CN112090433B - Preparation and application of glyoxylic acid methyl ester catalyst - Google Patents
Preparation and application of glyoxylic acid methyl ester catalyst Download PDFInfo
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- CN112090433B CN112090433B CN202010967411.3A CN202010967411A CN112090433B CN 112090433 B CN112090433 B CN 112090433B CN 202010967411 A CN202010967411 A CN 202010967411A CN 112090433 B CN112090433 B CN 112090433B
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
Abstract
The invention relates to preparation and application of a methyl glyoxylate catalyst, and belongs to the technical field of catalyst preparation. The preparation and application of the methyl glyoxylate catalyst synthesize a catalyst with excellent performance by taking iron phosphate and cobalt phosphate as carriers and loading highly dispersed iron oxide and cobalt oxide on the surface of the carrier, the catalyst is used for catalyzing oxygen to oxidize methyl glycolate to selectively oxidize methyl glyoxylate to synthesize methyl glyoxylate, the same raw material is used for simultaneously obtaining the carrier and the active component required by the catalyst, the catalyst is applied to synthesize methyl glyoxylate by using methyl glycolate to obtain better catalytic effect, the conversion rate of the raw material and the target selectivity are both improved compared with the traditional catalyst, and the catalyst has wide application prospect.
Description
Technical Field
The invention relates to preparation and application of a methyl glyoxylate catalyst, and belongs to the technical field of catalyst preparation.
Background
Methyl glyoxylate has chemical properties of aldehyde and ester, so that methyl glyoxylate is widely applied to the fields of chemical industry, medicines, materials and the like, and attracts the attention of researchers. Various methods for producing methyl glyoxylate have been reported, but the development of the methyl glyoxylate is limited by the defects of severe reaction conditions, poor product quality, low yield and the like. In comparison, the method for preparing the glyoxylic acid methyl ester by oxidizing the methyl glycolate has the advantages of simple process, low cost, high product quality and environmental protection, and has the greatest development prospect.
Many transition metals have been used as catalysts for the oxidation of alcohols to produce aldehydes. Among them, the iron, copper, molybdenum, palladium and vanadium based catalysts have the most excellent performance. At present, researchers mainly focus on the research on the catalyst system in two directions of iron-based supported molybdenum oxide or vanadium-based supported titanium oxide. Iron phosphate and cobalt phosphate are used as carriers, highly dispersed iron oxide and cobalt oxide are loaded on the surfaces of the carriers, a catalyst with excellent performance is obtained, and the catalyst is used for catalyzing oxygen to oxidize methyl glycolate to selectively oxidize and synthesize methyl glyoxylate, so that a good catalytic effect is obtained.
In view of the above drawbacks, the present inventors have made active research and innovation to create a preparation and application of glyoxylic acid methyl ester catalyst, so that glyoxylic acid methyl ester catalyst has industrial application value.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method and application of a glyoxylic acid methyl ester catalyst.
The invention relates to a preparation method of a glyoxylic acid methyl ester catalyst, which comprises the following specific preparation steps:
(1) Preparation of the precursor
Adding iron phosphate and cobalt nitrate into deionized water containing glucose, performing two procedures of coarse grinding and fine grinding, mixing and grinding the iron phosphate, the cobalt nitrate and the glucose solution into grinding slurry, putting the grinding slurry into an oven for drying, and crushing the dried material;
(2) Preparation of the catalyst
And (3) putting the crushed material into a muffle furnace with an inert atmosphere, and carrying out temperature programming and roasting to obtain a catalyst finished product.
Further, the time for mixing and grinding the ferric phosphate, the cobalt nitrate and the glucose solution in the step (1) is 3 hours.
Further, the drying temperature of the grinding slurry in the step (1) is 120 ℃, and the drying time is 12 hours.
Further, the termination temperature of the temperature programming in the step (2) is 750 ℃, and the temperature programming rate is 10 ℃/min.
The synthesis method of the methyl glyoxylate takes methyl glycolate as a raw material and prepares the methyl glyoxylate by reacting the methyl glycolate in the presence of the catalyst.
Further, the specific synthesis steps are as follows:
crushing the catalyst to 20 meshes, filling the crushed catalyst into a fixed bed reactor, introducing mixed gas of nitrogen and oxygen, carrying out temperature programming and constant temperature treatment to ensure that ferrous phosphate fully reacts with oxygen to generate ferric phosphate and ferric oxide, then cooling the system to 180 ℃, pumping methyl glycolate after the system is stabilized, carrying out catalytic reaction, cooling and collecting reaction liquid, and analyzing the reaction liquid.
Furthermore, the termination temperature of the temperature programming is 360 ℃, and the time of the constant temperature treatment is 4h.
By means of the scheme, the invention at least has the following advantages:
the preparation and application of the methyl glyoxylate catalyst provided by the invention synthesize a catalyst with excellent performance by taking ferric phosphate and cobalt phosphate as carriers and loading highly dispersed iron oxide and cobalt oxide on the surface of the carrier, the catalyst is used for catalyzing oxygen to oxidize methyl glycolate to selectively oxidize methyl glyoxylate to synthesize methyl glyoxylate, the same raw material is used for simultaneously obtaining the carrier and the active component required by the catalyst, and the catalyst is applied to synthesize methyl glyoxylate by using methyl glycolate to obtain a better catalytic effect, and the conversion rate of the raw material and the target selectivity are both improved compared with those of the traditional catalyst, so that the catalyst has a wide application prospect.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
The following examples are given to further illustrate embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The preparation and application of the glyoxylic acid methyl ester catalyst comprise the following steps:
(1) Preparation of the precursor
Adding iron phosphate and cobalt nitrate into deionized water containing glucose, performing two procedures of coarse grinding and fine grinding, mixing and grinding the iron phosphate, the cobalt nitrate and the glucose solution for 3 hours to obtain grinding slurry, drying the grinding slurry in a drying oven at 120 ℃ for 12 hours, and crushing the dried material;
(2) Preparation of the catalyst
Placing the crushed materials into a muffle furnace in an inert atmosphere, raising the temperature to 750 ℃ by a program, completing roasting to obtain a catalyst finished product, reducing iron phosphate into ferrous phosphate by glucose under low-temperature roasting, combining excessive phosphate radical with bivalent cobalt ions to generate cobalt phosphate, and carbonizing the glucose after the reduction action is exerted under high-temperature roasting, wherein the glucose can be used as a heat-conducting agent and a mold release agent;
(3) The synthesis method of the glyoxylic acid methyl ester comprises the following steps:
crushing the catalyst to 20 meshes, filling the crushed catalyst into a fixed bed reactor, introducing mixed gas of nitrogen and oxygen, raising the temperature by program, keeping the temperature at 360 ℃ for 4 hours to ensure that ferrous phosphate fully reacts with oxygen to generate ferric phosphate and ferric oxide, then lowering the temperature of the system to 180 ℃, pumping methyl glycolate after the system is stabilized, carrying out catalytic reaction, cooling, collecting reaction liquid, and analyzing the reaction liquid.
Example 1
37.705g of anhydrous iron phosphate, 72.7575g of cobalt nitrate hexahydrate and 6.875g of glucose monohydrate are put into a ball milling tank, 250mL of deionized water is poured, 500g of zirconium beads with the diameter of 5 mm are added, and ball milling is carried out for 3 hours. Filtering the slurry, drying at 120 ℃ for 12h, then transferring into a muffle furnace in an inert atmosphere, and roasting at 750 ℃ to obtain a catalyst finished product.
Crushing the catalyst to 20 meshes, filling the crushed catalyst into a fixed bed reactor, introducing mixed gas of nitrogen and oxygen, heating to 360 ℃, keeping the temperature for 4 hours, naturally cooling to 180 ℃, pumping methyl glycolate after the system is stable, cooling and collecting reaction liquid. The reaction solution was analyzed by chromatography, and the conversion of methyl glycolate was 99.37% and the selectivity of methyl glyoxylate was 96.56%.
Example 2
37.705g of anhydrous iron phosphate, 75.410g of cobalt nitrate hexahydrate and 6.875g of glucose monohydrate are placed in a ball milling tank, 250mL of deionized water is poured, 500g of zirconium beads with the diameter of 5 mm are added, and ball milling is carried out for 3 hours. Filtering the slurry, drying at 120 ℃ for 12h, then transferring into a muffle furnace in an inert atmosphere, and roasting at 750 ℃ to obtain a catalyst finished product.
Crushing the catalyst to 20 meshes, filling the crushed catalyst into a fixed bed reactor, introducing mixed gas of nitrogen and oxygen, heating to 360 ℃, keeping the temperature for 4 hours, naturally cooling to 180 ℃, pumping methyl glycolate after the system is stable, cooling and collecting reaction liquid. The reaction solution was analyzed by chromatography, and the conversion of methyl glycolate was 99.36% and the selectivity of methyl glyoxylate was 98.16%.
Example 3
Putting 37.705g of anhydrous iron phosphate, 78.226g of cobalt nitrate hexahydrate and 6.875g of glucose monohydrate into a ball milling tank, pouring 250mL of deionized water, adding 500g of zirconium beads with the diameter of 5 mm, performing ball milling for 3h, filtering slurry, drying at 120 ℃ for 12h, then transferring into a muffle furnace in an inert atmosphere, and roasting at 750 ℃ to obtain a catalyst finished product.
Crushing the catalyst to 20 meshes, filling the crushed catalyst into a fixed bed reactor, introducing mixed gas of nitrogen and oxygen, heating to 360 ℃, keeping the temperature for 4 hours, naturally cooling to 180 ℃, pumping methyl glycolate after the system is stable, cooling and collecting reaction liquid. The reaction solution was analyzed by chromatography, and the conversion of methyl glycolate was 99.35% and the selectivity of methyl glyoxylate was 98.13%.
Example 4
37.705g of anhydrous iron phosphate, 83.603g of cobalt nitrate hexahydrate and 6.875g of glucose monohydrate are placed into a ball milling tank, 250mL of deionized water is poured, 500g of zirconium beads with the diameter of 5 mm are added, ball milling is carried out for 3h, slurry is filtered, drying is carried out for 12h at 120 ℃, then the slurry is moved into a muffle furnace in inert atmosphere, and roasting is carried out at 750 ℃ to obtain the catalyst finished product.
Crushing the catalyst to 20 meshes, filling the crushed catalyst into a fixed bed reactor, introducing mixed gas of nitrogen and oxygen, heating to 360 ℃, keeping the temperature for 4 hours, naturally cooling to 180 ℃, pumping methyl glycolate after the system is stable, cooling and collecting reaction liquid. The chromatographic analysis of the reaction liquid shows that the conversion rate of methyl glycolate is 98.85 percent, and the selectivity of methyl glyoxylate is 98.10 percent.
Example 5
Putting 37.705g of anhydrous iron phosphate, 87.309g of cobalt nitrate hexahydrate and 6.875g of glucose monohydrate into a ball milling tank, pouring 250mL of deionized water, adding 500g of zirconium beads with the diameter of 5 mm, performing ball milling for 3h, filtering slurry, drying at 120 ℃ for 12h, then transferring into a muffle furnace in an inert atmosphere, and roasting at 750 ℃ to obtain a catalyst finished product.
Crushing the catalyst to 20 meshes, filling the crushed catalyst into a fixed bed reactor, introducing mixed gas of nitrogen and oxygen, heating to 360 ℃, keeping the temperature for 4 hours, naturally cooling to 180 ℃, pumping methyl glycolate after a system is stabilized, cooling and collecting reaction liquid. The reaction solution was analyzed by chromatography, and the conversion of methyl glycolate was 96.55% and the selectivity of methyl glyoxylate was 98.32%.
Comparative example 1: the synthesis method of methyl glyoxylate is basically the same as that of example 2 of the invention, except that methyl glyoxylate is synthesized in the same manner by using an iron-based molybdenum oxide-supported catalyst in place of the catalyst of the invention;
comparative example 2: the synthesis method of methyl glyoxylate is basically the same as that of example 2 of the invention, except that methyl glyoxylate is synthesized in the same manner by using a vanadium-based supported titania catalyst in place of the catalyst of the invention;
the reaction solutions of comparative example 1 and comparative example 2 were analyzed by gas chromatography to calculate the conversion of methyl glycolate and the selectivity of the target product, and the results are shown in table 1:
TABLE 1 Performance test results
| Detecting items | Comparative example 1 | Comparative example 2 |
| Conversion of methyl glycolate (%) | 92.65 | 92.39 |
| Selectivity of target product (%) | 98.10 | 98.09 |
As can be seen from the detection data in the table above, in comparative example 1 and comparative example 2, since the self-made catalyst of the present invention is replaced by the conventional iron-based supported molybdenum oxide and vanadium-based supported titanium oxide catalysts, the conversion rate of methyl glycolate and the selectivity of the target product are both reduced correspondingly, and thus, the self-made catalyst of the present invention has a superior synthesis effect and a broad application prospect compared with the conventional catalyst.
The above description is only a preferred embodiment 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, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (3)
1. A synthetic method of methyl glyoxylate is characterized by comprising the following steps:
(1) Preparation of the precursor
Adding iron phosphate and cobalt nitrate into deionized water containing glucose, performing two procedures of coarse grinding and fine grinding, mixing and grinding the iron phosphate, the cobalt nitrate and the glucose solution into grinding slurry, putting the grinding slurry into an oven for drying, and crushing the dried material;
(2) Preparation of the catalyst
Placing the crushed material into a muffle furnace in an inert atmosphere, and carrying out temperature programming and roasting to obtain a catalyst;
(3) Synthesis of methyl glyoxylate
Crushing the catalyst to 20 meshes, filling the crushed catalyst into a fixed bed reactor, introducing mixed gas of nitrogen and oxygen, carrying out temperature programming and constant-temperature treatment to ensure that ferrous phosphate fully reacts with oxygen to generate ferric phosphate and ferric oxide, then cooling the system to 180 ℃, pumping methyl glycolate after the system is stabilized, carrying out catalytic reaction, cooling and collecting reaction liquid to obtain methyl glyoxylate;
the termination temperature of the temperature programming in the step (2) is 750 ℃, and the rate of the temperature programming is 10 ℃/min;
the termination temperature of the temperature rise in the step (3) is 360 ℃, and the time of constant temperature treatment is 4 hours.
2. The method for synthesizing methyl glyoxylate according to claim 1, characterized in that:
and (2) mixing and grinding the ferric phosphate, the cobalt nitrate and the glucose solution in the step (1) for 3 hours.
3. The method for synthesizing methyl glyoxylate according to claim 1, wherein the method comprises the following steps:
the drying temperature of the grinding slurry in the step (1) is 120 ℃, and the drying time is 12h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4900864A (en) * | 1988-08-09 | 1990-02-13 | Anantaneni Prakasa R | Manufacture of alkyl glyoxylates with ferric phosphate catalyst |
| US5118652A (en) * | 1988-02-18 | 1992-06-02 | Monsanto Company | Ferric phosphate catalyst for use in the manufacture of alkyl glyoxylate |
| US5523459A (en) * | 1994-03-25 | 1996-06-04 | Ube Industries, Ltd. | Preparation of α-keto acid ester |
| CN1792447A (en) * | 2005-12-30 | 2006-06-28 | 黑龙江大学 | Catalyst for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde, its prepn. method and application thereof |
| CN107876055A (en) * | 2017-11-24 | 2018-04-06 | 上海应用技术大学 | A kind of methyl glycollate glyoxalic acid catalyst, preparation method and application |
-
2020
- 2020-09-15 CN CN202010967411.3A patent/CN112090433B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5118652A (en) * | 1988-02-18 | 1992-06-02 | Monsanto Company | Ferric phosphate catalyst for use in the manufacture of alkyl glyoxylate |
| US4900864A (en) * | 1988-08-09 | 1990-02-13 | Anantaneni Prakasa R | Manufacture of alkyl glyoxylates with ferric phosphate catalyst |
| US5523459A (en) * | 1994-03-25 | 1996-06-04 | Ube Industries, Ltd. | Preparation of α-keto acid ester |
| CN1792447A (en) * | 2005-12-30 | 2006-06-28 | 黑龙江大学 | Catalyst for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde, its prepn. method and application thereof |
| CN107876055A (en) * | 2017-11-24 | 2018-04-06 | 上海应用技术大学 | A kind of methyl glycollate glyoxalic acid catalyst, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| Redox cycling of polycyclic aromatic hydrocarbon o-quinones: metal ion-catalyzed oxidation of catechols bypasses inhibition by superoxide dismutase;Jarabak, R,et al.;《CHEMICO-BIOLOGICAL INTERACTIONS》;19981002;第201-213页 * |
| 乙醇酸甲酯法制备乙醛酸;周维友等;《化工进展》;20111130;第2536-2539页 * |
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