CN113275020B - Regeneration method of catalyst for preparing chlorine by oxidizing hydrogen chloride - Google Patents

Regeneration method of catalyst for preparing chlorine by oxidizing hydrogen chloride Download PDF

Info

Publication number
CN113275020B
CN113275020B CN202010100666.XA CN202010100666A CN113275020B CN 113275020 B CN113275020 B CN 113275020B CN 202010100666 A CN202010100666 A CN 202010100666A CN 113275020 B CN113275020 B CN 113275020B
Authority
CN
China
Prior art keywords
catalyst
regeneration method
roasting
regenerated catalyst
regenerated
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
Application number
CN202010100666.XA
Other languages
Chinese (zh)
Other versions
CN113275020A (en
Inventor
楼家伟
周波
赵东科
李军冉
衡华
张宏科
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
Original Assignee
Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Group Co Ltd, Wanhua Chemical Ningbo Co Ltd filed Critical Wanhua Chemical Group Co Ltd
Priority to CN202010100666.XA priority Critical patent/CN113275020B/en
Publication of CN113275020A publication Critical patent/CN113275020A/en
Application granted granted Critical
Publication of CN113275020B publication Critical patent/CN113275020B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
    • B01J38/62—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids organic
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C01B7/04—Preparation of chlorine from hydrogen chloride
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention provides a regeneration method of a catalyst for preparing chlorine by oxidizing hydrogen chloride, which comprises the following steps: (1) roasting the deactivated ruthenium-based catalyst to obtain a regenerated catalyst I; (2) putting the regenerated catalyst I into an aqueous solution of sulfamic acid, carrying out ultrasonic treatment simultaneously, and then separating out solids to obtain a regenerated catalyst II; (3) putting the regenerated catalyst II into a hydrochloric acid solution, carrying out co-heat treatment on the catalyst and the hydrochloric acid solution, and then stirring and drying to obtain a regenerated catalyst III; (4) the regenerated catalyst III is reacted with O2The regenerated ruthenium-based catalyst is obtained by roasting. The method can reduce the influence of the regeneration process on a reaction system, reduce the consumption of waste acid, reduce the influence on the environment, treat sulfur substances poisoned on the surface of the catalyst, reduce the coverage of the deactivated noble metal ruthenium salt on active sites, improve the regeneration activity and the regeneration efficiency of the catalyst and prolong the regeneration life of the catalyst.

Description

Regeneration method of catalyst for preparing chlorine by oxidizing hydrogen chloride
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a regeneration method of a catalyst for preparing chlorine by hydrogen chloride oxidation.
Background
Chlorine (Cl)2) As an important basic chemical, it is widely used in chemical raw materials, agricultural chemicals, building materials andin the production process of various products such as medicinal preparations and the like. However, in most chlorine-related reaction processes, the utilization rate of chlorine resources is low, and chlorides mainly exist in the form of reaction intermediates and do not enter final target products. At present, more than 20 organic chlorine chemicals are available on a large scale in China, wherein large amounts of hydrogen chloride byproduct are produced from large-scale chlorine products such as isocyanate, methane chloride, epichlorohydrin and chloroacetic acid, and the problem of digestion and utilization of a large amount of hydrogen chloride byproduct and hydrochloric acid becomes a common problem restricting development of polyurethane, chlor-alkali, pesticide, pharmaceutical chemicals, chemical fertilizers and other industries.
At present, the most effective way for industrially treating the byproduct hydrogen chloride is to directly convert the byproduct hydrogen chloride into chlorine for recycling. On one hand, the method not only can solve the production pressure of a large amount of byproduct hydrogen chloride on enterprises, but also conforms to the economic development mode of resource circulation, and is vital to the promotion of the sustainable development of chlorine-related industries and the environmental protection. The method for preparing chlorine by catalytic oxidation of hydrogen chloride (also called Deacon reaction) has the advantages of simple and convenient operation, low energy consumption, no other side reaction, high efficiency and the like, and the specific stoichiometric formula is as follows:
Figure BDA0002386767140000011
among the hydrogen chloride oxidation catalysts reported in the prior art, ruthenium oxide-based catalysts supported on inert support materials are the main ones. Common inert support materials are titanium oxide, aluminum oxide, and silicon dioxide, for example, alpha-Al2O3、r-TiO2And so on. The activity of ruthenium oxide based catalysts depends on RuO on the support2The size of the particles. The smaller the particle size, the higher the activity of the catalyst-the active component is highly dispersed on the support surface.
At present, the mechanism research of ruthenium-based catalyst deactivation in hydrogen chloride oxidation atmosphere in the industry mainly comprises the following two aspects:
firstly, the chlorine preparation by HCl gas phase catalytic oxidation always faces the active center RuO of ruthenium-based catalyst2Is easy to sinter and deactivate, although the rutile phase is usedTiO2Or SnO2After being used as a carrier, the active component RuO is obviously improved2Stability under oxidizing atmosphere, but RuO2/TiO2Always faces to RuO in the process of industrial production and operation2Sintering deactivation and chlorination of3Leading to a situation where the reactivity is decreased.
② in the HCl oxidation system, raw gas constitutes a circulating gas from the system, the circulating gas is dried by concentrated sulfuric acid tower, inevitably carries SO2、H2SO4And the like, so that the sulfide enters the oxidation reactor together with the recycle gas, resulting in RuO (ruthenium oxide) as an active center of the ruthenium-based catalyst2React with the ruthenium sulfate to finally generate the ruthenium sulfate. The ruthenium sulfate salt can cover the active site of the ruthenium oxide microcrystal, and compared with the yield of the catalyst, the ruthenium sulfate salt can produce a certain amount of chlorine less per unit of catalyst under the condition of longer normal operation life, so that the production cost of the industrial chlorine is greatly improved.
Because ruthenium is expensive and the replacement cost of the catalyst is high, the deactivated catalyst needs to be regenerated, so that the utilization value of the noble metal ruthenium is provided.
CN101754808A describes a process for reactivating a ruthenium oxide containing hydrogen chloride oxidation catalyst, wherein the deactivated catalyst is contacted at 200 to 400 ℃ with oxygen or an inert gas which has no oxidizing or reducing properties and neither acidic nor basic properties. CN102271807A describes a regeneration method of catalyst containing ruthenium oxide for chlorination oxidation, wherein the deactivated catalyst is activated by reducing the catalyst in a gas flow of hydrogen chloride and any inert gas at 300-500 ℃, and then calcining the catalyst in an oxygen-containing gas flow at 200-450 ℃. CN102405298A the method comprises the following steps: a) reducing the ruthenium oxide-containing catalyst in a gas stream comprising hydrogen chloride and/or an inert gas at 300 to 500 ℃; b) treating the reduced catalyst comprising metallic ruthenium on a less soluble support material from step a) with hydrochloric acid in the presence of an oxygen-containing gas to dissolve the metallic ruthenium present on the support to ruthenium (III) chloride and obtain an aqueous ruthenium (III) chloride solution; c) the ruthenium (III) chloride solution from step b) is worked up further, if appropriate.
When the existing method is adopted to regenerate the ruthenium-based catalyst, experiments show that the following two operation defects still exist:
1. the existing reactor has the defects that the temperature of the hydrogen chloride gas is high and the flow rate is large after the treated hydrogen chloride gas is regenerated by the inactivated catalyst containing ruthenium oxide, the safety risk exists when the existing device condition is adopted for regeneration, and the pure HCl gas with high flow rate and high temperature can not be trapped.
2. The existing regeneration technology of chlorine catalyst prepared by hydrogen chloride oxidation does not provide an effective treatment method for ruthenium sulfate in the deactivated ruthenium-based catalyst, and the regenerated catalyst cannot recover to a higher activity level due to the coverage of the activity sites of the ruthenium oxide microcrystals.
Therefore, a method for simply regenerating the deactivated catalyst of the supported ruthenium oxide for preparing chlorine by oxidizing hydrogen chloride is needed, which can effectively reduce the influence of the regeneration process on the reaction system, treat the sulfur substances poisoned on the surface of the catalyst, reduce the coverage of the deactivated noble metal ruthenium salt on the active sites, and improve the regeneration activity and the regeneration life of the catalyst on the premise of having the technical effect of the existing regeneration method.
Disclosure of Invention
The invention aims to provide a regeneration method of a catalyst for preparing chlorine by oxidizing hydrogen chloride. The catalyst has the advantages of low cost, simple process, reproduction of the hydrogen chloride oxidation catalyst, shape maintenance and higher hydrogen chloride oxidation performance after regeneration.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a regeneration method of a catalyst for preparing chlorine by oxidizing hydrogen chloride comprises the following steps:
(1) roasting the inactivated ruthenium-based catalyst to obtain a regenerated catalyst I;
(2) putting the regenerated catalyst I into an aqueous solution of sulfamic acid, carrying out ultrasonic treatment simultaneously, and then separating out solids to obtain a regenerated catalyst II;
(3) putting the regenerated catalyst II into a hydrochloric acid solution, carrying out co-heat treatment on the catalyst and the hydrochloric acid solution, and then stirring and drying to obtain a regenerated catalyst III;
(4) the regenerated catalyst III is put into O2The regenerated ruthenium-based catalyst is obtained by roasting.
In the step (1) of the regeneration method, the inactivated ruthenium-based catalyst is a supported ruthenium catalyst, and the active component is RuO2The carrier is selected from TiO2、Al2O3、SiO2Etc., preferably TiO2；
The supported ruthenium catalyst can be prepared by any currently available method, and in some examples of the invention, is preferably prepared by an impregnation method, as follows: the carrier is added into aqueous solution of ruthenium salt for dipping, and then the carrier is prepared by drying and roasting. Among them, ruthenium salts such as ruthenium chloride, ruthenium nitrate and the like are preferable.
The roasting treatment is carried out, wherein the roasting temperature is 300-600 ℃, preferably 400-550 ℃, such as 300 ℃, 400 ℃, 500 ℃, 550 ℃, 600 ℃ and the like; the roasting time is 2-10 h, preferably 4-7 h, such as 2h, 4h, 6h, 10h, 7h and the like.
In some examples of the invention, step (1) is specifically operative to: and roasting the deactivated ruthenium-based catalyst at the temperature of 300-600 ℃, preferably 400-550 ℃, for 2-10 hours, preferably 4-7 hours in an air atmosphere to obtain a regenerated catalyst I. The aim of the step is to mix carbon deposit and single metal Ru on the surface of the deactivated catalyst with O at high temperature by roasting operation2Fully reacts to eliminate carbon deposition, and simultaneously converts the single metal Ru into RuO2。
In step (2) of the regeneration method of the present invention, the concentration of the sulfamic acid aqueous solution is 5 to 30wt%, preferably 10 to 20wt%, such as 5 wt%, 10wt%, 15 wt%, 20wt%, 30 wt%. The dosage of the sulfamic acid aqueous solution is 2-10 times, preferably 4-6 times, such as 2 times, 4 times, 5 times, 6 times and 10 times of the mass of the regenerated catalyst I.
The ultrasonic treatment is carried out for 20-60 min, preferably 30-45 min, such as 20min, 30min, 40min, 45min and 60 min; the ultrasonic power is 100-500 w, preferably 200-300 w, such as 100w, 200w, 250w, 300w, 500 w.
The separation method comprises the step of screening through a standard screen, wherein the aperture of the standard screen is 100-400 meshes, preferably 150-300 meshes, such as 100 meshes, 150 meshes, 200 meshes, 300 meshes and 400 meshes.
In some examples of the invention, step (2) is specifically operative to: placing the regenerated catalyst I into sulfamic acid water solution with the concentration of 5-30 wt%, preferably 10-20 wt%, and assisting with ultrasonic cleaning, wherein the ultrasonic time is 20-60 min, preferably 30-45 min, the ultrasonic power is 100-500 w, preferably 200-300 w, screening through a standard sieve with 100-400 meshes, preferably 200-300 meshes, and collecting solids on the sieve to obtain a regenerated catalyst II. The surface of the deactivated ruthenium chloride hydroxide-based catalyst is attached with difficultly regenerated sulfide products such as ruthenium sulfate and the like, after the treatment of the operation step, the sulfide products such as ruthenium sulfate and sulfamic acid, the surface of the regenerated catalyst I is covered with active sites of the catalyst, are combined to form a ruthenium sulfate-sulfamic acid complex, and then the deactivated ruthenium sulfate is separated from the surface of the regenerated catalyst I in a liquid phase complex form through ultrasonic treatment and standard sieve screening treatment, is transferred into filtrate and is removed.
In step (3) of the regeneration method of the present invention, the hydrochloric acid solution is an aqueous solution of hydrochloric acid, and the concentration of the aqueous solution is 2 to 10wt%, preferably 4 to 8wt%, such as 2 wt%, 4 wt%, 6 wt%, 8wt%, 10 wt%. Further, the amount of the hydrochloric acid solution is 115-140% by mass, preferably 120-130% by mass, such as 115%, 120%, 125%, 130%, 140% by mass, of the regenerated catalyst ii.
The co-heat treatment is carried out at a temperature of 80-150 ℃, preferably 100-120 ℃, such as 80 ℃, 100 ℃, 110 ℃, 120 ℃ and 150 ℃; a pressure of 0.1 to 0.6MPa (G), preferably 0.1 to 0.3MPa (G), such as 0.1MPa (G), 0.2MPa (G), 0.3MPa (G), 0.6MPa (G); the time is 0.5-50 h, preferably 10-20 h, such as 0.5h, 10h, 15h, 20h and 50 h.
The stirring is carried out at the temperature of 105-150 ℃, preferably at the temperature of 110-130 ℃, such as 105 ℃, 110 ℃, 120 ℃, 130 ℃ and 150 ℃; the time is 2-10 h, preferably 4-6 h, such as 2h, 4h, 5h, 6h and 10 h; the pressure is 0.1 to 0.6MPa (G), preferably 0.1 to 0.3MPa (G), such as 0.1MPa (G), 0.2MPa (G), 0.4MPa (G); the stirring speed is 600-1500 r/min, preferably 900-1200 r/min, such as 600r/min, 900r/min, 1100r/min, 1200r/min, 1500 r/min.
The drying treatment is carried out at the drying temperature of 105-150 ℃, preferably at 110-120 ℃, such as 105 ℃, 110 ℃, 115 ℃ and 120 ℃; the drying time is 2-10 h, preferably 2-6 h, such as 2h, 4h and 6 h.
In some examples of the invention, step (3) is specifically operative to: soaking the regenerated catalyst II in 2-10 wt%, preferably 4-8 wt% hydrochloric acid water solution, the amount of the hydrochloric acid water solution is 15-40 wt%, preferably 20-30 wt% of the deactivated ruthenium-based catalyst, the temperature is 80-150 ℃, preferably 100-120 ℃, the pressure is 0.1-0.6 Mpa (G), preferably 0.1-0.3 Mpa (G), the catalyst and the hydrochloric acid solution are subjected to co-heat treatment for 0.5-50 h, preferably 10-20 h, so that RuO highly aggregated on the surface of the deactivated hydrogen chloride oxidation catalyst is formed2Fully react with hydrochloric acid to generate RuCl3The catalyst is dispersed on the surface of a carrier uniformly (in a liquid phase), after the co-heat treatment is finished, the catalyst is stirred for 2 to 10 hours, preferably 4 to 6 hours at the temperature of 105 to 150 ℃, the pressure of 0.1 to 0.4MPa (G), preferably 0.1 to 0.2MPa (G) and the rotating speed of 600 to 1500r/min, preferably 900 to 1200r/min, and then is dried for 2 to 10 hours, preferably 2 to 6 hours at the temperature of 105 to 150 ℃, preferably 105 to 120 ℃, so as to obtain a regenerated catalyst III;
in the step (4) of the regeneration method, the roasting temperature is 250-350 ℃, preferably 280-310 ℃, such as 250 ℃, 280 ℃, 300 ℃ and 310 ℃; the roasting time is 0.5-50 h, preferably 2-10 h, such as 0.5h, 2h, 5h and 10 h; the gas mass space velocity in the roasting process is 0.03-0.3 h-1Preferably 0.05 to 0.2h-1E.g. 0.03h-1、0.05h-1、0.1h-1、0.2h-1、0.3h-1。
In some examples of the invention, step (4) is specifically operative to: the regenerated catalyst III is used for a mass space velocity of 0.03-0.3 h-1Preferably 0.05-0.2 h-1O of (A) to (B)2In the method, the temperature is controlled to be 250-350 ℃, preferably 280-310 DEG CRoasting at 0.5-50 deg.c for 2-10 hr preferably. RuCl capable of regenerating surface of catalyst III by roasting3Oxidation to RuO2Generated RuO2The catalyst is highly dispersed on the surface of a catalyst carrier, so that the crystalline phase and the crystalline form of the active component of the catalyst are promoted to be restored to the state of a fresh catalyst, and the regenerated ruthenium-based catalyst is obtained.
The catalyst regeneration method provided by the invention comprises the steps of firstly roasting RuCl on the surface of a ruthenium-based catalyst at high temperature3Reaction to RuO2Removing carbon deposition on the surface of the catalyst, and fully chlorinating the hydrochloric acid to obtain highly dispersed RuO for the next step2Pretreatment is carried out, and the regeneration efficiency is improved. Then sulfur substances generated by poisoning on the surface of the catalyst are removed through sulfamic acid treatment, the problem that the deactivated noble metal ruthenium salt covers an active point position is solved, and the regeneration activity and the regeneration life of the catalyst are further improved. Then the active component RuO is added by adding hydrochloric acid with proper concentration2Sufficient chlorination to produce RuCl3And then dried by stirring sufficiently to make RuCl3Can be well dispersed in the carrier TiO2Surface, final RuCl production by high temperature oxygen calcination3Fully oxidizing to obtain the regenerated ruthenium-based catalyst.
The regenerated ruthenium-based catalyst obtained by the method can reach 80 percent or more of the service life of a fresh catalyst. The method can reduce the influence of the regeneration process on a reaction system, improve the regeneration activity and the regeneration efficiency of the catalyst, reduce the consumption of waste acid, reduce the influence on the environment, treat sulfur substances poisoned on the surface of the catalyst, reduce the coverage of the inactivated noble metal ruthenium salt on an active site, and further improve the regeneration activity and the regeneration service life of the catalyst.
Detailed Description
The invention is further illustrated by the following examples. The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical features of the present invention and to enable the same to be carried into effect in accordance with the present specification, preferred embodiments of the present invention are described in detail below.
The embodiment of the invention has the following main raw material sources:
name(s) Manufacturer of the product Purity of
RuCl3·6H2O RIYN >99.5％
TiO(OH)2 All industries in Hubei province 98％
Sulfamic acid Shanghai test Analytical purity
Hydrochloric acid Shanghai test 31％
Ruthenium-based catalyst (RuO) for use in the present invention2/TiO2Catalyst) was prepared by the following method:
(1) using metatitanic acid (TiO (OH)2) Taking a certain amount of rutile seed metatitanic acid powder as a precursor, putting the rutile seed metatitanic acid powder into a muffle furnace, and roasting at 550 ℃ respectively to obtain rutile type titanium dioxide as a carrier for later use;
(2) weighing 5% of ruthenium trichloride hydrate (RuCl) based on the weight of the carrier3·xH2O) in a beaker, adding water and stirring to RuCl3·xH2Completely dissolving O to obtain a hydrated ruthenium trichloride aqueous solution;
(3) taking the carrier TiO obtained by roasting in the step (1)2Adding the mixture into the aqueous solution of ruthenium trichloride hydrate in the step (2), stirring for 5 hours at room temperature, transferring the suspension into a rotary evaporation device, carrying out rotary evaporation at 90 ℃, and drying the obtained preliminarily dried catalyst for 24 hours;
(4) the dried catalyst is put into a muffle furnace to be roasted for 8 hours at the temperature of 500 ℃, and the supported RuO is prepared2/TiO2A catalyst.
Loading RuO as above2/TiO2The catalyst is used for preparing chlorine by oxidizing hydrogen chloride, and the conversion rate is 85% at the initial temperature of 300 ℃. After running for 1000h, the temperature needs to be raised to about 330 ℃, and the conversion rate reaches 85%. Continuing the reaction, and judging RuO when the conversion rate reaches 85% only when the temperature needs to be raised to more than 400 DEG C2/TiO2The catalyst was completely deactivated, at which point the sulfur content in the deactivated catalyst was 0.15 wt% as measured by XRF.
The reaction conditions for preparing chlorine by oxidizing hydrogen chloride adopted by the embodiment of the invention are controlled as follows: v (HCl): v (O)2) 2:1, HCl mass space velocity of 0.67h-1The initial reaction temperature is controlled to be 300 ℃, and the catalyst conversion rate is ensured to reach 80% by increasing the temperature in the experimental period.
The main test methods adopted in the examples and comparative examples of the present invention are as follows:
1. the test instrument is a fixed bed small test reaction device, and the evaluation method comprises the steps of carrying out redox titration and acid-base titration analysis according to an operation method, and calculating the HCl conversion rate and the sampling chlorine balance.
2. The method for calculating the recoverable service life of the catalyst comprises the following steps: RuO2/TiO2The change trend of the service life of the catalytic HCl oxidation catalyst is stable and linear reduction, so that the normal activity temperature change interval of the catalyst reaching 85% conversion rate is 300-400 ℃, the recoverable service life of the catalyst is converted by the temperature value reaching 85% conversion rate, namely 300 ℃ reaches 85% after regeneration, the recoverable service life of the catalyst is 100%, 400 ℃ reaches 85%, and the recoverable service life of the catalyst is 0%. E.g. after regeneration85% at 330 deg.C, and the catalyst has recoverable service life of about 70%.
Example 1:
(1) taking deactivated RuO2/TiO21000g of catalyst is subjected to roasting treatment for 6 hours at the high temperature of 500 ℃ to obtain a regenerated catalyst I;
(2) putting the regenerated catalyst I into an aqueous solution of sulfamic acid with the concentration of 15 wt% and the mass of 5 times of the regenerated catalyst I, and assisting ultrasonic cleaning, wherein the time is 40min, the ultrasonic power is 250w, and the regenerated catalyst I is obtained by sieving through a standard sieve of 200 meshes, and the solid is used as a regenerated catalyst II;
(3) soaking the regenerated catalyst II in 6 wt% concentration hydrochloric acid solution in the amount of 125 wt% of the regenerated catalyst II, heat treating at 0.2MPa (G) at 110 deg.c for 15 hr, stirring at 0.2MPa (G) and 120 deg.c at 1100r/min for 5 hr, and stoving at 115 deg.c for 4 hr to obtain regenerated catalyst III;
(4) the regenerated catalyst III is added into O2The roasting is carried out for 5 hours, the temperature is controlled at 300 ℃, and the air speed of the gas is controlled at 0.1 hour-1To obtain regenerated RuO2/TiO2A catalyst.
Regenerating the RuO2/TiO2The catalyst is used for preparing chlorine by oxidizing hydrogen chloride, and the reaction conditions are as follows: temperature 320 ℃, v (hcl): v (O)2) 2:1, HCl mass space velocity of 0.67h-1And the hydrogen chloride conversion rate is 85 percent, which shows that the catalyst prepared by the method can recover more than 80 percent of the original service life of the catalyst, and the sulfur content in the regenerated catalyst is 0.02 percent by weight through XRF detection.
Example 2:
(1) taking the inactivated RuO2/TiO2Roasting 1000g of catalyst at the high temperature of 300 ℃ for 2h to obtain regenerated catalyst I;
(2) placing the regenerated catalyst I in 2 times of sulfamic acid aqueous solution with the concentration of 5 wt% by mass, assisting with ultrasonic cleaning, carrying out 20min, carrying out 100w of ultrasonic power, and screening by using a standard sieve of 100 meshes to obtain a solid, namely a regenerated catalyst II;
(3) soaking the regenerated catalyst II in 2 wt% concentration hydrochloric acid solution in the amount of 115 wt% of the regenerated catalyst II, heat treating at 0.1MPa (G) at 80 deg.c for 0.5 hr, stirring at 0.1MPa (G) and 105 deg.c at 600r/min for 2 hr, and stoving at 105 deg.c for 2 hr to obtain regenerated catalyst III;
(4) the regenerated catalyst III is added into O2The roasting is carried out for 0.5h, the temperature is controlled at 250 ℃, and the gas mass space velocity is controlled at 0.03h-1To obtain regenerated RuO2/TiO2A catalyst.
Regenerating the RuO2/TiO2The catalyst is used for preparing chlorine by oxidizing hydrogen chloride, and the reaction conditions are as follows: temperature 350 ℃, v (hcl): v (O)2) 2:1, HCl space velocity 0.67h-1And the hydrogen chloride conversion rate is 85%, which indicates that the catalyst prepared by the method can recover more than 50% of the original service life of the catalyst, and the sulfur content in the regenerated catalyst is 0.081% by XRF detection.
Example 3:
(1) taking deactivated RuO2/TiO21000g of catalyst is roasted for 10 hours at the high temperature of 600 ℃ to obtain a regenerated catalyst I;
(2) putting the regenerated catalyst I into a 10-time mass of 30wt% sulfamic acid aqueous solution, and performing ultrasonic cleaning for 60min at the ultrasonic power of 500w, and sieving by a standard sieve of 400 meshes to obtain a solid, namely a regenerated catalyst II;
(3) soaking the regenerated catalyst II in 10wt% concentration hydrochloric acid solution of 140 wt% of the regenerated catalyst II, heat treating at 0.6MPa (G) at 150 deg.c for 50 hr, stirring at 0.4MPa (G) and 150 deg.c for 10 hr at 1500r/min, and stoving at 120 deg.c for 6 hr to obtain regenerated catalyst III;
(4) the regenerated catalyst III is added into O2The roasting is carried out for 0.5h, the temperature is controlled at 310 ℃, and the gas space velocity is controlled at 0.3h-1To obtain regenerated RuO2/TiO2A catalyst.
Regenerating the RuO2/TiO2The catalyst is used for preparing chlorine by oxidizing hydrogen chloride, and the reaction conditions are as follows: temperature 360 ℃, v (hcl): v (O)2) 2:1, HCl mass space velocity of 0.67h-1And the hydrogen chloride conversion rate is 85%, which indicates that the catalyst prepared by the method can recover more than 40% of the original service life of the catalyst, and the sulfur content in the regenerated catalyst is 0.09 wt% by XRF detection.
Example 4:
(1) taking the inactivated RuO2/TiO2Roasting 1000g of catalyst at the high temperature of 400 ℃ for 4h to obtain regenerated catalyst I;
(2) putting the regenerated catalyst I into an aqueous solution of sulfamic acid with the concentration of 10wt% and the mass of 4 times of that of the regenerated catalyst I, and assisting with ultrasonic cleaning for 30min, wherein the ultrasonic power is 200w, and screening the regenerated catalyst I by a standard sieve of 150 meshes to obtain a solid, namely a regenerated catalyst II;
(3) soaking the regenerated catalyst II in 4 wt% concentration hydrochloric acid solution in the amount of 120 wt% of the regenerated catalyst II, heat treating at 0.1MPa (G) at 100 deg.c for 10 hr, stirring at 0.1MPa (G) and 110 deg.c at 900r/min for 4 hr, and stoving at 110 deg.c for 2 hr to obtain regenerated catalyst III;
(4) the regenerated catalyst III is added into O2Roasting for 2 hours, controlling the temperature at 280 ℃ and the gas space velocity at 0.05 hour-1To obtain regenerated RuO2/TiO2A catalyst.
Regenerating the RuO2/TiO2The catalyst is used for preparing chlorine by oxidizing hydrogen chloride, and the reaction conditions are as follows: temperature 337 ℃, v (hcl): v (O)2) 2:1, HCl mass space velocity of 0.67h-1And the hydrogen chloride conversion rate is 85 percent, which shows that the catalyst prepared by the method can recover more than 63 percent of the original service life of the catalyst, and the sulfur content in the regenerated catalyst is 0.06 percent by weight through XRF detection.
Example 5:
(1) taking the inactivated RuO2/TiO2Roasting 1000g of catalyst at the high temperature of 550 ℃ for 7 hours to obtain regenerated catalyst I;
(2) putting the regenerated catalyst I into an aqueous solution of sulfamic acid with the concentration of 20wt% and the mass of 6 times of that of the regenerated catalyst I, and assisting with ultrasonic cleaning for 45min, wherein the ultrasonic power is 300w, and screening the regenerated catalyst I by a standard sieve of 300 meshes to obtain a solid, namely a regenerated catalyst II;
(3) soaking the regenerated catalyst II in 8wt% concentration hydrochloric acid solution of 130 wt% of the regenerated catalyst II, co-heat treating at 0.3MPa (G) at 120 deg.c for 20 hr, stirring at 0.2MPa (G) and 130 deg.c at 1200r/min for 6 hr, and stoving at 120 deg.c for 6 hr to obtain regenerated catalyst III;
(4) the regenerated catalyst III is added into O2The roasting is carried out for 10 hours, the temperature is controlled at 310 ℃, and the gas space velocity is controlled at 0.2 hour-1To obtain regenerated RuO2/TiO2A catalyst.
Regenerating the RuO2/TiO2The catalyst is used for preparing chlorine by oxidizing hydrogen chloride, and the reaction conditions are as follows: temperature 330 ℃, v (hcl): v (O)2)2:1, HCl mass space velocity 0.67h-1And the hydrogen chloride conversion rate is 85 percent, which shows that the catalyst prepared by the method can recover more than 70 percent of the original service life of the catalyst, and the sulfur content in the regenerated catalyst is 0.05 percent by weight through XRF detection.
Comparative example 1:
taking deactivated RuO2/TiO2Catalyst regeneration: the only difference from example 1 is that an aqueous sulfamic acid solution having a concentration of 15 wt% was replaced by NH having a concentration of 15 wt%3An aqueous solution.
Regenerating the RuO2/TiO2The catalyst is used for preparing chlorine gas by oxidizing hydrogen chloride, 362 ℃, v (HCl): v (O)2) 2:1, HCl mass space velocity of 0.67h-1The conversion rate of the catalyst obtained under the condition reaches about 85 percent, which shows that the catalyst prepared by the method can recover over 38 percent of the original service life of the catalyst, and the sulfur content in the regenerated catalyst V is 0.11 percent by weight through XRF detection.
Comparative example 2:
taking the inactivated RuO2/TiO2Catalyst regeneration: the only difference from example 1 is that an aqueous solution of sulfamic acid having a concentration of 15 wt% was replaced with an aqueous solution of sulfuric acid having a concentration of 15 wt%.
Regenerating the RuO2/TiO2Catalyst for preparing chlorine by hydrogen chloride oxidationGas, 370 ℃, v (HCl): v (O)2) 2:1, HCl mass space velocity of 0.67h-1The conversion rate of the catalyst can reach about 85% under the condition, which shows that the catalyst prepared by the method can recover more than 30% of the original service life of the catalyst, and the sulfur content in the regenerated catalyst V is 0.15 wt% by XRF detection.
Comparative example 3:
(1) in a fixed bed reactor with a diameter of 24mm, a height of 990mm and a bed height of 300 to 350mm, to deactivated RuO2/TiO2292.5 l.h of catalyst is introduced at 400 DEG C-1The HCl of (a) purges the catalyst.
(2) After 24h, the gas was changed to 60 l.h-1O of (a)2And 240 l.h-1N of (A)2And the catalyst was reactivated by calcination at 400 c for an additional 30 minutes.
(3) After this treatment, at 360 ℃, v (hcl): v (O)2) 2:1, mass space velocity of 0.67h-1Under the condition, the catalyst achieves 85% conversion rate to HCl; the catalyst prepared by the method can recover more than 40% of the original service life of the catalyst, and XRF detection shows that the sulfur content in the regenerated catalyst V is 0.10 wt%.
Comparative example 4: taking deactivated RuO2/TiO2Catalyst regeneration: the only differences from example 1 are: replacing the operation steps of the step (2) and the step (3)
(1) Taking deactivated RuO2/TiO21000g of catalyst is subjected to roasting treatment for 6 hours at the high temperature of 500 ℃ to obtain a regenerated catalyst I;
(2) the regenerated catalyst I is soaked in 8wt% hydrochloric acid aqueous solution, the dosage of which is inactivated RuO2/TiO230 percent of the weight of the catalyst, keeping the temperature of 110 ℃ for heat treatment for 15h under 0.2MPa (G), then stirring for 5h under the speed of 1200r/min under the conditions of 0.2MPa (G) and 110 ℃, and drying for 4h under the temperature of 105 ℃ to obtain a regenerated catalyst II;
(3) placing the regenerated catalyst II in 1/5 of the mass of an aqueous solution of sulfamic acid with the concentration of 15 wt%, and assisting ultrasonic cleaning for 45min at the ultrasonic power of 300w, and sieving the regenerated catalyst II by a standard sieve of 200 meshes to obtain a solid, namely a regenerated catalyst III;
(4) the regenerated catalyst III is reacted with O2The roasting is carried out for 5 hours, the temperature is controlled at 300 ℃, and the air speed of the gas is controlled at 0.1 hour-1To obtain regenerated RuO2/TiO2A catalyst.
Regenerating the RuO2/TiO2The catalyst is used for preparing chlorine by oxidizing hydrogen chloride, and the reaction conditions are as follows: temperature at 378 ℃, v (hcl): v (O)2) 2:1, HCl mass space velocity of 0.67h-1And the hydrogen chloride conversion rate is 85 percent, which shows that the catalyst prepared by the method only recovers over 22 percent of the original service life of the catalyst, and the sulfur content in the regenerated catalyst is 0.14 percent by weight through XRF detection.
The above description includes the preferred embodiments of the present invention, and is not intended to limit the present invention, and it should be noted that, for those skilled in the art, it is possible to make several modifications and variations without departing from the technical principle of the present invention, and these modifications and variations should be regarded as the protection scope of the present invention.

Claims (22)

1. A regeneration method of a catalyst for preparing chlorine by oxidizing hydrogen chloride is characterized by comprising the following steps:
(1) roasting the deactivated ruthenium-based catalyst to obtain a regenerated catalyst I;
(2) putting the regenerated catalyst I into an aqueous solution of sulfamic acid, carrying out ultrasonic treatment simultaneously, and then separating out solids to obtain a regenerated catalyst II;
(3) putting the regenerated catalyst II into a hydrochloric acid solution, carrying out co-heat treatment on the catalyst and the hydrochloric acid solution, and then stirring and drying to obtain a regenerated catalyst III;
(4) the regenerated catalyst III is put into O2The regenerated ruthenium-based catalyst is obtained by roasting.
2. The regeneration method according to claim 1, wherein, in the step (1), the deactivated ruthenium-based catalyst is a supported ruthenium catalyst, and the active component is RuO2The carrier is selected from TiO2、Al2O3、SiO2。
3. Regeneration process according to claim 2, characterised in that the support is TiO2。
4. The regeneration method according to claim 1, wherein in the step (1), the roasting treatment is performed at a roasting temperature of 300 to 600 ℃ for 2 to 10 hours.
5. The regeneration method according to claim 4, wherein the roasting temperature is 400 to 550 ℃ and the roasting time is 4 to 7 hours.
6. The regeneration method of claim 1, wherein in the step (2), the concentration of the sulfamic acid aqueous solution is 5-30 wt%; the dosage of the sulfamic acid aqueous solution is 2-10 times of the mass of the regenerated catalyst I.
7. The regeneration method according to claim 6, wherein the concentration of the sulfamic acid aqueous solution is 10 to 20 wt%.
8. The regeneration method according to claim 6, wherein the amount of the sulfamic acid aqueous solution is 4 to 6 times the mass of the regenerated catalyst I.
9. The regeneration method of claim 1, wherein in the step (2), the ultrasonic treatment is performed for 20-60 min at an ultrasonic power of 100-500 w.
10. The regeneration method of claim 9, wherein the ultrasonic time is 30-45 min, and the ultrasonic power is 200-300 w.
11. The regeneration method of claim 1, wherein in the step (2), the separation is performed by sieving through a standard sieve with a pore size of 100-400 meshes.
12. The regeneration process of claim 11, wherein the standard screen size is 150 to 300 mesh.
13. The regeneration method according to claim 1, wherein in the step (3), the hydrochloric acid solution is an aqueous hydrochloric acid solution, and the concentration of the aqueous hydrochloric acid solution is 2 to 10 wt%.
14. The regeneration method according to claim 13, wherein the concentration of the aqueous hydrochloric acid solution is 4 to 8 wt%.
15. The regeneration method according to claim 1, wherein in the step (3), the amount of the hydrochloric acid solution is 115-140% of the mass of the regenerated catalyst II.
16. The regeneration method as claimed in claim 15, wherein the amount of the hydrochloric acid solution is 120-130% of the mass of the regenerated catalyst II.
17. The regeneration method according to claim 1, wherein in the step (3), the co-heat treatment is performed at a temperature of 80 to 150 ℃ under a pressure of 0.1 to 0.6MPaG for a period of 0.5 to 50 hours.
18. The recycling method of claim 17, wherein the co-heat treatment is performed at 100 to 120 ℃ under 0.1 to 0.3MPaG for 10 to 20 hours.
19. The regeneration method of claim 1, wherein in the step (3), the stirring is performed at 105-150 ℃, for 2-10 h, under 0.1-0.6 MPaG and at a stirring speed of 600-1500 r/min; and/or
And (3) drying, wherein the drying temperature is 105-150 ℃, and the drying time is 2-10 h.
20. The regeneration method of claim 19, wherein the stirring is performed at a temperature of 110 to 130 ℃, for 4 to 6 hours, under a pressure of 0.1 to 0.3MpaG, and at a stirring rate of 900 to 1200 r/min; and/or
And (3) drying, wherein the drying temperature is 110-120 ℃, and the drying time is 2-6 h.
21. The regeneration method of claim 1, wherein in the step (4), the roasting temperature is 250-350 ℃, the roasting time is 0.5-50 h, and the gas mass space velocity in the roasting process is 0.03-0.3 h-1。
22. The regeneration method of claim 21, wherein the roasting is carried out at a roasting temperature of 280-310 ℃ for 2-10 h, and the gas mass space velocity in the roasting process is 0.05-0.2 h-1。
CN202010100666.XA 2020-02-19 2020-02-19 Regeneration method of catalyst for preparing chlorine by oxidizing hydrogen chloride Active CN113275020B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010100666.XA CN113275020B (en) 2020-02-19 2020-02-19 Regeneration method of catalyst for preparing chlorine by oxidizing hydrogen chloride

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010100666.XA CN113275020B (en) 2020-02-19 2020-02-19 Regeneration method of catalyst for preparing chlorine by oxidizing hydrogen chloride

Publications (2)

Publication Number Publication Date
CN113275020A CN113275020A (en) 2021-08-20
CN113275020B true CN113275020B (en) 2022-07-12

Family

ID=77274875

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010100666.XA Active CN113275020B (en) 2020-02-19 2020-02-19 Regeneration method of catalyst for preparing chlorine by oxidizing hydrogen chloride

Country Status (1)

Country Link
CN (1) CN113275020B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115155672A (en) * 2022-06-24 2022-10-11 西安近代化学研究所 Regeneration method of hydrogen chloride oxidation catalyst

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4656147A (en) * 1984-04-05 1987-04-07 Mitsubishi Jukogyo Kabushiki Kaisha Method for recovering denitrating catalyst for ammonia catalytic reduction
CN101977683A (en) * 2008-03-22 2011-02-16 拜尔材料科学股份公司 Process for regenerating a catalyst containing ruthenium or a ruthenium compound poisoned by sulfur in the form of a sulfur compound
CN104785271A (en) * 2014-01-21 2015-07-22 万华化学集团股份有限公司 Preparation method of catalyst used for chlorine preparation, catalyst, and method used for preparing chlorine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4656147A (en) * 1984-04-05 1987-04-07 Mitsubishi Jukogyo Kabushiki Kaisha Method for recovering denitrating catalyst for ammonia catalytic reduction
CN101977683A (en) * 2008-03-22 2011-02-16 拜尔材料科学股份公司 Process for regenerating a catalyst containing ruthenium or a ruthenium compound poisoned by sulfur in the form of a sulfur compound
CN104785271A (en) * 2014-01-21 2015-07-22 万华化学集团股份有限公司 Preparation method of catalyst used for chlorine preparation, catalyst, and method used for preparing chlorine

Also Published As

Publication number Publication date
CN113275020A (en) 2021-08-20

Similar Documents

Publication Publication Date Title
CN102405298B (en) Method for recovering ruthenium from spent catalysts containing ruthenium oxide
WO2019137020A1 (en) Transition metal and nitrogen co-doped carbon composite material for use in formaldehyde purification and preparation method therefor
CN107159313A (en) A kind of core shell structure TiO2The preparation method of nanotube@Ti MOF catalyst
CN111097422B (en) Catalyst for removing formaldehyde and preparation method and application thereof
WO2013131453A1 (en) Method for recovering ruthenium from waste catalyst of aluminum oxide loaded with ruthenium
CN110368924A (en) A kind of bismuth titanates/bismuth/pucherite compound photochemical catalyst and its application in photo-thermal catalytic purification organic gaseous contamination object
CN113996291A (en) Low-temperature HVOCs catalytic combustion catalyst, and preparation method and application thereof
CN101357337B (en) Heavy oil hydrogenating treatment catalyst and preparation method thereof
CN111744521A (en) Method for preparing cobaltosic oxide with different morphologies in recoverable mode by taking metal organic framework as precursor ligand and application of method
CN112609079B (en) Treatment and recovery method for regeneration waste liquid of inactivated denitration catalyst and application thereof
CN113275020B (en) Regeneration method of catalyst for preparing chlorine by oxidizing hydrogen chloride
WO2013131451A1 (en) Method for preparing solid nitrosyl ruthenium nitrate by using waste catalyst containing ruthenium
CN108906044B (en) Manganese-cerium-ruthenium composite oxide catalyst and preparation method and application thereof
CN114774701A (en) Resource utilization method of industrial waste salt and waste denitration catalyst
CN110586200B (en) Regeneration method of gold-carbon catalyst for acetylene hydrochlorination
US20150360210A1 (en) Process for the oxidation of hydrogen chloride over a catalyst having a low surface roughness
CN113877638B (en) Preparation method for preparing denitration and dioxin removal VOCs integrated catalyst by fractional precipitation method and prepared catalyst
CN108435171A (en) The preparation method and a kind of method of selective catalytic oxidation glycerine DHA of a kind of bimetallic Pt-Bi catalyst
CN107670697B (en) Catalyst for catalyzing selective oxidation of cyclohexane by visible light and preparation method thereof
CN111468159B (en) MOF-derived catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method thereof
CN107952436A (en) A kind of preparing chlorine by oxidizing hydrogen chloride copper-zirconium based catalyst and its preparation method and application
CN101722019A (en) Catalyst and process for preparing chlorine by gas phase oxidation
CN113893662B (en) Novel high-temperature dechlorinating agent and preparation method thereof
CN115999607A (en) Preparation method and application of hydrogen chloride catalytic oxidation catalyst
JPH0413283B2 (en)

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