CN113968716A - Harmless treatment method for electrolytic manganese slag - Google Patents
Harmless treatment method for electrolytic manganese slag Download PDFInfo
- Publication number
- CN113968716A CN113968716A CN202111314529.7A CN202111314529A CN113968716A CN 113968716 A CN113968716 A CN 113968716A CN 202111314529 A CN202111314529 A CN 202111314529A CN 113968716 A CN113968716 A CN 113968716A
- Authority
- CN
- China
- Prior art keywords
- electrolytic manganese
- manganese slag
- parts
- water
- harmless
- 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 239000002893 slag Substances 0.000 title claims abstract description 128
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 124
- 239000011572 manganese Substances 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 43
- 239000010440 gypsum Substances 0.000 claims abstract description 42
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000006227 byproduct Substances 0.000 claims abstract description 34
- 239000004568 cement Substances 0.000 claims abstract description 27
- 229940037003 alum Drugs 0.000 claims abstract description 26
- 230000032683 aging Effects 0.000 claims abstract description 25
- 238000000227 grinding Methods 0.000 claims abstract description 17
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 9
- 239000000920 calcium hydroxide Substances 0.000 claims description 9
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- 235000012255 calcium oxide Nutrition 0.000 claims description 9
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical group O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 230000008569 process Effects 0.000 abstract description 14
- 238000001035 drying Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 235000019691 monocalcium phosphate Nutrition 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052567 struvite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/142—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/144—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being a flue gas desulfurization product
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/142—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/143—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being phosphogypsum
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/32—Aluminous cements
- C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
- C04B2111/00784—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes for disposal only
Abstract
The invention discloses a harmless treatment method of electrolytic manganese slag, which comprises the following steps: crushing and grinding the electrolytic manganese slag, adding sulphoaluminate cement clinker, alkaline materials, industrial by-product gypsum, alum and water, adjusting the water temperature, uniformly stirring to obtain a mixture, fully reacting the mixture under the condition of micro negative pressure, and aging to obtain harmless electrolytic manganese slag. The method has the advantages of low cost, easily obtained raw materials, simple process method, easy control, no need of calcination treatment at high temperature and drying compared with the traditional treatment method, greatly improved speed for treating the electrolytic manganese slag, greatly reduced energy consumption, greatly improved speed for treating the electrolytic manganese slag, and suitability for large-scale low-cost quick harmless treatment of electrolytic manganese slag discharge enterprises.
Description
Technical Field
The invention belongs to the technical field of solid waste treatment, and particularly relates to a harmless treatment method for electrolytic manganese residues.
Background
Manganese metal is an important strategic resource in China and is widely applied to various fields such as metallurgy, chemical engineering, food, aerospace and the like. According to statistics, the yield of electrolytic manganese metal in 2016 years in China is up to 115 ten thousand tons, and the percentage of the electrolytic manganese metal in the manganese metal yield in the world is extremely high and reaches more than 98.5%. The production, consumption and export of electrolytic manganese metal in China are at the first place in the world, wherein the areas of Hunan, Hubei, Guizhou, Sichuan and the like are electrolytic manganese enterprise concentration areas. With the rapid development of the electrolytic manganese industry, pollutants generated by the electrolytic manganese industry seriously harm the environment, and the problem of electrolytic manganese slag pollution is the most prominent. The process of producing electrolytic manganese metal by utilizing manganese carbonate ore can produce electrolytic manganese slag which is industrial solid waste discharged when the manganese metal is produced by the electrolytic manganese process, the manganese ore reacts with sulfuric acid, when manganese salt solution is prepared by heating, a large amount of ammonia water is required to be added as a buffering agent, and the ammonium ions and sulfuric acid residual acid finally enter the electrolytic manganese slag to be discharged together, thereby belonging to acidic waste slag. The electrolytic manganese slag is black and sticky, contains more than 80% of fine-grain components with the granularity of less than 80 mu m, contains manganese, sulfate, ammonia nitrogen, heavy metal ions, SiO2, MgO, K +, Na + and other substance components, and has large disposal and utilization difficulty. The electrolytic manganese slag is not listed in the national hazardous waste list for a moment, and belongs to the II-class general industrial solid waste. It is investigated that 8-16t of electrolytic manganese slag is produced for every 1t of electrolytic manganese metal produced. At present, only south Africa MMC companies are used for producing electrolytic manganese in foreign countries, electrolytic manganese slag is mainly treated in a landfill mode, the treatment cost is extremely high, manganese slag in China is mainly piled up in a damming wet method, land is occupied, heavy metals and the like easily permeate into soil, underground water and surface water and finally enter human bodies under the action of food chains, and serious environmental pollution and potential safety hazards exist.
At present, there are some documents on harmless treatment of electrolytic manganese slag, such as:
the patent application document with the publication number of CN102161048B discloses a harmless treatment method of electrolytic manganese slag, which comprises the steps of crushing the manganese slag, adding the crushed manganese slag into a stirrer, adding quicklime powder, water and a certain amount of silicate additives, stirring to form a uniform mixture, and recovering ammonia; adding water-soluble resin sulfonate additive and ferric oxide, stirring again, and recovering ammonia gas; fully stirring, drying, and performing landfill treatment after the inspection is qualified. The method described in this patent document aims to remove ammonia gas by adding a water reducing agent (additive of water-soluble resin sulfonate type) and a flocculant (iron oxide) to electrolytic manganese slag with ordinary stirring. However, the process is complicated, organic water reducing agent components are introduced, a small amount of soluble salt is brought in, the residue property in the treated electrolytic manganese residue is not changed (the soluble salt is more than 2%), the electrolytic manganese residue is still the type II common industrial solid waste, and the electrolytic manganese residue cannot enter a type II residue field for stockpiling. Meanwhile, the method has long stirring time, needs secondary stirring, has a normal low-speed stirring speed, and can not completely remove ammonia because the reaction temperature is normal room temperature and ammonia released by full reaction can be dissolved in water again.
The patent application document with the publication number of CN110639158B discloses a method for harmlessly treating electrolytic manganese slag, which is characterized in that calcium superphosphate and low-grade magnesium oxide are used for synergistically and stably solidifying manganese and ammonia nitrogen in the electrolytic manganese slag, heavy metals are mainly precipitated and stably solidified as phosphate under the condition of weak alkali, and the ammonia nitrogen is mainly stably solidified as struvite, so that secondary pollution is avoided. According to the method, calcium superphosphate, a rare resource material, is introduced by a chemical method, ammonia nitrogen is removed, heavy metals are solidified, however, the risk that magnesium oxide is continuously remained in electrolytic manganese slag in the form of soluble magnesium salt exists, the problem of ammonia volatilization under the condition of weak alkali cannot be thoroughly solved, the risk of secondary pollution exists, the market price of calcium superphosphate is high, and the disposal cost is greatly increased.
Patent application publication No. CN109626853A discloses a harmless treatment process for electrolytic manganese slag, which comprises adding calcium hydroxide into electrolytic manganese slag to obtain a product I, adding a compound agent into a sodium chloride solution to obtain a product II, mixing the product I with the product II to obtain a product III, heating the product III, washing with hot water, filtering, and drying. Wherein the compound agent consists of citrate and aluminum sulfate. The aluminum sulfate added in the method plays a role of a flocculating agent in the process, soluble salt is additionally introduced after the sodium chloride solution is added, so that the utilization difficulty of the electrolytic manganese slag is increased, and the added aluminum sulfate and sodium chloride belong to pure industrial raw materials, so that the cost is high, the disposal difficulty is increased, and the industrialization is difficult to implement.
Therefore, the existing electrolytic manganese slag harmless treatment method has many problems.
Disclosure of Invention
The invention provides a harmless treatment method of electrolytic manganese slag to solve the technical problems.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a harmless treatment method of electrolytic manganese slag comprises the following steps: crushing and grinding the electrolytic manganese slag, adding sulphoaluminate cement clinker, alkaline materials, industrial by-product gypsum, alum and water, adjusting the water temperature, uniformly stirring to obtain a mixture, fully reacting the mixture under the condition of micro negative pressure, and aging to obtain harmless electrolytic manganese slag.
Further, the aging time is 23-25 h.
Further, the water content of the harmless electrolytic manganese slag is less than 10%.
Further, the materials are prepared from the following components in parts by weight: 50-80 parts of sulphoaluminate cement clinker, 150-250 parts of electrolytic manganese slag, 10-50 parts of alkaline material, 50-150 parts of industrial byproduct gypsum, 2-10 parts of alum and 500-800 parts of water.
Further, the alkaline material is quick lime, slaked lime or carbide slag containing alkaline substances.
Further, the water temperature is adjusted to 50-80 ℃.
Further, the pressure condition of the micro negative pressure is-20 to-40 kPa, and the reaction time is 3 to 10 min.
Further, the industrial byproduct gypsum is phosphogypsum or desulfurized gypsum.
Further, the rotating speed of the stirring is 10-500 revolutions per minute, and the stirring time is 3-10 min.
Further, the harmless treatment method of the electrolytic manganese slag specifically comprises the following steps:
(1) crushing and grinding the electrolytic manganese slag, adding sulphoaluminate cement clinker, alkaline materials, industrial by-product gypsum, alum and water, adjusting the water temperature, and uniformly stirring to obtain a mixture;
(2) and (2) placing the mixture obtained in the step (1) under the condition of micro negative pressure for full reaction, and then performing aging treatment to obtain harmless electrolytic manganese slag.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
(1) in the invention, sulphoaluminate cement clinker, alkaline materials or alkaline waste residues, industrial by-product gypsum, alum and water are added into the electrolytic manganese residues, and the full removal of harmful substances and the full solidification of the harmful substances in the electrolytic manganese residues are realized by combining the processes of heating, stirring and micro negative pressure.
(2) The method has the advantages of low cost, easily obtained raw materials, simple process method, easy control, no need of calcination treatment at high temperature and drying compared with the traditional treatment method, greatly improved speed for treating the electrolytic manganese slag, greatly reduced energy consumption, greatly improved speed for treating the electrolytic manganese slag, and suitability for large-scale low-cost quick harmless treatment of electrolytic manganese slag discharge enterprises.
(3) The invention provides a technology for harmlessly disposing harmful substances in electrolytic manganese slag to remove the harmful substances in the electrolytic manganese slag, and the disposed electrolytic manganese slag can be largely used in the production of cement, concrete and wall materials.
Drawings
In order to illustrate the embodiments of the present invention or the technical solutions in the prior art more clearly, the drawings needed in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only some examples of the present invention, and for a person skilled in the art, without inventive step, other drawings can be obtained according to these drawings:
FIG. 1 is a process flow chart of the harmless treatment method of electrolytic manganese slag.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
A harmless treatment method of electrolytic manganese slag comprises the following steps: crushing and grinding the electrolytic manganese slag, adding sulphoaluminate cement clinker, alkaline materials, industrial by-product gypsum, alum and water, adjusting the water temperature, uniformly stirring to obtain a mixture, fully reacting the mixture under the condition of micro negative pressure, and aging to obtain harmless electrolytic manganese slag; the method specifically comprises the following steps:
(1) crushing and grinding the electrolytic manganese slag, adding sulphoaluminate cement clinker, alkaline materials, industrial by-product gypsum, alum and water, adjusting the water temperature, and uniformly stirring to obtain a mixture;
(2) and (2) placing the mixture obtained in the step (1) under the condition of micro negative pressure for full reaction, and then performing aging treatment to obtain harmless electrolytic manganese slag.
Further, the aging time is 23 h; the water content of the harmless electrolytic manganese slag is less than 10 percent; the materials are prepared from the following components in parts by weight: 50 parts of sulphoaluminate cement clinker, 250 parts of electrolytic manganese slag, 50 parts of alkaline material, 120 parts of industrial by-product gypsum, 5 parts of alum and 525 parts of water; the alkaline material is quicklime, slaked lime or carbide slag containing alkaline substances; the water temperature is adjusted to 50 ℃; the pressure condition of the micro negative pressure is-20 kPa, and the reaction time is 5 min; the industrial byproduct gypsum is phosphogypsum or desulfurized gypsum; the stirring speed is 300 r/min, and the stirring time is 6 min.
Example 2
A harmless treatment method of electrolytic manganese slag comprises the following steps: crushing and grinding the electrolytic manganese slag, adding sulphoaluminate cement clinker, alkaline materials, industrial by-product gypsum, alum and water, adjusting the water temperature, uniformly stirring to obtain a mixture, fully reacting the mixture under the condition of micro negative pressure, and aging to obtain harmless electrolytic manganese slag; the method specifically comprises the following steps:
(1) crushing and grinding the electrolytic manganese slag, adding sulphoaluminate cement clinker, alkaline materials, industrial by-product gypsum, alum and water, adjusting the water temperature, and uniformly stirring to obtain a mixture;
(2) and (2) placing the mixture obtained in the step (1) under the condition of micro negative pressure for full reaction, and then performing aging treatment to obtain harmless electrolytic manganese slag.
Further, the aging time is 25 h; the water content of the harmless electrolytic manganese slag is less than 10 percent; the materials are prepared from the following components in parts by weight: 60 parts of sulphoaluminate cement clinker, 200 parts of electrolytic manganese slag, 40 parts of alkaline material, 100 parts of industrial by-product gypsum, 6 parts of alum and 594 parts of water; the alkaline material is quicklime, slaked lime or carbide slag containing alkaline substances; the water temperature is adjusted to 60 ℃; the pressure condition of the micro negative pressure is-30 kPa, and the reaction time is 6 min; the industrial byproduct gypsum is phosphogypsum or desulfurized gypsum; the stirring speed is 400 r/min, and the stirring time is 6 min.
Example 3
A harmless treatment method of electrolytic manganese slag comprises the following steps: crushing and grinding the electrolytic manganese slag, adding sulphoaluminate cement clinker, alkaline materials, industrial by-product gypsum, alum and water, adjusting the water temperature, uniformly stirring to obtain a mixture, fully reacting the mixture under the condition of micro negative pressure, and aging to obtain harmless electrolytic manganese slag; the method specifically comprises the following steps:
(1) crushing and grinding the electrolytic manganese slag, adding sulphoaluminate cement clinker, alkaline materials, industrial by-product gypsum, alum and water, adjusting the water temperature, and uniformly stirring to obtain a mixture;
(2) and (2) placing the mixture obtained in the step (1) under the condition of micro negative pressure for full reaction, and then performing aging treatment to obtain harmless electrolytic manganese slag.
Further, the aging time is 24 hours; the water content of the harmless electrolytic manganese slag is less than 10 percent; the materials are prepared from the following components in parts by weight: 70 parts of sulphoaluminate cement clinker, 200 parts of electrolytic manganese slag, 30 parts of alkaline material, 80 parts of industrial by-product gypsum, 7 parts of alum and 613 parts of water; the alkaline material is quicklime, slaked lime or carbide slag containing alkaline substances; the water temperature is adjusted to 50-80 ℃; the pressure condition of the micro negative pressure is-30 kPa, and the reaction time is 7 min; the industrial byproduct gypsum is phosphogypsum or desulfurized gypsum; the stirring speed is 400 r/min, and the stirring time is 7 min.
Example 4
A harmless treatment method of electrolytic manganese slag comprises the following steps: crushing and grinding the electrolytic manganese slag, adding sulphoaluminate cement clinker, alkaline materials, industrial by-product gypsum, alum and water, adjusting the water temperature, uniformly stirring to obtain a mixture, fully reacting the mixture under the condition of micro negative pressure, and aging to obtain harmless electrolytic manganese slag; the method specifically comprises the following steps:
(1) crushing and grinding the electrolytic manganese slag, adding sulphoaluminate cement clinker, alkaline materials, industrial by-product gypsum, alum and water, adjusting the water temperature, and uniformly stirring to obtain a mixture;
(2) and (2) placing the mixture obtained in the step (1) under the condition of micro negative pressure for full reaction, and then performing aging treatment to obtain harmless electrolytic manganese slag.
Further, the aging time is 24 hours; the water content of the harmless electrolytic manganese slag is less than 10 percent; the materials are prepared from the following components in parts by weight: 80 parts of sulphoaluminate cement clinker, 250 parts of electrolytic manganese slag, 20 parts of alkaline material, 60 parts of industrial by-product gypsum, 8 parts of alum and 582 parts of water; the alkaline material is quicklime, slaked lime or carbide slag containing alkaline substances; the water temperature is adjusted to 80 ℃; the pressure condition of the micro negative pressure is-40 kPa, and the reaction time is 8 min; the industrial byproduct gypsum is phosphogypsum or desulfurized gypsum; the stirring speed is 500 r/min, and the stirring time is 8 min.
Example 5
A harmless treatment method of electrolytic manganese slag comprises the following steps: crushing and grinding the electrolytic manganese slag, adding sulphoaluminate cement clinker, alkaline materials, industrial by-product gypsum, alum and water, adjusting the water temperature, uniformly stirring to obtain a mixture, fully reacting the mixture under the condition of micro negative pressure, and aging to obtain harmless electrolytic manganese slag; the method specifically comprises the following steps:
(1) crushing and grinding the electrolytic manganese slag, adding sulphoaluminate cement clinker, alkaline materials, industrial by-product gypsum, alum and water, adjusting the water temperature, and uniformly stirring to obtain a mixture;
(2) and (2) placing the mixture obtained in the step (1) under the condition of micro negative pressure for full reaction, and then performing aging treatment to obtain harmless electrolytic manganese slag.
Further, the aging time is 23 h; the water content of the harmless electrolytic manganese slag is less than 10 percent; the materials are prepared from the following components in parts by weight: 50 parts of sulphoaluminate cement clinker, 250 parts of electrolytic manganese slag, 10 parts of alkaline material, 50 parts of industrial by-product gypsum, 2 parts of alum and 500 parts of water; the alkaline material is quicklime, slaked lime or carbide slag containing alkaline substances; the water temperature is adjusted to 50 ℃; the pressure condition of the micro negative pressure is-20 kPa, and the reaction time is 3 min; the industrial byproduct gypsum is phosphogypsum or desulfurized gypsum; the stirring speed is 10 r/min, and the stirring time is 3 min.
Example 6
A harmless treatment method of electrolytic manganese slag comprises the following steps: crushing and grinding the electrolytic manganese slag, adding sulphoaluminate cement clinker, alkaline materials, industrial by-product gypsum, alum and water, adjusting the water temperature, uniformly stirring to obtain a mixture, fully reacting the mixture under the condition of micro negative pressure, and aging to obtain harmless electrolytic manganese slag; the method specifically comprises the following steps:
(1) crushing and grinding the electrolytic manganese slag, adding sulphoaluminate cement clinker, alkaline materials, industrial by-product gypsum, alum and water, adjusting the water temperature, and uniformly stirring to obtain a mixture;
(2) and (2) placing the mixture obtained in the step (1) under the condition of micro negative pressure for full reaction, and then performing aging treatment to obtain harmless electrolytic manganese slag.
Further, the aging time is 25 h; the water content of the harmless electrolytic manganese slag is less than 10 percent; the materials are prepared from the following components in parts by weight: 80 parts of sulphoaluminate cement clinker, 150 parts of electrolytic manganese slag, 50 parts of alkaline material, 150 parts of industrial by-product gypsum, 10 parts of alum and 800 parts of water; the alkaline material is quicklime, slaked lime or carbide slag containing alkaline substances; the water temperature is adjusted to 80 ℃; the pressure condition of the micro negative pressure is-40 kPa, and the reaction time is 10 min; the industrial byproduct gypsum is phosphogypsum or desulfurized gypsum; the stirring speed is 500 r/min, and the stirring time is 10 min.
The applicant sends the harmless electrolytic manganese slag prepared by the method in the embodiment 1-4 to a professional qualification organization for detection, the amount of released ammonia is detected according to GB18588-2001, the content of soluble manganese, soluble lead, soluble mercury and soluble arsenic is detected according to GB5085.3-2007, the content of magnesium oxide and alkali is detected according to GB/T176-2017, the water content is detected according to GB/T1596-2017, untreated original state electrolytic manganese slag is used as a control group, and the detection results are shown in the following table 1:
TABLE 1
According to the experimental data of Standard 1, the electrolytic manganese slag treated by the method can achieve the harmless treatment effect, and the pollutant content of the treated product is greatly reduced.
To further illustrate that the present invention can achieve the technical effects, the following experiments were performed:
comparative example 1
The treatment of electrolytic manganese slag was carried out according to the examples in patent application CN102161048B (a harmless treatment method for electrolytic manganese slag).
Comparative example 2
The treatment of electrolytic manganese slag was carried out according to the examples in patent application CN110639158B, a method for the harmless treatment of electrolytic manganese slag.
Comparative example 3
The treatment of electrolytic manganese slag was carried out according to the examples in patent application CN109626853A (a process for the harmless treatment of electrolytic manganese slag).
In the experimental process, the problems of comparative examples 1 to 3 are found, the process of the comparative example 1 is complicated, the property of slag in the treated electrolytic manganese slag is not changed (soluble salt is more than 2%), the treated product is still type II common industrial solid waste, the treated product cannot enter a type II slag field for stockpiling, the stirring time is long, and ammonia cannot be completely removed. The method of the comparative example 2 has the risk that magnesium oxide is continuously remained in the electrolytic manganese slag in the form of soluble magnesium salt, the problem of ammonia volatilization under the condition of weak alkali cannot be thoroughly solved, the risk of secondary pollution exists, and meanwhile, the market price of calcium superphosphate is higher, so that the disposal cost is greatly improved. The method of the comparative example 3 can increase the utilization difficulty of the electrolytic manganese slag, and the added aluminum sulfate and sodium chloride belong to pure industrial raw materials, so the cost is higher, the disposal difficulty is increased, and the industrialization is difficult to implement. However, the above problems do not occur in any of the embodiments 1 to 5 of the present application.
In conclusion, the invention realizes the full removal of harmful substances and the full solidification of the harmful substances in the electrolytic manganese slag by combining the heating, stirring and micro negative pressure processes. The method has the advantages of low treatment cost, easily obtained raw materials, simple process method, capability of obtaining the electrolytic manganese slag with lower moisture without drying, easy control, greatly improved speed of treating the electrolytic manganese slag compared with the traditional treatment method, and suitability for large-scale low-cost quick harmless treatment of electrolytic manganese slag discharging enterprises.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. The harmless treatment method of the electrolytic manganese slag is characterized by comprising the following steps: crushing and grinding the electrolytic manganese slag, adding sulphoaluminate cement clinker, alkaline materials, industrial by-product gypsum, alum and water, adjusting the water temperature, uniformly stirring to obtain a mixture, fully reacting the mixture under the condition of micro negative pressure, and aging to obtain harmless electrolytic manganese slag.
2. The method for harmlessly disposing the electrolytic manganese slag according to claim 1, wherein: the aging time is 23-25 h.
3. The method for harmlessly disposing the electrolytic manganese slag according to claim 1, wherein: the water content of the harmless electrolytic manganese slag is less than 10 percent.
4. The method for harmlessly disposing the electrolytic manganese slag according to claim 1, wherein: the materials are prepared from the following components in parts by weight: 50-80 parts of sulphoaluminate cement clinker, 150-250 parts of electrolytic manganese slag, 10-50 parts of alkaline material, 50-150 parts of industrial byproduct gypsum, 2-10 parts of alum and 500-800 parts of water.
5. The method for harmlessly disposing the electrolytic manganese slag according to claim 1, wherein: the alkaline material is quicklime, slaked lime or carbide slag containing alkaline substances.
6. The method for harmlessly disposing the electrolytic manganese slag according to claim 1, wherein: the water temperature is adjusted to 50-80 ℃.
7. The method for harmlessly disposing the electrolytic manganese slag according to claim 1, wherein: the pressure condition of the micro negative pressure is-20 to-40 kPa, and the reaction time is 3 to 10 min.
8. The method for harmlessly disposing the electrolytic manganese slag according to claim 1, wherein: the industrial byproduct gypsum is phosphogypsum or desulfurized gypsum.
9. The method for harmlessly disposing the electrolytic manganese slag according to claim 1, wherein: the stirring speed is 10-500 r/min, and the stirring time is 3-10 min.
10. The method for harmlessly disposing the electrolytic manganese residues according to any one of claims 1 to 9, which comprises the following steps:
(1) crushing and grinding the electrolytic manganese slag, adding sulphoaluminate cement clinker, alkaline materials, industrial by-product gypsum, alum and water, adjusting the water temperature, and uniformly stirring to obtain a mixture;
(2) and (2) placing the mixture obtained in the step (1) under the condition of micro negative pressure for full reaction, and then performing aging treatment to obtain harmless electrolytic manganese slag.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111314529.7A CN113968716A (en) | 2021-11-08 | 2021-11-08 | Harmless treatment method for electrolytic manganese slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111314529.7A CN113968716A (en) | 2021-11-08 | 2021-11-08 | Harmless treatment method for electrolytic manganese slag |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113968716A true CN113968716A (en) | 2022-01-25 |
Family
ID=79589579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111314529.7A Pending CN113968716A (en) | 2021-11-08 | 2021-11-08 | Harmless treatment method for electrolytic manganese slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113968716A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114505323A (en) * | 2022-03-10 | 2022-05-17 | 广西建筑材料科学研究设计院有限公司 | Harmless treatment method and equipment for electrolytic manganese slag |
| CN114871240A (en) * | 2022-03-30 | 2022-08-09 | 湖南博一环保科技有限公司 | Electrolytic manganese filter-press residue for removing ammonia nitrogen and desulfurization as well as preparation method and application thereof |
| CN115382886A (en) * | 2022-08-10 | 2022-11-25 | 桂林理工大学 | Mechanical homogenization-low-temperature thermal activation accurate harmless treatment method for electrolytic manganese slag |
| CN115780478A (en) * | 2023-01-03 | 2023-03-14 | 重庆交通大学 | Formula, treatment method and finished product for synergistically stabilizing, solidifying and recovering electrolytic manganese slag |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102876330A (en) * | 2012-10-10 | 2013-01-16 | 北京中科通用能源环保有限责任公司 | Curing agent for heavy metal contaminated soil restoration and heavy metal contaminated soil restoration method |
| CN108262336A (en) * | 2018-02-24 | 2018-07-10 | 昆明理工大学 | A kind of solidification processing method of electrolytic manganese residues |
| CN109127650A (en) * | 2018-07-26 | 2019-01-04 | 四川海沛环保科技有限公司 | A method of utilizing cement kiln intermediate product harmless treatment electrolytic manganese residues |
| CN109912288A (en) * | 2019-02-28 | 2019-06-21 | 西南科技大学 | A kind of electrolytic manganese residues cooperate with harmless disposal method with ardealite |
-
2021
- 2021-11-08 CN CN202111314529.7A patent/CN113968716A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102876330A (en) * | 2012-10-10 | 2013-01-16 | 北京中科通用能源环保有限责任公司 | Curing agent for heavy metal contaminated soil restoration and heavy metal contaminated soil restoration method |
| CN108262336A (en) * | 2018-02-24 | 2018-07-10 | 昆明理工大学 | A kind of solidification processing method of electrolytic manganese residues |
| CN109127650A (en) * | 2018-07-26 | 2019-01-04 | 四川海沛环保科技有限公司 | A method of utilizing cement kiln intermediate product harmless treatment electrolytic manganese residues |
| CN109912288A (en) * | 2019-02-28 | 2019-06-21 | 西南科技大学 | A kind of electrolytic manganese residues cooperate with harmless disposal method with ardealite |
Non-Patent Citations (2)
| Title |
|---|
| 贡长生主编, vol. 1, 湖北科学技术出版社, pages: 113 * |
| 陶长元等: "《电解锰节能减排理论与工程应用》", vol. 1, 30 November 2018, 重庆大学出版社, pages: 78 - 80 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114505323A (en) * | 2022-03-10 | 2022-05-17 | 广西建筑材料科学研究设计院有限公司 | Harmless treatment method and equipment for electrolytic manganese slag |
| CN114871240A (en) * | 2022-03-30 | 2022-08-09 | 湖南博一环保科技有限公司 | Electrolytic manganese filter-press residue for removing ammonia nitrogen and desulfurization as well as preparation method and application thereof |
| CN114871240B (en) * | 2022-03-30 | 2023-05-30 | 湖南博一环保科技有限公司 | Electrolytic manganese filter pressing slag for ammonia nitrogen removal and desulfurization as well as preparation method and application thereof |
| CN115382886A (en) * | 2022-08-10 | 2022-11-25 | 桂林理工大学 | Mechanical homogenization-low-temperature thermal activation accurate harmless treatment method for electrolytic manganese slag |
| CN115382886B (en) * | 2022-08-10 | 2023-06-20 | 桂林理工大学 | Mechanical homogenization-low-temperature thermal activation accurate harmless treatment method for electrolytic manganese slag |
| CN115780478A (en) * | 2023-01-03 | 2023-03-14 | 重庆交通大学 | Formula, treatment method and finished product for synergistically stabilizing, solidifying and recovering electrolytic manganese slag |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113968716A (en) | Harmless treatment method for electrolytic manganese slag | |
| CN107628632B (en) | Method for preparing flocculant polyaluminium chloride by using fly ash | |
| Yang et al. | Solidification/stabilization and separation/extraction treatments of environmental hazardous components in electrolytic manganese residue: a review | |
| CN114349413B (en) | Barium slag harmless recycling treatment method and prepared building material | |
| CN113213789B (en) | Paving brick prepared based on household garbage incineration fly ash and preparation method thereof | |
| CN114804668B (en) | Preparation method of activated carbon negative material for producing recycled aggregate | |
| CN112830699B (en) | Cement admixture, preparation method and application | |
| CN101948142A (en) | Method for producing sludge modifier by utilizing coal gangue | |
| CN112125537B (en) | Industrial preparation technology of calcium hydroxide | |
| CN113648586A (en) | Wet harmless treatment method for electrolytic manganese slag | |
| CN112624651A (en) | Resource utilization method of electrolytic manganese filter-pressing residues | |
| CN108516707B (en) | Ionic curing agent and red mud fly ash cementing material | |
| CN103030312A (en) | Treatment method of magnesium metal smelting waste slag | |
| Liu et al. | Harmless treatment of electrolytic manganese residue: Ammonia nitrogen recovery, preparation of struvite and nonsintered bricks | |
| CN107759176A (en) | The solid waste comprehensive utilization of slag powders makes building material | |
| CN113213498B (en) | Cement-based material carbonization recycling method and calcium carbonate whisker material | |
| CN111153610A (en) | Method for comprehensively utilizing high-iron high-calcium high-silicon waste magnesite and boron mud | |
| CN114804177A (en) | Industrial solid waste electrolytic manganese slag mineralized CO 2 Resource utilization method | |
| CN112875832B (en) | Preparation method of alkaline slow-release material | |
| CN114405962A (en) | Method for efficiently removing ammonia nitrogen in electrolytic manganese slag | |
| CN111039299B (en) | Method for efficiently recycling lead-zinc tailings | |
| CN108751872B (en) | Curing agent for treating inorganic distillation residues rich in chloride | |
| CN112979321A (en) | Method for utilizing drilling waste | |
| CN108793815A (en) | A kind of technique of ardealite and red mud relieving haperacidity coproduction concrete accelerator | |
| CN114804681A (en) | Method for preparing composite modified magnesium oxychloride cement by using industrial waste salt |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220125 |