CN1432533A - Algae killing and inhibiting method for water body - Google Patents

Algae killing and inhibiting method for water body Download PDF

Info

Publication number
CN1432533A
CN1432533A CN 02110566 CN02110566A CN1432533A CN 1432533 A CN1432533 A CN 1432533A CN 02110566 CN02110566 CN 02110566 CN 02110566 A CN02110566 A CN 02110566A CN 1432533 A CN1432533 A CN 1432533A
Authority
CN
China
Prior art keywords
algae
water
copper
killing
water body
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
Application number
CN 02110566
Other languages
Chinese (zh)
Inventor
陈丹
陈匀
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to CN 02110566 priority Critical patent/CN1432533A/en
Publication of CN1432533A publication Critical patent/CN1432533A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/4606—Treatment of water, waste water, or sewage by electrochemical methods for producing oligodynamic substances to disinfect the water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/008—Mobile apparatus and plants, e.g. mounted on a vehicle

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (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)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The present invention discloses algae killing and inhibiting method for water body. Electrolysis equipment is set on vehicle, boat, floated apparatus, cooling tower system or other apparatus near the water body, and the electrodes are contacted with water body. The anode is made of copper material, and the cathode material is copper, iron, aluminium, graphite or other conductive material. The copper density in the water body is 0.4-4 mg/L for inhibiting algae and 3-8 mg/L for killing algae. Produced copper hydroxide is exhausted to water body continuously or intermittently to kill or inhibit algae. The said method can be used for killing and inhibit algae and bacteria without producing environmental pollution.

Description

Method for killing and inhibiting algae in water body
The technical field is as follows:
the invention relates to the technical field of water treatment in environmental protection, in particular to the water body of rivers, lakes and coastal water bodies with algae killing, algae inhibiting, sterilizing, bacteriostasis, fluidity or non-fluidity for cooling circulating water, swimming pool water and tap water.
Background art:
due to accumulation eutrophication in long-term water quality and small ecological cycle of fixed water, the method is particularly suitable for algae growth, so that the dissolved oxygen in the water body is reduced, the ecological balance is damaged, the water quality generates peculiar smell, the wall of a water containing pool is sticky and slippery, and a filter pool and a water delivery facility are easy to block. Is composed ofOvercomes the growth of algae, adopts medicament feeding all the time, has a plurality of inconveniences and has certain influence on water quality environment, and in recent years, micro-electrolysis algae killing devices, electronic water treatment devices, ozone/ultrasonic waves and O are adopted in a small range3The/uv is used for killing and inhibiting the algae, but has the disadvantages of large equipment, large investment and high cost, and is still used for killing and inhibiting the algae and tests on a small scale in application.
The invention content is as follows:
the invention aims to provide a method for killing and inhibiting algae in water, which is simple, convenient, safe and reliable in application of killing and inhibiting algae in water, can be suitable for killing and inhibiting algae in a small-range water body, can also be suitable for killing and inhibiting algae in a large-area water body, and is beneficial to environmental protection.
The technical scheme of the invention is realized as follows: a method for killing and inhibiting algae in water is characterized in that: the electrolysis equipment is arranged on a vehicle, a ship, a water body floating device, a cooling tower system or a water body side facility with power supply, an electrode in the electrolysis equipment is in contact with the water body, the anode of the electrode is made of copper material, the cathode material can be copper, iron, aluminum, graphite or other conductive materials, the algae inhibiting copper concentration in the water body is 0.4-4 mg/L, and the algae killing copper concentration is 3-8 mg/L.
The invention selects a physical and chemical mode, namely an electrolytic method, direct current voltage can be adopted within the range of 1-220V, and particularly, the electrode is arranged in the water body needing to be subjected to algae killing, algae inhibiting, sterilization and bacteriostasis, and movable electrolysis is directly carried out or the water body needing to be subjected to algae killing, algae inhibiting, sterilization and bacteriostasis is continuously or intermittently sucked, treated by an electrolysis device and then continuously or intermittently discharged into the water body for dilution and circulation, thus achieving the main purposes of algae killing and algae inhibiting. The experiment shows that the invention can be suitable for small-range water bodies to kill, inhibit, sterilize and inhibit bacteria, can be suitable for large-area water bodies to kill, inhibit, sterilize and inhibit bacteria, does not cause new pollution and is beneficial to environmental protection.
The specific implementation mode is as follows:
the invention is further described and illustrated by the following examples
During electrolysis, the water body is used as electrolyte, and the water body is water or tap water to be treated; their reaction mechanism is that when water is applied to the cathode region H of the electrode under the action of electric current2O is ionized to form H+And OH-Ion, cathode H+Is reduced into hydrogen atoms, the two hydrogen atoms are combined into hydrogen molecule air floatation and escape, and under the action of anode region current, the copper loses electrons and undergoes oxidation reaction and is dissolved to form Cu2+Ions, Cu in water2+Ions with OH-The ions attract each other to form inorganic copper protective broad-spectrum bactericide-Cu (OH)2 2+Is the main substance.
Electrolysis
Cu(OH)2 2+The water-insoluble, small molecular weight synthesized in water, good dispersibility, good instant suspension property, and crystallization only under a certain concentration. Due to Cu (OH)2 2+Belongs to cations, the surface of organisms is mainly anionic, and is combined with the organisms in water, the reaction speed is also called as the reaction speed, is faster than the crystallization speed, if the crystallization precipitation needs to be in Cu (OH)2With various substances which are easy to react, on the basis of the balance of potential difference reduction, concentration and the like, Cu (OH)2Excess free is formed until the crystalline concentration is reached. Therefore, the invention directly solves the problems of the prior Cu (OH)2The bactericide can not be widely applied to algae killing and sterilization in water; meanwhile, the cost and the cost of the central links of extraction, preparation, packaging, sale and the like of a copper hydroxide product are reduced when the copper hydroxide floating device is applied to algae killing of a water body, the water body floating device has certain buoyancy and can float on the water surface and is provided with power supply equipment, and similar to a navigation mark, the water body floating device and the electrolysis equipment are the prior art and are not specifically described herein.
The invention is shown to be one step more advanced than micro-electrolysis SC sterilization patent products, electronic water treatment devices and more reported electric field modes by the fuzzy theory of killing hydroxyl radical free oxide formed under the ionization action. Hydroxyl free radical has killing effect, but the main effect in algae killing is short-term inhibiting effect, and the main killing and inhibiting effect of hydroxide on organisms depends on the property of metal ions, and whether the hydroxide can replace and chelate elements in a protein structure to denature and inactivate the elements. The hydroxyl is alkaline, has strong potential and poor reaction selectivity, is easy to combine with protective lipid and protein on the surface of the biological cell wall to change the permeability, but is difficult to directly permeate without consumption. The hydroxide is reduced in the binding with cell membranes and cell walls to release ions, and if the ions do not have a certain potential and binding force with proteins, the proteins cannot be denatured and inactivated, and the hydroxide does not have stronger killing power. The killing of hydroxyl free radicals is mainly the binding damage of biological surfaces and belongs to the equivalent relation of molecules. Systemic damage to vital body proteins is critical to killing. While the magnesium element copper ion in the biological chlorophyll can be replaced, the sugar source can reduce the inorganic copper, and the copper ion can form a chelate with the amino acid. Thus, it was established that copper hydroxide has a large denaturing effect on organisms in hydroxide. The electrolytic algae-killing and sterilizing material with copper as the base material is confirmed, the water quantity and time for killing and inhibiting algae can be calculated according to the copper loss, the equipment can be conveniently combined according to the size of the required treatment capacity, and the problem that the conventional electrolytic algae-killing mode cannot be popularized and expanded arbitrarily due to insufficient understanding of the conventional electrolytic algae-killing mode is solved.
The mode is the most basic equipment process improvement of modern industry, and changes the concept of electrode loss fearing during the conventional electrolysis and the deep research direction of generating substance elements by the application of electrolytic sterilization and algae killing. The copper hydroxide produced by adopting the method of imitating and improving the electrolytic method to produce the cuprous oxide is directly applied to sterilization and algae killing. The invention relates to an example of applying copper hydroxide to water sterilization and algae killing. The method can combine with oxygen charging or ozone according to the requirement of copper ion content in water quality, and adopts an oxidation method to reduce copper ions to form copper oxide precipitate according to different water quality requirements after sterilization and algae killing.
Tests show that by applying different electrode materials at the same current, voltage and time, the algae starts to grow after the stainless steel electrode and the graphite electrode are subjected to electrolytic algae killing treatment for three days, the algae is increased after one week, but the algae is still obviously inhibited compared with a control group without killing the algae, but the copper electrode does not have the growth sign after the electrolytic algae killing; copper hydroxide ions are easy to form different coordination complexes with a plurality of free amino acids, cyano groups and carbonic acid in water, and have certain loss on the algae killing dosage, generally, the copper hydroxide synthesized by water electrolysis is directly dissolved in water or inhibited by a copper hydroxide preparation, because of different impurity contents, the copper concentrationof the algae inhibited by the water is 0.4mg/L-4mg/L, and the algae killing copper concentration is 3mg/L-8mg/L, so that the effect can be achieved, and the unit used for the copper concentration is the milligram required by each liter and is close to the algae killing example content of copper sulfate. Therefore, the inorganic copper algae killing and inhibiting application takes the copper concentration of the water body as a reference value. However, the oral LD50 of the copper sulfate toxicity rat is 3.33 times larger than that of copper hydroxide, the algae killing application amount is doubled, and the toxicity is reduced by multiple times when the copper hydroxide is applied to higher-level organisms at the early stage in an intangible manner to kill algae. The invention is applied to lakes, rivers and ponds, can fix control equipment such as a generator, voltage, current and the like on vehicles, ships and water floating equipment, and can sterilize and kill algae in a movable mode by placing the electrodes in water or in water when in use. The electrodes and other equipment can also be integrally arranged on vehicles and ships to be connected with movable or fixed power supplies, and water is sucked and discharged into the water and diluted after being electrolyzed when the water treatment device is used.
In order to reduce the maintenance and personnel cost of vehicle and ship flow equipment and reduce the algae killing cost, wind power and solar power generation can be used, the water is clustered and dispersed to be arranged beside a river or lake or a water floating device is arranged in the lake, electrodes are arranged in water and combined with an air increasing pump, electrolysis algae killing operation is carried out in the early stage of algae growth and the full growth stage according to the water quality, and the air increasing pump is switched to work to improve the water quality at ordinary times.
In the prior numerous cooling circulating water works, algae killing and inhibiting are still inconvenient, in order to overcome the defect that the growth of algae blocks a circulating system, a cooling fin in a cooling tower can be replaced by an electrode, the electrode can also be arranged in a water tank or front and rear pipelines of a circulating pump, a power supply is switched on to kill and inhibit the algae, the release speed of copper ions is controlled according to the rule that the water volume is large in current and small in current, and the algae-free operation is achieved.
The swimming pool water needs to be kept clean continuously, the chlorine content is too high, which is not good for human body, and the electrolytic circulation at the outlet of the pump is changed to 1mg/L-4mg/L of copper ions for sterilization, bacteriostasis, algae killing and algae inhibition. Has no influence on human body contact. At present, copper element is not enough to be absorbed by human body. In addition, after the disinfection of chlorine elements is changed into the disinfection of copper ions, the smell of water in the swimming pool can be reduced, and meanwhile, the copper ions and substances mainly comprising a water body external floating nitrogen source are easy to complex and enlarge, and are convenient for circulating filtration.
The raw water is electrolyzed and disinfected by copper ions, so that the sterilization and algae killing effects can be realized, impurities can be complexed, and biological enzyme toxin can be complexed. The water quality is controlled to prevent the residual of excessive copper element in the drinking water and further purify the water quality, and finally, the ozone is used for sterilizing and oxidizing impurities to reduce copper ions to form copper oxide precipitate. The alternate sterilization, oxidation and purification effects of the two different modes are higher than that of single-mode treatment. The defects that the single mode can not be oxidized and decomposed after the potential balance after the molecular complexation, the displacement and the molecular chain scission are changed.
The main killing and inhibiting effect of hydroxide on organism depends on the property of metal ion, and whether it can replace, chelate and denature the elements in protein structure. The hydroxyl is alkaline, has strong potential and poor reaction selectivity, is easy to combine with protective lipid and protein on the surface of the biological cell wall to change the permeability, but is difficult to directly permeate without consumption. The hydroxide is reduced in the binding with cell membranes and cell walls to release ions, and if the ions do not have a certain potential and binding force with proteins, the proteins cannot be denatured and inactivated, and the hydroxide does not have stronger killing power. While the magnesium element copper ion in the biological chlorophyll can be replaced, the sugar source can reduce the inorganic copper, and the copper ion can form a chelate with the amino acid. The algae killing mechanism of copper ions is that the copper ions and anions on the surface of cell membraneK+、H+The above-mentioned exchanges, in which proteins on cell membranes are coagulated and part of copper ions permeate into cells and bind to some enzymes to influence the activities thereof, have established that copper hydroxide has a large denaturing effect on organisms in hydroxide, and have confirmed electrolytic algicidal and bactericidal materials based on copper.
Copper hydroxide ions are easy to form different coordination complexes with a plurality of free amino acids, cyano groups and carbonic acid in water, have certain loss on the algae killing dosage, and generally adopt water as electrolyte to synthesize copper hydroxide which is directly dissolved in water or inhibited by a copper hydroxide preparation. Becauseof different impurity contents, the impurities are consumed and complexed more. The effect can be achieved by controlling and inhibiting the concentration of the immediate copper-containing ions in the algae water body to be 3mg/L-8 mg/L.
Copper ions function to bind to proteins and denature proteins by coagulation. Copper ions belong to cations, the potential is relatively high, the reaction is relatively fast, the selective combination to protein is poorer than that of anions,
because the water solubility of the copper hydroxide is extremely poor, the application of the copper hydroxide in the water body cannot be popularized and deepened in the past. At present, the mode of directly generating copper hydroxide by an electrolysis method and directly dissolving the copper hydroxide into water is adopted, the synthesized molecular weight in water is small, the volume is nano, the dispersibility is good, the instant suspension property is good, the copper hydroxide can be crystallized only under a certain concentration, the electrolysis to generate the copper hydroxide is very convenient and has small hazard, and the method for killing algae and sterilizing the copper hydroxide, the equipment investment and the use cost and the like are considered to be the most suitable method and variety to be popularized at present.
Example 1
And (2) killing algae in the water body, controlling the direct current voltage to be 8V, controlling the anode of the electrode to be brass, controlling the cathode to be red copper, directly placing the two electrodes at an interval of 2 cm in the water body, stopping electrolysis when the copper consumption reaches 5mg/L of the average water body, detecting contrast culture water samples before and after treatment after 10 days, and continuously observing the water body for one month without algae growth, wherein the untreated chlorophyll α is 113.3, and the treated chlorophyll α is 2.73.
Example 2
In daily lifeWhen the raw water is treated in spring, a group of electrodes are arranged at the outlet of a water suction pump, the direct-current voltage is 36V, the two electrodes are spaced by 2.5 cm and are directly placed in a water body, and the treated water quantity is 35m of electricity consumption3The raw water, which has a copper consumption of 175 g and a copper content of 5mg/L, is reduced by 80% compared with untreated bacteria.
Example 3
When raw water of domestic water is treated in winter, a group of electrodes with direct current voltage of 36V and interval of 2.5 cm are arranged at the outlet of a water suction pump and directly placed in a water body, and the treated water amount is 58.5m of electricity consumption3KW, copper consumption 175 g, reduced copper concentration 3 mg/L.
Example 4
The electrolysis equipment is arranged at a water return port of a circulating water pool, the anode of the electrode is red copper, the cathode of the electrode is cast iron, and the treatment water flow is 3000m according to the power consumption3The copper-containing ion concentration is 0.5mg/L in KW, and the growth of the algae can be controlled.

Claims (2)

1. A method for killing and inhibiting algae in water is characterized in that: the electrolysis equipment is arranged on a vehicle, a ship, a water body floating device, a cooling tower system or a water body side facility, an electrode in the electrolysis equipment is in contact with the water body, the anode of the electrode is made of copper material, the cathode material can be copper, iron, aluminum, graphite or other conductive materials, the concentration of copper for inhibiting algae in the water body is 0.4-4 mg/L, and the concentration of copper for killing algae and sterilizing is 3-8 mg/L.
2. One of the features of claim 1, wherein: the water body is water or tap water to be treated.
CN 02110566 2002-01-16 2002-01-16 Algae killing and inhibiting method for water body Pending CN1432533A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 02110566 CN1432533A (en) 2002-01-16 2002-01-16 Algae killing and inhibiting method for water body

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 02110566 CN1432533A (en) 2002-01-16 2002-01-16 Algae killing and inhibiting method for water body

Publications (1)

Publication Number Publication Date
CN1432533A true CN1432533A (en) 2003-07-30

Family

ID=27628189

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 02110566 Pending CN1432533A (en) 2002-01-16 2002-01-16 Algae killing and inhibiting method for water body

Country Status (1)

Country Link
CN (1) CN1432533A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101993135B (en) * 2009-08-28 2012-05-09 明达实业(厦门)有限公司 Two-in-one cupric chloride/cupric bromide disinfecting apparatus for swimming pool
CN102627377A (en) * 2012-04-18 2012-08-08 波鹰(厦门)科技有限公司 Method and device for purifying seriously eutrophic river water
CN102633395A (en) * 2012-04-18 2012-08-15 波鹰(厦门)科技有限公司 Eutrophicated river water quality purifying method and purifying device thereof
CN102633391A (en) * 2012-04-18 2012-08-15 波鹰(厦门)科技有限公司 Purification method and purification device of eutrophic river
CN104030411A (en) * 2014-06-27 2014-09-10 东南大学 Shipborne water electrolysis blue-green algae eliminating device and method
CN104058535A (en) * 2014-07-17 2014-09-24 上海船研环保技术有限公司 Ship ballast water treatment system with biologic resurgence inhibition function
CN104229943A (en) * 2014-08-29 2014-12-24 冯胜 Device applied to eutrophic water for light-electrical-catalytic degradation of organic matter in water
CN108950654A (en) * 2018-08-30 2018-12-07 齐昊 A kind of antibacterial applications of copper sulphate in painting dressing automobiles cathode electrodip painting

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101993135B (en) * 2009-08-28 2012-05-09 明达实业(厦门)有限公司 Two-in-one cupric chloride/cupric bromide disinfecting apparatus for swimming pool
CN102627377A (en) * 2012-04-18 2012-08-08 波鹰(厦门)科技有限公司 Method and device for purifying seriously eutrophic river water
CN102633395A (en) * 2012-04-18 2012-08-15 波鹰(厦门)科技有限公司 Eutrophicated river water quality purifying method and purifying device thereof
CN102633391A (en) * 2012-04-18 2012-08-15 波鹰(厦门)科技有限公司 Purification method and purification device of eutrophic river
CN104030411A (en) * 2014-06-27 2014-09-10 东南大学 Shipborne water electrolysis blue-green algae eliminating device and method
CN104030411B (en) * 2014-06-27 2015-07-15 东南大学 Shipborne water electrolysis blue-green algae eliminating device and method
CN104058535A (en) * 2014-07-17 2014-09-24 上海船研环保技术有限公司 Ship ballast water treatment system with biologic resurgence inhibition function
CN104229943A (en) * 2014-08-29 2014-12-24 冯胜 Device applied to eutrophic water for light-electrical-catalytic degradation of organic matter in water
CN108950654A (en) * 2018-08-30 2018-12-07 齐昊 A kind of antibacterial applications of copper sulphate in painting dressing automobiles cathode electrodip painting

Similar Documents

Publication Publication Date Title
Ghernaout et al. From chemical disinfection to electrodisinfection: The obligatory itinerary?
AU2007257247B2 (en) Electrolytic activation of water
JP3364518B2 (en) Wastewater treatment method
Ricordel et al. Electrocoagulation–electroflotation as a surface water treatment for industrial uses
JP3913923B2 (en) Water treatment method and water treatment apparatus
US8287702B2 (en) Electrolytic activation of water
Irki et al. Decolorizing methyl orange by Fe-electrocoagulation process—a mechanistic insight
CN103459328B (en) Water purification
GB2444114A (en) An electrolytic process for the treatment of effluent
JPH06134465A (en) Water treatment process
CN1392865A (en) Method and apparatus for clarification of water
CN1432533A (en) Algae killing and inhibiting method for water body
JPS6059995B2 (en) Impure salt water electrolysis method and device
Baneshi et al. Removal of remazol black B dye from aqueous solution by electrocoagulation equipped with iron and aluminium electrodes
CN106977013A (en) A kind of purifying treatment method of high chlorine waste water containing thallium and its application
EP0642824A1 (en) Method for adjusting the pH of water to a value adjustable in the range from 1 to 13 and apparatus for carrying out said method
Ignatov et al. Studying electrochemically activated naCl solutions of anolyte and catholyte by methods of non-Equilibrium energy spectrum (NES) and differential non-equilibrium energy spectrum (DNES)
Uğurlu et al. Experimental Investigation of Chemical Oxygen Demand, Lignin and Phenol Removal from Paper Mill Effluents Using Three-Phase Three-Dimensional Electrode Reactor.
KR100878350B1 (en) Continuous removing apparatus and method of algaes and nutrient salts by using potential difference method
CN111924939A (en) Method for removing ammonia nitrogen and nitrite in aquaculture water body through microelectrode
KR100233775B1 (en) Apparatus for producing sterilized water
CN2504260Y (en) Water purifier
Ignatov et al. Studying Electrochemically Activated NaCl Solutions of Anolyte and Catholyte by Methods of Non-Equilibrium Energy Spectrum (NES) and Differential Non-Equilibrium Energy Spectrum (DNES)
KR20070057064A (en) Manufacturing methods of a mineral additives from deep sea water
CN113493239A (en) Electrochemical treatment device, seawater desalination system and method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication