CN112062293A - New application of molasses fermentation liquor, high-efficiency environment-friendly grey water scale inhibition and dispersion agent and application of high-efficiency environment-friendly grey water scale inhibition and dispersion agent in grey water treatment process in coal chemical industry - Google Patents
New application of molasses fermentation liquor, high-efficiency environment-friendly grey water scale inhibition and dispersion agent and application of high-efficiency environment-friendly grey water scale inhibition and dispersion agent in grey water treatment process in coal chemical industry Download PDFInfo
- Publication number
- CN112062293A CN112062293A CN202010910023.1A CN202010910023A CN112062293A CN 112062293 A CN112062293 A CN 112062293A CN 202010910023 A CN202010910023 A CN 202010910023A CN 112062293 A CN112062293 A CN 112062293A
- Authority
- CN
- China
- Prior art keywords
- grey water
- scale inhibition
- dispersion agent
- friendly
- water scale
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses an application of molasses fermentation liquor as a grey water scale inhibition and dispersion agent in a grey water treatment process in coal chemical industry, an efficient environment-friendly grey water scale inhibition and dispersion agent and an application in the grey water treatment process in coal chemical industry, wherein the efficient environment-friendly grey water scale inhibition and dispersion agent comprises the following components in percentage by mass: 30-100% of molasses fermentation liquor (by solid content); 0-50% of hydrolyzed polymaleic anhydride (based on solid content); 0-50% of polyepoxysuccinic acid (based on solid content); 0 to 50% of polyaspartic acid (based on solid content). The molasses fermentation liquor is used as the grey water scale inhibition and dispersion agent in the grey water treatment process in the coal chemical industry, so that the method is green and pollution-free, low in raw material and production cost and high in production process safety; the invention has the advantages of no need of high adding concentration, reduction of the cost of treating the grey water, obvious improvement of scale inhibition rate, reduction of discharge capacity and improvement of the reutilization rate of the grey water.
Description
Technical Field
The invention relates to the technical field of coal chemical industry grey water treatment, in particular to a novel application of molasses fermentation liquor, a high-efficiency environment-friendly grey water scale inhibition and dispersion agent and an application of the dispersion agent in a coal chemical industry grey water treatment process.
Background
The coal gasification grey water treatment process comprises the procedures of cooling black water, recovering heat, removing dissolved gas, separating slag and water, recycling grey water and the like. The grey water has the characteristics of high temperature, high pressure, high turbidity, high hardness, high alkalinity and the like, so that adverse phenomena such as deposition, scaling, corrosion and the like are easily generated in the circulating operation process of the grey water, and the normal and stable operation of coal gasification equipment is seriously influenced.
In order to effectively slow down the influence of scaling and corrosion of the grey water on production equipment, reduce the discharge capacity and improve the repeated utilization rate of the grey water, the coal gasification grey water treatment process generally adopts a chemical agent treatment method of adding a grey water scale inhibition and dispersion agent. The grey water scale inhibition and dispersion agent in the current market generally comprises a compound product consisting of organic phosphonic acid, polycarboxylic acid, sulfonate copolymer, hydrolyzed polymaleic anhydride, polyepoxysuccinic acid, polyaspartic acid and the like, and has the functions of dispersing and inhibiting scales on suspended particles such as carbonate, sulfate, silicate, hydrated iron oxide and the like.
The raw materials and the production process thereof adopted by the production of most chemical components of the grey water scale inhibition and dispersion agent belong to hazardous chemicals and hazardous chemical processes, the requirements on production safety and environmental protection supervision are high, and the production cost is high. And the scale inhibition performance of the grey water scale inhibition and dispersion agent product is not ideal when the adding concentration of the grey water scale inhibition and dispersion agent product in the coal gasification grey water is low, so that the adding concentration requirement is high, and the comprehensive use cost is high.
The molasses fermentation liquor is a residual waste liquor produced in the process of producing yeast, alcohol and the like by microbial fermentation by using cane molasses as a raw material, and is rich in chemical components such as humic acid, biochemical fulvic acid, organic acid (citric acid, tartaric acid, acetic acid and the like), protein, amino acid, polysaccharide, vitamin, higher alcohol (such as trihydric alcohol and tetrahydric alcohol), trace elements and the like. The ecological organic fertilizer contains rich nutrient components required by the growth of animals and plants, belongs to a pure natural fermentation product, is green and pollution-free, and is widely applied to the fields of ecological organic fertilizers and feed raw materials.
At present, molasses fermentation liquor is generally used as a component of a fertilizer, such as a preparation method of an ecological fertilizer special for mudflat described in patent with publication number CN 104628470A; a carbohydrase granule water-soluble fertilizer and a method for producing the same described in patent publication No. CN 105367296A; a method for preparing a biological organic carbon fertilizer disclosed in patent publication No. CN 104671988A. In the above five patents, the molasses fermentation liquid is used as fertilizer.
Disclosure of Invention
The first purpose of the invention is to provide a new application of molasses fermentation liquor, so as to solve the problems of high production safety and environmental protection supervision requirements, high production cost, high addition concentration requirement, high comprehensive use cost and the like of the existing grey water scale inhibition and dispersion agent.
In order to achieve the purpose, the invention is realized by the following technical scheme: the molasses fermentation liquor is used as a grey water scale inhibition and dispersion agent in the coal chemical industry grey water treatment process.
The second purpose of the invention is to provide a high-efficiency environment-friendly grey water scale inhibition and dispersion agent, which is used for solving the problems of the existing grey water scale inhibition and dispersion agent.
In order to achieve the purpose, the invention is realized by the following technical scheme: an efficient environment-friendly grey water scale inhibition and dispersion agent comprises the following components in percentage by mass: 30-100% of molasses fermentation liquor (by solid content); 0-50% of hydrolyzed polymaleic anhydride (based on solid content); 0-50% of polyepoxysuccinic acid (based on solid content); 0 to 50% of polyaspartic acid (based on solid content).
The further scheme is that the paint comprises the following components in percentage by mass: 50 to 90 percent of molasses fermentation liquor (by solid content); 0-30% of hydrolyzed polymaleic anhydride (by solid content); 0-25% of polyepoxysuccinic acid (based on solid content); 0 to 25% of polyaspartic acid (based on solid content).
The third purpose of the invention is to provide the application of the high-efficiency environment-friendly grey water scale inhibition and dispersion agent in the grey water treatment process in the coal chemical industry.
In order to achieve the purpose, the invention is realized by the following technical scheme: the high-efficiency environment-friendly grey water scale inhibition and dispersion agent is applied to the grey water treatment process in the coal chemical industry, reduces the influence of grey water scaling and corrosion on production, reduces the discharge capacity and improves the reuse rate of the grey water.
The invention provides a novel, efficient and environment-friendly implementation approach of a grey water scale inhibition and dispersion agent. The unit quantity and the effect of active groups with scale inhibition and dispersion functions in a grey water system are effectively improved by utilizing active substance components such as humic acid, biochemical fulvic acid, organic acid, protein, amino acid, polysaccharide, higher alcohol and the like which are rich in concentrated molasses fermentation liquor and a unique macromolecular structure thereof and by synergistic compounding with the functions of hydrolyzed polymaleic anhydride, polyepoxysuccinic acid sodium and polyaspartic acid, so that the adding concentration of the grey water scale inhibition and dispersion agent and the comprehensive cost of grey water treatment are reduced. On the other hand, the concentrated molasses fermentation liquor prepared by taking agricultural products as raw materials through a fermentation method is nontoxic and strong in biodegradability, the formula of the concentrated molasses fermentation liquor belongs to an environment-friendly design, can effectively reduce environmental pollution, has the advantage of environmental protection of products, meets the requirements of green and ecological protection, and can realize efficient comprehensive utilization of the fermentation residual waste liquor.
The invention utilizes active functional groups such as carboxyl, phenolic group, hydroxyl, carbonyl, amino, methoxyl and the like which are rich in the concentrated molasses fermentation liquor and molecular structures which can generate complexation and chelation with metal ions to form stable chelation and complex with scaling ions (calcium and magnesium ions) in the coal gasification ash water, thereby effectively inhibiting the growth of scaling crystals and having solubilization function on the scaling ions; meanwhile, macromolecule structures and active groups in the concentrated molasses fermentation liquor adsorb and disperse ash suspended matters and colloids in the ash water, so that dirt is soft and easy to clean.
The invention has excellent adaptability, heat stability and high concentration scaling factor tolerance of the coal gasification grey water, can exert excellent dispersion and scale inhibition performance in a grey water system with high temperature (less than or equal to 300 ℃), high hardness, high alkalinity and high turbidity, and ensures the long-period stable operation of a gasification device; meanwhile, the corrosion inhibitor has excellent corrosion inhibition performance, and the service life of equipment is effectively prolonged; the method is suitable for treating the ash water in coal water slurry gasification processes such as Texaco (Texaco), multi-nozzle opposed type, E-Gas and Jinhua furnaces and powdered coal gasification processes such as space furnaces, can effectively slow down the influence of scaling and corrosion of the ash water on production equipment, can reduce the discharge capacity, and can improve the reutilization rate of the ash water.
The invention has the beneficial effects that: 1) in the invention, molasses fermentation liquor is used as the grey water scale inhibition and dispersion agent in the grey water treatment process in the coal chemical industry, and compared with the existing grey water scale inhibition and dispersion agent, the molasses fermentation liquor belongs to a pure natural fermentation product, is green and pollution-free, has low raw material and production cost, and has high production process safety; 2) the high-efficiency environment-friendly grey water scale inhibition and dispersion agent is used in the grey water treatment process in the coal chemical industry, the adding concentration is not required to be high, and the grey water treatment cost in the coal chemical industry can be obviously reduced; 3) compared with the existing grey water scale inhibition and dispersion agent, the high-efficiency environment-friendly grey water scale inhibition and dispersion agent provided by the invention can obviously improve the scale inhibition rate, slow down the influence of grey water scaling and corrosion on production, reduce the discharge capacity and improve the reuse rate of grey water.
Detailed Description
The technical solutions of the present invention are described clearly and completely by the following embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An efficient environment-friendly grey water scale inhibition and dispersion agent, which is concentrated molasses fermentation liquor.
Example 2
An efficient environment-friendly grey water scale inhibition and dispersion agent comprises the following components in percentage by mass: 90% of concentrated molasses fermentation liquor and 10% of hydrolyzed polymaleic anhydride.
Example 3
An efficient environment-friendly grey water scale inhibition and dispersion agent comprises the following components in percentage by mass: 90% of concentrated molasses fermentation liquor and 10% of polyepoxysuccinic acid.
Example 4
An efficient environment-friendly grey water scale inhibition and dispersion agent comprises the following components in percentage by mass: 90% of concentrated molasses fermentation liquor and 10% of polyaspartic acid.
Example 5
An efficient environment-friendly grey water scale inhibition and dispersion agent comprises the following components in percentage by mass: 50% of concentrated molasses fermentation broth and 50% of hydrolyzed polymaleic anhydride.
Example 6
An efficient environment-friendly grey water scale inhibition and dispersion agent comprises the following components in percentage by mass: 50% of concentrated molasses fermentation liquor and 50% of polyepoxysuccinic acid.
Example 7
An efficient environment-friendly grey water scale inhibition and dispersion agent comprises the following components in percentage by mass: 50% of concentrated molasses fermentation broth and 50% of polyaspartic acid.
Example 8
An efficient environment-friendly grey water scale inhibition and dispersion agent comprises the following components in percentage by mass: 50% of concentrated molasses fermentation liquor, 25% of hydrolyzed polymaleic anhydride and 25% of polyepoxysuccinic acid.
Example 9
An efficient environment-friendly grey water scale inhibition and dispersion agent comprises the following components in percentage by mass: 50% of concentrated molasses fermentation liquor, 25% of hydrolyzed polymaleic anhydride and 25% of polyaspartic acid.
Example 10
An efficient environment-friendly grey water scale inhibition and dispersion agent comprises the following components in percentage by mass: 50% of concentrated molasses fermentation liquor, 25% of polyepoxysuccinic acid and 25% of polyaspartic acid.
Example 11
An efficient environment-friendly grey water scale inhibition and dispersion agent comprises the following components in percentage by mass: 50% of concentrated molasses fermentation liquor, 30% of hydrolyzed polymaleic anhydride, 10% of polyepoxysuccinic acid and 10% of polyaspartic acid.
Example 12
An efficient environment-friendly grey water scale inhibition and dispersion agent comprises the following components in percentage by mass: 30% of concentrated molasses fermentation liquor, 30% of hydrolyzed polymaleic anhydride, 20% of polyepoxysuccinic acid and 20% of polyaspartic acid.
The above examples 1 to 12 list several formulation schemes of molasses fermentation liquid and hydrolyzed polymaleic anhydride, polyepoxysuccinic acid and polyaspartic acid, but for those skilled in the art, these formulation schemes are not all formulation schemes, and with the inspiration of the present invention that molasses fermentation liquid is used as a grey water scale inhibition dispersant in the grey water treatment process in the coal chemical industry, those skilled in the art can think that molasses fermentation liquid and other existing grey water scale inhibition dispersants are used in combination, and can also achieve the effects of reducing cost and increasing scale inhibition rate, and in the present invention, an exhaustive list cannot be made, but these schemes should fall within the protection scope of the present invention.
The use effects of the solutions of examples 1 to 12 of the present invention and the existing grey water scale inhibiting and dispersing agents are compared by comparative tests.
The test method comprises the following steps: adding 80mg/L of the high-efficiency environment-friendly grey water scale inhibition and dispersion agent in the embodiments 1-12 into a plurality of high-pressure reaction kettles containing grey water samples as an embodiment, adding 80mg/L and 100mg/L of the existing grey water scale inhibition and dispersion agent into the other two high-pressure reaction kettles containing grey water samples as a comparative example, heating to 300 ℃, controlling the pressure to be 6.5MPa, preserving the heat for 8 hours, cooling to the normal temperature, carrying out index analysis on the grey water sample after the test, observing the scale sample state, and calculating the scale inhibition rate, wherein the calculation method of the scale inhibition rate comprises the following steps:
and the scale inhibition rate is (total hardness after the test by adding the reagent test solution-total hardness after the test by adding the reagent blank test solution)/(total hardness before the test by adding the reagent blank test solution-total hardness after the test by adding the reagent blank test solution).
The test results are as follows:
as can be seen from the above table, compared with the existing grey water scale inhibition and dispersion agent, when the adding concentration of the high-efficiency environment-friendly grey water scale inhibition and dispersion agent is 80mg/L, the scale inhibition effect is obviously higher than that of the existing grey water scale inhibition and dispersion agent with the same adding concentration, and is higher than that of the existing grey water scale inhibition and dispersion agent with the adding concentration of 100 mg/L. The production cost of the high-efficiency environment-friendly grey water scale inhibition and dispersion agent is lower than that of the existing grey water scale inhibition and dispersion agent, and the high scale inhibition rate can be achieved by using low addition concentration, so that the cost of a grey water treatment process can be greatly reduced, and the scale inhibition effect is improved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. The new application of molasses fermentation liquor is characterized in that: the molasses fermentation liquor is used as a grey water scale inhibition and dispersion agent in the coal chemical industry grey water treatment process.
2. An efficient environment-friendly grey water scale inhibition and dispersion agent is characterized in that: the composite material comprises the following components in percentage by mass: 30-100% of molasses fermentation liquor (by solid content); 0-50% of hydrolyzed polymaleic anhydride (based on solid content); 0-50% of polyepoxysuccinic acid (based on solid content); 0 to 50% of polyaspartic acid (based on solid content).
3. The high-efficiency environment-friendly grey water scale inhibition and dispersion agent according to claim 2, which is characterized in that: the composite material comprises the following components in percentage by mass: 50 to 90 percent of molasses fermentation liquor (by solid content); 0-30% of hydrolyzed polymaleic anhydride (by solid content); 0-25% of polyepoxysuccinic acid (based on solid content); 0 to 25% of polyaspartic acid (based on solid content).
4. The application of the high-efficiency environment-friendly grey water scale inhibition and dispersion agent as claimed in any one of claims 2 or 3 in the grey water treatment process in the coal chemical industry, is characterized in that: the high-efficiency environment-friendly grey water scale inhibition and dispersion agent is used for the grey water treatment process in the coal chemical industry, slows down the influence of scaling and corrosion of the grey water on production, reduces the discharge capacity and improves the reuse rate of the grey water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010910023.1A CN112062293A (en) | 2020-09-02 | 2020-09-02 | New application of molasses fermentation liquor, high-efficiency environment-friendly grey water scale inhibition and dispersion agent and application of high-efficiency environment-friendly grey water scale inhibition and dispersion agent in grey water treatment process in coal chemical industry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010910023.1A CN112062293A (en) | 2020-09-02 | 2020-09-02 | New application of molasses fermentation liquor, high-efficiency environment-friendly grey water scale inhibition and dispersion agent and application of high-efficiency environment-friendly grey water scale inhibition and dispersion agent in grey water treatment process in coal chemical industry |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112062293A true CN112062293A (en) | 2020-12-11 |
Family
ID=73666272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010910023.1A Pending CN112062293A (en) | 2020-09-02 | 2020-09-02 | New application of molasses fermentation liquor, high-efficiency environment-friendly grey water scale inhibition and dispersion agent and application of high-efficiency environment-friendly grey water scale inhibition and dispersion agent in grey water treatment process in coal chemical industry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112062293A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508492A (en) * | 2009-03-10 | 2009-08-19 | 同济大学 | Environment-friendly composite dirt dispersion agent for oil-field flooding treatment |
| CN109135852A (en) * | 2018-09-03 | 2019-01-04 | 宁夏宝塔石化煤化工研究院有限公司 | A kind of modification of molasses waste liquid and the preparation method of coal water slurry dispersing agent |
| CN109231510A (en) * | 2018-11-22 | 2019-01-18 | 山东正祎环保科技有限公司 | A kind of novel corrosion-retarding dispersing agent |
| CN109835989A (en) * | 2019-04-02 | 2019-06-04 | 常州工程职业技术学院 | A kind of recirculated cooling water composite scale inhibitor and preparation method thereof |
-
2020
- 2020-09-02 CN CN202010910023.1A patent/CN112062293A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508492A (en) * | 2009-03-10 | 2009-08-19 | 同济大学 | Environment-friendly composite dirt dispersion agent for oil-field flooding treatment |
| CN109135852A (en) * | 2018-09-03 | 2019-01-04 | 宁夏宝塔石化煤化工研究院有限公司 | A kind of modification of molasses waste liquid and the preparation method of coal water slurry dispersing agent |
| CN109231510A (en) * | 2018-11-22 | 2019-01-18 | 山东正祎环保科技有限公司 | A kind of novel corrosion-retarding dispersing agent |
| CN109835989A (en) * | 2019-04-02 | 2019-06-04 | 常州工程职业技术学院 | A kind of recirculated cooling water composite scale inhibitor and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101700937B (en) | Composite scale inhibitor | |
| CN100551933C (en) | A kind of method of extracting bacteria alginate | |
| CN113264588B (en) | Composite carbon source for sewage treatment | |
| CN106242085A (en) | A kind of circularly-cooling sea water non-phosphorus scale and corrosion inhibitor and preparation method thereof | |
| CN111205934A (en) | Cleaning agent suitable for descaling of landfill leachate evaporator, and preparation method and application thereof | |
| CN104692545A (en) | Scale inhibitor for boiler and water supply pipeline | |
| CN102796577B (en) | Method for producing methane by utilizing papermaking black liquid caused by ammonium sulfite method | |
| CN108017763B (en) | Corrosion and scale inhibition combined medicament and preparation method thereof | |
| CN106007017A (en) | Green and environment-friendly composite scale and corrosion inhibition chemical and preparation method thereof | |
| CN117800507A (en) | Nitrogen carbide quantum dot scale inhibitor with fucoidin carboxylate as stabilizer and preparation method thereof | |
| CN112441664A (en) | Composite carbon source sewage treatment agent and preparation method thereof | |
| CN112062293A (en) | New application of molasses fermentation liquor, high-efficiency environment-friendly grey water scale inhibition and dispersion agent and application of high-efficiency environment-friendly grey water scale inhibition and dispersion agent in grey water treatment process in coal chemical industry | |
| CN103466791A (en) | Improved pre-acidifying treatment process of citric acid wastewater | |
| CN111826163A (en) | Conditioner for adjusting soil acid-base balance and preparation method thereof | |
| CN116618415A (en) | Method for preparing high-concentration biomass carbon source by utilizing kitchen waste | |
| CN114149087B (en) | Method for treating arsenic-containing waste liquid by agricultural waste in cooperation with microorganisms | |
| CN109019883A (en) | Phosphate-free corrosion inhibition antisludging agent and preparation method thereof for Waste Water Reuse technology | |
| CN1470464A (en) | Efficient water-saving phosphine-free water treatment chemical for environmental protection | |
| CN111499155B (en) | Anti-freezing sludge deep dehydration conditioner and preparation and application methods thereof | |
| CN108640446B (en) | Composite organic acid red mud dealkalizing agent and red mud dealkalizing method | |
| CN113403084A (en) | Salinized soil composite modifier produced by using agricultural waste, preparation method and application thereof | |
| CN111517607B (en) | Organic sludge treatment method | |
| CN112624537A (en) | Method and system for decrement treatment of biochemical excess sludge | |
| CN110564467B (en) | Environment-friendly coal water slurry additive and application thereof in coal water slurry waste blending preparation process | |
| CN115449361B (en) | Microbial oil displacement agent for high-temperature high-mineralization oil reservoir and preparation method thereof |
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 |