to 4Mpa, Mpa in Mpa is a pressure unit megapascal, and g represents a pressure indicated by a pressure gauge, that is, gauge pressure. Illustratively, the compression stage number j +1 of the reformed hydrogen production can be set according to the pressure of a hydrogen pipe network, and the compression stage number of the reformed hydrogen production and the purification degree form a positive correlation relationship, that is, the higher the compression stage number of the reformed hydrogen production is, the higher the pressure when the reformed hydrogen production is output is, the higher the purification degree of the reformed hydrogen production is, and meanwhile, the higher the energy consumption is.
By way of example, the other downstream equipment refers to other equipment used in the processing of reformate, such as an olefin extraction unit for reformate.
In summary, the recovery device for liquefied gas in reformed hydrogen production provided by this embodiment compresses reformed hydrogen production forward through the pressurization liquid separation device, and liquefies a mixed liquid phase from the reformed hydrogen production; and then the reformed hydrogen produced by the pressurized liquid separation device and the reformed oil produced by the product separation device are in reverse contact, and the reformed oil absorbs liquefied gas again from the separated reformed hydrogen produced, namely the liquefied gas in the secondary separation and reforming hydrogen production. The device can rapidly recover the liquefied gas by combining a gas compression mode and a reformed oil absorption mode, the liquefied gas in the reformed hydrogen production is not required to be absorbed by the reformed oil for many times, the flow of recovering the liquefied gas from the reformed hydrogen production is simplified, the recovery efficiency of the liquefied gas is improved, the yield of the liquefied gas and the reformed oil is improved, and the purification effect of the reformed hydrogen production is also improved. In addition, as the reformed hydrogen is not mixed with the reformed oil in the compression process, the risk of coking of the cylinder of the reformed hydrogen compressor is reduced.
Fig. 2 is a schematic diagram showing the structure of a recovery apparatus for reforming liquefied gas in hydrogen production according to another exemplary embodiment of the present application, which includes 1 absorption apparatus 320, 1 product separation apparatus 340, 1 pressurized liquid separation apparatus 360, and 1 intercooler 380;
the pressurizing and liquid-separating device 360 comprises a first-stage booster 362, a first-stage air cooler 364, a first-stage water cooler 366 and a first-stage liquid-separating tank 368; the absorption device 320 comprises a secondary booster 322, a tower bottom heat exchanger 324, an tower top heat exchanger 326 and an absorption tower 328;
a first-stage gas inlet for reforming and producing hydrogen is arranged on the first-stage booster 362, a boosting outlet of the first-stage booster 362 is connected with an air cooling inlet of a first-stage air cooler 364, an air cooling outlet of the first-stage air cooler 364 is connected with a water cooling inlet of a first-stage water cooler 366, a water cooling outlet of the first-stage water cooler 366 is connected with a liquid separation inlet of a first-stage liquid separation tank 368, a first-stage gas outlet arranged on the top of the first-stage liquid separation tank 368 is connected with a second-stage gas inlet on the second-stage booster 322, a liquid outlet arranged on the bottom of the first-stage liquid separation tank 368 is connected with a liquid inlet of the product separation device 340, or is connected with liquid inlets of other downstream devices;
a pressurizing outlet of the second-stage supercharger 322 is connected with a first heat exchange inlet of the tower bottom heat exchanger 324, a first heat exchange outlet of the tower bottom heat exchanger 324 is connected with a first heat exchange inlet of the tower top heat exchanger 326, a first heat exchange outlet of the tower top heat exchanger 326 is connected with a gas inlet arranged at the lower part of the tower body of the absorption tower 328, a reformed oil outlet of the product separation device 340 is connected with an absorption liquid inlet arranged at the upper part of the tower body of the absorption tower 328 through an intercooler 380, a tower bottom liquid outlet of the absorption tower 328 is connected with a second heat exchange inlet of the tower bottom heat exchanger 324, and a tower top gas outlet of the absorption tower 328 is connected with a second heat exchange inlet of the tower top heat exchanger 326;
the tower bottom heat exchanger 324 is provided with an absorption liquid outlet for the reformed oil, and the tower top heat exchanger 326 is provided with a purified gas outlet for the reformed hydrogen production.
In some embodiments, the intercooler 380 is configured to cool the reformate output from the reformate outlet to a temperature range of 0 to 40 degrees celsius, which includes 0 degrees celsius and 40 degrees celsius.
In some embodiments, the absorber column 328 is a tray column or a packed column.
In some embodiments, the gas pressure at the purified gas outlet is within the range of the gas pressure of the hydrogen pipe network.
In summary, the recovery device for liquefied gas in reformed hydrogen production provided by this embodiment compresses reformed hydrogen production forward through the pressurization liquid separation device, and liquefies a mixed liquid phase from the reformed hydrogen production; and then the reformed hydrogen produced by the pressurized liquid separation device and the reformed oil produced by the product separation device are in reverse contact, and the reformed oil absorbs liquefied gas again from the separated reformed hydrogen produced, namely the liquefied gas in the secondary separation and reforming hydrogen production. The device can rapidly recover the liquefied gas by combining a gas compression mode and a reformed oil absorption mode, the liquefied gas in the reformed hydrogen production is not required to be absorbed by the reformed oil for many times, the flow of recovering the liquefied gas from the reformed hydrogen production is simplified, the recovery efficiency of the liquefied gas is improved, the yield of the liquefied gas and the reformed oil is improved, and the purification effect of the reformed hydrogen production is also improved. In addition, as the reformed hydrogen is not mixed with the reformed oil in the compression process, the risk of coking of the cylinder of the reformed hydrogen compressor is reduced.
For example, on a continuous reforming scale of 100 ten thousand tons/year, the pressure of the delivered hydrogen (i.e., the pressure of the reformed hydrogen delivered to the hydrogen pipe network) is 2.7mpa g, and the two-stage compression is required for the reformed hydrogen production, the effect of recovering the liquefied gas in the reformed hydrogen production is verified, that is, the effect is verified based on the apparatus shown in fig. 2, and the experimental data shown in tables 1 and 2 are obtained. Compared with the recovery effect of the traditional recovery method of the liquefied gas in the reformed hydrogen production, the recovery method of the liquefied gas in the reformed hydrogen production can obviously recover more liquefied gas, and compared with the traditional recovery method (the device adopted by the traditional recovery method is shown in figure 3), the recovery method of the liquefied gas in the reformed oil increases 56% and the hydrogen purity is purified to 95.6%. Wherein C5+ refers to hydrocarbons containing a carbon number greater than or equal to 5.
TABLE 1
| Hydrogen production, kilogram per hour (kg/h) | Purity of hydrogen, mole (mol) | |
| Conventional recovery method | 10022 | 94.7％ |
| Recovery method of the present application | 8779 | 95.6％ |
TABLE 2
Illustratively, the icons in FIG. 3 are illustrated as follows: 501, a first-stage compressor; 502, air cooler; 503, a water cooler; 504, No. 1 recontacting tank; 505, a secondary compressor; 506, an air cooler; 507, a water cooler; 508, a refrigeration system; 509, No. 2, then contact the can.
To sum up, liquefied gas's recovery unit in hydrogen is produced in reforming, this application retrieves liquefied gas and reformate effect in the hydrogen is produced from reforming better, can also improve the purity of improving the hydrogen is produced in reforming.
It should be understood that reference to "a plurality" herein means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
The above description is only exemplary of the present application and should not be taken as limiting, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The device for recovering the liquefied gas in the reformed hydrogen production is characterized by comprising an absorption device, a product separation device and n pressurized liquid separation devices;
an i-level gas inlet for reforming to produce hydrogen is arranged on the ith pressurizing liquid separation device in the n pressurizing liquid separation devices; the i-stage gas outlet of the ith pressurizing and liquid separating device is connected with the i + 1-stage gas inlet of the (i + 1) th pressurizing and liquid separating device; the n-stage gas outlet of the nth pressurized liquid separation device in the n pressurized liquid separation devices is connected with the gas inlet of the absorption device; the absorption device is provided with a purified gas outlet for reforming to produce hydrogen;
the liquid outlet of each of the n pressurized liquid separation devices is connected with the liquid inlet of the product separation device, or is connected with the liquid inlets of other downstream devices; the reformate outlet of the product separation device is connected with the absorption liquid inlet of the absorption device; the absorption device is provided with an absorption liquid outlet for recovering the reformed oil; wherein i is a positive integer, n is a positive integer greater than 1, and i +1 is less than or equal to n.
2. The apparatus of claim 1, wherein said ith pressurized liquid separation device comprises an i-stage booster, an i-stage cooler, and an i-stage liquid tank;
an i-stage gas inlet of the ith pressurizing and liquid separating device in the n pressurizing and liquid separating devices is arranged on the i-stage supercharger, a pressurizing outlet of the i-stage supercharger is connected with a cooling inlet of the i-stage cooler, a cooling outlet of the i-stage cooler is connected with a liquid separating inlet of the i-stage liquid separating tank, and an i-stage gas outlet arranged on the top of the i-stage liquid separating tank is connected with the i + 1-stage gas inlet; a liquid outlet arranged at the bottom of the i-fraction liquid tank is connected with the liquid inlet of the product separation device or is connected with the liquid inlet of the other downstream device.
3. The apparatus of claim 2, wherein the i-stage cooler comprises at least one of an air cooler, a water cooler, and a heat exchanger.
4. The apparatus according to any one of claims 1 to 3, wherein the absorption apparatus comprises an n +1 stage booster, an overhead heat exchanger, a bottom heat exchanger and an absorption column;
the gas inlet of the absorption device is arranged on the n + 1-stage supercharger, the supercharging outlet of the n + 1-stage supercharger is connected with the first heat exchange inlet of the tower bottom heat exchanger, a first heat exchange outlet of the tower bottom heat exchanger is connected with a first heat exchange inlet of the tower top heat exchanger, a first heat exchange outlet of the tower top heat exchanger is connected with a gas inlet arranged at the lower part of the tower body of the absorption tower, the reformed oil outlet is connected with the absorption liquid inlet arranged at the upper part of the tower body of the absorption tower, the tower bottom liquid outlet of the absorption tower is connected with the second heat exchange inlet of the tower bottom heat exchanger, the tower top gas outlet of the absorption tower is connected with the second heat exchange inlet of the tower top heat exchanger, the tower bottom heat exchanger is provided with the absorption liquid outlet, and the tower top heat exchanger is provided with the purified gas outlet.
5. The apparatus according to claim 4, wherein the reformate outlet and the absorption liquid inlet are connected by an intercooler; the intercooler is configured to cool the temperature of the reformate output from the reformate outlet to a temperature range of 0 to 40 degrees celsius, and the temperature range includes 0 degree celsius and 40 degrees celsius.
6. The apparatus of claim 4, wherein the absorption column is a tray column or a packed column.
7. The apparatus of claim 4, wherein the purified gas outlet has a gas pressure within a range of a gas pressure of a hydrogen pipe network.
8. The device for recovering the liquefied gas in the reforming hydrogen production is characterized by comprising 1 absorption device, 1 product separation device, 1 pressurizing liquid separation device and 1 intercooler;
the pressurizing and liquid-separating device comprises a primary supercharger, a primary air cooler, a primary water cooler and a primary liquid-separating tank; the absorption device comprises a secondary supercharger, a tower top heat exchanger, a tower bottom heat exchanger and an absorption tower;
a first-stage gas inlet for reforming to produce hydrogen is arranged on the first-stage supercharger, a supercharging outlet of the first-stage supercharger is connected with an air cooling inlet of the first-stage air cooler, an air cooling outlet of the first-stage air cooler is connected with a water cooling inlet of the first-stage water cooler, a water cooling outlet of the first-stage water cooler is connected with a liquid separating inlet of the first-stage liquid separating tank, a first-stage gas outlet arranged on the top of the first-stage liquid separating tank is connected with a second-stage gas inlet on the second-stage supercharger, a liquid outlet arranged on the bottom of the first-stage liquid separating tank is connected with a liquid inlet of the product separating device, or is connected with liquid inlets of other downstream devices;
a pressurizing outlet of the secondary booster is connected with a first heat exchange inlet of the tower bottom heat exchanger, a first heat exchange outlet of the tower bottom heat exchanger is connected with a first heat exchange inlet of the tower top heat exchanger, a first heat exchange outlet of the tower top heat exchanger is connected with a gas inlet arranged at the lower part of the tower body of the absorption tower, a reformate outlet in the product separation device is connected with an absorption liquid inlet arranged at the upper part of the tower body of the absorption tower through the intercooler, a tower bottom liquid outlet of the absorption tower is connected with a second heat exchange inlet of the tower bottom heat exchanger, and a tower top gas outlet of the absorption tower is connected with a second heat exchange inlet of the tower top heat exchanger;
an absorption liquid outlet of the reformed oil is arranged on the tower bottom heat exchanger, and a purified gas outlet of the reformed hydrogen production is arranged on the tower top heat exchanger.
9. The apparatus of claim 8, wherein the intercooler is configured to cool the temperature of the reformate output by the reformate outlet to a temperature interval of 0 to 40 degrees celsius, the temperature interval including 0 degrees celsius and 40 degrees celsius.
10. The apparatus of claim 8, wherein the absorption column is a tray column or a packed column.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110147400.5A CN114854448B (en) | 2021-02-03 | 2021-02-03 | Recovery device for liquefied gas in hydrogen production by reforming |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110147400.5A CN114854448B (en) | 2021-02-03 | 2021-02-03 | Recovery device for liquefied gas in hydrogen production by reforming |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114854448A true CN114854448A (en) | 2022-08-05 |
| CN114854448B CN114854448B (en) | 2024-03-26 |
Family
ID=82622994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110147400.5A Active CN114854448B (en) | 2021-02-03 | 2021-02-03 | Recovery device for liquefied gas in hydrogen production by reforming |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114854448B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60118602A (en) * | 1983-11-30 | 1985-06-26 | Mitsui Toatsu Chem Inc | Reforming or decomposition of hydrocarbon |
| CN202297110U (en) * | 2011-10-12 | 2012-07-04 | 中国石油化工股份有限公司 | Hydrogen cold recycling system for continuous reforming device |
| CN102994146A (en) * | 2011-09-19 | 2013-03-27 | 中国石油化工集团公司 | System and method for improving liquid yield of reforming device |
| CN204958819U (en) * | 2015-09-17 | 2016-01-13 | 中国海洋石油总公司 | Liquefied gas recovery unit in intensive natural gas |
| US20170015913A1 (en) * | 2015-07-15 | 2017-01-19 | IFP Energies Nouvelles | Process for the treatment of a hydrocarbon feed containing hydrogen and hydrocarbons |
| US20180066889A1 (en) * | 2016-09-06 | 2018-03-08 | Lummus Technology Inc. | Pretreatment of natural gas prior to liquefaction |
| CN108239553A (en) * | 2016-12-23 | 2018-07-03 | 中国石油天然气集团公司 | A kind of reforming reaction product separation system and method |
| CN108603129A (en) * | 2016-06-07 | 2018-09-28 | 环球油品公司 | The method and apparatus of removing benzene for gasoline concoction |
| CN108865251A (en) * | 2018-06-28 | 2018-11-23 | 上海河图工程股份有限公司 | A kind of re-contact process reducing catalytic reforming unit energy consumption |
| CN109694041A (en) * | 2017-10-20 | 2019-04-30 | 中国石化工程建设有限公司 | The method of reforming hydrogen-preparation reactor and reburner, reformation hydrogen production reaction |
| CN110776947A (en) * | 2019-11-15 | 2020-02-11 | 中国石油化工股份有限公司 | Catalytic reforming energy-saving system, energy-saving method and catalytic reforming reaction system |
-
2021
- 2021-02-03 CN CN202110147400.5A patent/CN114854448B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60118602A (en) * | 1983-11-30 | 1985-06-26 | Mitsui Toatsu Chem Inc | Reforming or decomposition of hydrocarbon |
| CN102994146A (en) * | 2011-09-19 | 2013-03-27 | 中国石油化工集团公司 | System and method for improving liquid yield of reforming device |
| CN202297110U (en) * | 2011-10-12 | 2012-07-04 | 中国石油化工股份有限公司 | Hydrogen cold recycling system for continuous reforming device |
| US20170015913A1 (en) * | 2015-07-15 | 2017-01-19 | IFP Energies Nouvelles | Process for the treatment of a hydrocarbon feed containing hydrogen and hydrocarbons |
| CN204958819U (en) * | 2015-09-17 | 2016-01-13 | 中国海洋石油总公司 | Liquefied gas recovery unit in intensive natural gas |
| CN108603129A (en) * | 2016-06-07 | 2018-09-28 | 环球油品公司 | The method and apparatus of removing benzene for gasoline concoction |
| US20180066889A1 (en) * | 2016-09-06 | 2018-03-08 | Lummus Technology Inc. | Pretreatment of natural gas prior to liquefaction |
| CN108239553A (en) * | 2016-12-23 | 2018-07-03 | 中国石油天然气集团公司 | A kind of reforming reaction product separation system and method |
| CN109694041A (en) * | 2017-10-20 | 2019-04-30 | 中国石化工程建设有限公司 | The method of reforming hydrogen-preparation reactor and reburner, reformation hydrogen production reaction |
| CN108865251A (en) * | 2018-06-28 | 2018-11-23 | 上海河图工程股份有限公司 | A kind of re-contact process reducing catalytic reforming unit energy consumption |
| CN110776947A (en) * | 2019-11-15 | 2020-02-11 | 中国石油化工股份有限公司 | Catalytic reforming energy-saving system, energy-saving method and catalytic reforming reaction system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114854448B (en) | 2024-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7452458B2 (en) | Process for the treatment of a hydrocarbon feedstock | |
| EP0675190B1 (en) | Olefin recovery method | |
| KR100338407B1 (en) | Compound Condensation-Absorbing Method to Recover Olefin | |
| CN101823709B (en) | Separation of carbon monoxide from gaseous mixtures containing carbon monoxide | |
| CN112028731B (en) | Method for separating propylene reaction product from propane dehydrogenation | |
| CN102382680A (en) | Combined technology of catalytic cracking absorbing stabilizing system and C3 intercooling oil absorption | |
| CN101348235B (en) | Hydrogen recovery method for hydrogenation plant | |
| CN113959176B (en) | System and method for separating helium from liquefied natural gas flash gas | |
| CN112341308A (en) | Production method of n-hexane and isohexane | |
| US9637426B2 (en) | Methods and apparatuses for reforming of hydrocarbons including recovery of products using a recontacting zone | |
| CN114854448B (en) | Recovery device for liquefied gas in hydrogen production by reforming | |
| CN108774545B (en) | Catalytic reforming re-contact process with cold quantity balance arrangement | |
| CN103725313B (en) | The B-grade condensation separation method and device of catalytic reforming pre-hydrotreating reaction product | |
| CN106350107A (en) | Process for the treatment of a hydrocarbon feed containing hydrogen and hydrocarbons | |
| CN101263215A (en) | Process for recovering ethylene from an autothermal cracking reactor effluent | |
| CN113122314B (en) | Gas-liquid separation process for hydrogenation reaction product | |
| US20060032787A1 (en) | Process for the recovery of a hydrogen-rich gas and a stabilized liquid | |
| CN108865251B (en) | Re-contact process for reducing energy consumption of catalytic reforming device | |
| CN108239553B (en) | Reforming reaction product separation system and method | |
| US20210172678A1 (en) | Method for generating refrigeration for a carbon monoxide cold box | |
| CN107916127B (en) | A kind of rectification process for Fischer-Tropsch synthetic separation | |
| CN111238164A (en) | Intercooling separation device and process for catalytic cracking product gas | |
| CN110156557A (en) | A kind of recovery method of petrochemical industry output gas | |
| CN116948680A (en) | Continuous reforming and re-contact method and system | |
| CN112708482B (en) | Fixed bed reformate treatment system and treatment method |
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 |