CN106422716B - SO in copper extraction tailings desorption flue gas 2 And resource method and device - Google Patents

SO in copper extraction tailings desorption flue gas 2 And resource method and device Download PDF

Info

Publication number
CN106422716B
CN106422716B CN201610716473.0A CN201610716473A CN106422716B CN 106422716 B CN106422716 B CN 106422716B CN 201610716473 A CN201610716473 A CN 201610716473A CN 106422716 B CN106422716 B CN 106422716B
Authority
CN
China
Prior art keywords
slurry
tank
desulfurization
tower
pump
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610716473.0A
Other languages
Chinese (zh)
Other versions
CN106422716A (en
Inventor
宁平
王学谦
殷在飞
殷梁淘
李凯
陈茂生
王郎郎
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.)
Kunming University of Science and Technology
Original Assignee
Kunming University of Science and Technology
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 Kunming University of Science and Technology filed Critical Kunming University of Science and Technology
Priority to CN201610716473.0A priority Critical patent/CN106422716B/en
Publication of CN106422716A publication Critical patent/CN106422716A/en
Application granted granted Critical
Publication of CN106422716B publication Critical patent/CN106422716B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77Liquid phase processes
    • B01D53/78Liquid phase processes with gas-liquid contact
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • B01D53/50Sulfur oxides
    • B01D53/501Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006Wet processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/40Alkaline earth metal or magnesium compounds
    • B01D2251/402Alkaline earth metal or magnesium compounds of magnesium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/40Alkaline earth metal or magnesium compounds
    • B01D2251/404Alkaline earth metal or magnesium compounds of calcium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/60Inorganic bases or salts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention relates to a method for removing SO in flue gas by copper extraction tailings 2 And a resource method and a device adopted by the method belong to the technical field of environmental protection. The invention utilizes the copper extraction tailings to contain desulphurizing active substances (ferrous silicate (Fe) 2 SiO 4 ) Magnesium ferrite (MgFe) 2 O 4 ) Spodumene (CaFeSi) 2 O 6 ) Etc. in aqueous solution, with SO in flue gas 2 Generating sulfite by reaction, generating sulfate under the action of oxygen in flue gas, and containing SO 2 Is contacted with the slurry of the copper extraction tailings SO 2 Absorbed and the flue gas is purified; and then, by adding ammonium sulfide, ammonium bicarbonate and lime milk step by step, iron ions, zinc ions, copper ions, ammonium ions and the like in the desulfurization slurry are recycled.

Description

SO in copper extraction tailings desorption flue gas 2 And resource method and device
Technical Field
The invention relates to a method for removing SO in flue gas by copper extraction tailings 2 And further to a method of recycling, and to the apparatus employed. The copper extraction tailings are solid waste discharged in copper smelting, and are used for removing SO in flue gas 2 The aim of treating waste by waste is achieved, and iron, copper, zinc and the like in the copper extraction tailings are recycled, and the method belongs to the technical field of environmental protection.
Background
Copper smelting is mainly carried out on copper ores, according to relevant literature records, the copper ores in China have ascertained that the resource reserves are 7048 ten thousand tons until 2007, wherein the basic reserves are 3070 ten thousand tons and account for 43.6% of the total reserves, the copper ores are mainly distributed in five provinces including Jiangxi, yunnan, gansu, hubei and Shanxi, and the resource reserves which are utilized at present account for over 70% of the utilized and reserved resource reserves in China. Copper mine resources in China are various, and mainly include primary copper sulfide mine and secondary copper oxide mine. The copper sulphide ore is accompanied by metal minerals such as pyrite, pentlandite, sphalerite, galena and the like; metal ores such as limonite, hematite, siderite and the like are also associated with the copper oxide ores; gangue minerals such as quartz, quartz stone, calcite and the like are associated in the copper ores; depending on the type and amount of associated minerals, the copper ores sometimes contain different and sometimes more different components.
Copper metallurgy methods are more and generally divided into two major categories, namely pyrogenic and wet. Pyrometallurgy is the main method of producing copper, 80% of which in the world is currently obtained by pyrometallurgy. The copper sulfide ore has good selectable performance and easy enrichment, and most of refined copper ores after mineral separation adopt a pyrometallurgy process.
The matte smelting is a fire smelting process widely adopted in the world at present, and the matte smelting process is to add copper concentrate ore into fluxing agent silicon dioxide (SiO) 2 ) And limestone (CaCO) 3 ) Smelting at 1150-1250 deg.c to produce copper and sulfur in the furnace material to produce sulfonium reaction to produce Cu 2 S+FeS (copper matte) melt and FeO are main products, and at the same time, a small amount of Fe is generated 2 O 3 FeO and Fe produced 2 O 3 With SiO in the furnace charge 2 MgO and CaO produce slag forming reaction to produce eutectic mainly of fayalite, magnesium ferrite and cadherite called slag.
Copper resources in China currently keep reserves of 7048 ten thousand, 4100 ten thousand has been developed, and the rest reserves which are not utilized are: the method has the advantages of less rich ore, more lean ore, low grade of raw ore, difficult mining and separation, poor construction conditions and development benefits and difficult recycling. The slag contains a small amount of copper, along with the sustainable development of copper smelting industry in China, copper ore resources are exhausted gradually, copper ores containing 0.2-0.3% of copper are mined and utilized at present, and the copper content of the slag produced in the copper smelting process is more than 0.5%. The copper content in the slag is higher than that of the primary copper ore, and recovery is necessary, and the process is called slag depletion treatment.
At present, slag depletion methods are more, and two main methods are a grinding float method and a reduction depletion method.
The method for treating slag by using float method is that after the slowly cooled slag is crushed, the crushed slag is ground into 200 meshes of granularity by using ball mill, and the copper-extracted slag is separated by using the difference of the surface physical properties of cuprous sulfide crystal and metallic copper particles in the slag and slag components or adding a flotation agent, and the separated slag is called copper-extracted tailings.
Polysulfides such as pyrite (FeS) during pyrometallurgical processes 2 ) And chalcopyrite (CuFeS) 2 ) Sulfur is decomposed in the furnace and oxidized into SO by oxygen in the air 2 Discharging SO in the flue gas along with the flue gas 2 The content is very high. Such as air blast, SO in the flue gas at the outlet of the reaction furnace 2 The content reaches 7.7 percent; SO in oxygen-enriched blast flue gas 2 The content is up to 15%, and the flue gas at the outlet of the reaction furnace is mostly provided with recovered SO 2 Apparatus for producing sulfuric acid, but recovering SO 2 The flue gas after the treatment still contains higher SO 2 The non-point source pollution intensity is increased, and the treatment is more difficult; on the other hand, no matter the sulfuric acid tail gas or the non-point source scattered smoke exhaust tail gas is purified, the currently adopted desulfurization method has the problems of high cost, inconvenient raw material source, comprehensive utilization and the like, and brings a heavy environmental protection burden to the development of enterprises. Therefore, aiming at the atmospheric pollution households of nonferrous metallurgy, developing a high-efficiency, applicable and local-appropriate low-concentration sulfur dioxide and heavy metal cooperative control technology is imperative.
Laboratory tests prove that the copper tailings have strong SO absorption 2 The thermodynamic parameter analysis of the copper extraction tailings shows that fayalite, magnesium ferrite, cadherite and the like are used for removing SO 2 The active substances of the catalyst can replace the currently commonly used desulfurizing agents such as lime, limestone, ammonia water and the like, the product is recovered in the desulfurizing process, the active substances are fully utilized, and a new way for recycling the copper extraction tailings is opened up.
Disclosure of Invention
The invention aims to provide a method for removing SO in flue gas by extracting copper tailings 2 And a recycling method, the invention removes SO in the flue gas 2 Based on the principle that the copper extraction tailings contain desulfurizing active substances such as ferrous silicate (Fe) 2 SiO 4 ) Magnesium ferrite (MgFe) 2 O 4 ) Spodumene (CaFeSi) 2 O 6 ) Etc. in aqueous solution, with SO in flue gas 2 Generating sulfite by reaction, generating sulfate under the action of oxygen in flue gas, and containing SO 2 Is contacted with the slurry of the copper extraction tailings SO 2 Absorbed and the flue gas is purified; because the main component in the copper extraction tailings is ferrous silicate, the product in the solution is mainly soluble ferrous sulfate, and SiO is generated in the solution 2 、Fe 2 O 3 、MgSO 4 And CaSO 4 And removing the sediment along with the tailings.
The invention is realized by the following technical scheme:
SO in copper smelting flue gas is removed to copper extraction tailings 2 The method for recycling the resources comprises the following steps:
(1) Removing SO in flue gas by copper extraction tailings 2 Preparing desulfurization slurry:
preparing water for extracting copper tailings into slurry serving as supplement of desulfurization circulating liquid and adjusting pH value, wherein the solid content of the slurry is 15-20wt%, introducing flue gas to contact the slurry for extracting copper tailings for desulfurization, and the ratio of liquid to gas (slurry for extracting copper tailings to flue gas) is 8-25L/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The pH of the copper extraction tailings slurry in the desulfurization process is reduced, and when the pH is less than 4.5, fresh copper extraction tailings slurry is replenished, so that the pH is kept at 4.5-5.
SO in flue gas 2 And O 2 The reaction with ferrous silicate, magnesium ferrite and spodumene in the copper extraction tailings slurry is as follows:
Fe 2 SiO 4(s) + 2SO 2(g) + O 2(g) = 2FeSO 4 + SiO 2
MgFe 2 O 4(s) + SO 2(g) + 0.5O 2(g) +7H 2 O = MgSO 4 ·7H 2 O↓+ Fe 2 O 3
CaFeSi 2 O 6(s) + 2SO 2(g) + O 2(g) = CaSO 4 ↓+ FeSO 4 +2SiO 2
the flue gas after desulfurization and purification is discharged after demisting, the copper extraction tailings slurry after desulfurization is filtered to obtain desulfurization slurry, and filter residues can be used as building materials or cement raw materials;
(2) Recycling of desulfurization slurry:
the desulfurization slurry obtained in the step (1) contains a large amount of iron ions, zinc ions and a small amount of copper, manganese, mercury, arsenic and other ions, wherein the ions are valuable substances and toxic and harmful substances, and cannot be discharged, otherwise, the desulfurization slurry pollutes a water body and needs to be treated. The invention adopts a chemical fractional precipitation method to treat the desulfurization slurry, and the treatment process is a recycling process.
(1) Adding 5-6.5 kg/m ammonium sulfide into the desulfurization slurry obtained in the step (1) 3 Zinc in the desulfurization slurry reacts with small amounts of copper, manganese, mercury, arsenic and other ions as follows:
(NH 4 ) 2 S + ZnSO 4 → ZnS↓+ (NH 4 ) 2 SO 4
(NH 4 ) 2 S + CuSO 4 → CuS↓+ (NH 4 ) 2 SO 4
(NH 4 ) 2 S + MnSO 4 → MnS↓+ (NH 4 ) 2 SO 4
(NH 4 ) 2 S + HgSO 4 → HgS↓+ (NH 4 ) 2 SO 4
(NH 4 ) 2 S + As 2 (SO 4 ) 3 → As 2 S 3 ↓+ (NH 4 ) 2 SO 4
the reaction liquid is filtered, the filtrate is subjected to the next treatment, the filter residue is zinc sulfide sludge which is mainly a mixture of zinc sulfide and copper sulfide, the main components are 75-80% of zinc sulfide, 15-20% of copper sulfide, 5-6% of manganese sulfide, and trace arsenic sulfide is contained, and the zinc sulfide sludge can be used for extracting zinc and copper.
(2) Adding 25-35 kg/m ammonium bicarbonate into the filtrate 3 The following reactions occur:
FeSO 4 + (NH 4 )HCO 3 = FeCO 3 ↓ + (NH 4 )HSO 4
(NH 4 )HSO 4 + (NH 4 )HCO3 = (NH 4 ) 2 SO 4 + CO 2 ↑ + H 2 O
filtering to obtain filtrate, further treating the filtrate as sewage, wherein the filter residue is ferrous carbonate, and the ferrous carbonate can be used for preparing ferric salt, magnetic ferric oxide, iron red pigment and the like.
(3) Sewage treatment and ammonia water recovery
The sewage obtained in the step (2) and the step (2) is also reserved with about 5.4g/L of ammonium sulfate, the ammonium sulfate is an eutrophication substance of a water body and can be discharged after being treated, and ammonia is also a fertilizer required by agriculture and has recycling value. The invention adopts an ammonia water-lime distillation method to treat sewage.
Lime milk is added into the sewage, the mol ratio of the ammonium sulfate to the lime milk is 1:1-1.5, and the reaction is as follows:
(NH 4 ) 2 SO 4 + Ca(OH) 2 = 2NH 3 ↑ + CaSO 4 ↓+ H 2 O
NH 3 + H 2 O = NH 3 •H 2 O
the concentration of ammonia water is regulated to 8-10%.
The device adopted by the invention comprises: the device comprises a pressurizing blower 1, a primary desulfurization tower 2, a secondary desulfurization tower 3, a demister 4, a slurry pump I5, a circulating pump I6, a circulating pump II 7, a slurry mixing tank 8, a desulfurization slurry storage tank 9, a slurry pump II 10, a desulfurization slurry overhead tank 11, a vacuum filter I12, a receiving tank I13, a vacuum pump I14, a dezincification tank 15, a screw pump 16, a plate-and-frame filter press 17, an iron removal tank 18, a slurry pump III 19, a concentration tank 20, a vacuum filter II 21, a receiving tank II 22, a vacuum pump II 23, a dryer 24, a sewage storage tank 25, a sewage pump 26, an ammonia-lime water distillation tower 27, a separator 28, a condenser 29 and an ammonia water tank 30;
the pressurizing blower 1 is connected with an air inlet of the primary desulfurization tower 2, an air outlet of the primary desulfurization tower 2 is connected with an air inlet of the secondary desulfurization tower 3, and an air outlet of the secondary desulfurization tower 3 is communicated with the outside through the demister 4;
the slurry mixing tank 8 is connected with a liquid inlet of the second-stage desulfurizing tower 3 through a slurry pump I5, a liquid outlet of the second-stage desulfurizing tower 3 is connected with a liquid inlet of the first-stage desulfurizing tower 2, a liquid outlet of the first-stage desulfurizing tower 2 is connected with a desulfurizing slurry storage tank 9, and the two-stage desulfurizing towers are all provided with circulating pumps for pressurizing slurry to the top of the tower and are provided with a plurality of corrosion-resistant wear-resistant rotational flow solid spray heads; the desulfurization slurry storage tank 9 is connected with an inlet of a desulfurization slurry high-level tank 11 through a slurry pump II 10, an outlet of the desulfurization slurry high-level tank 11 is connected with an inlet of a receiving tank I13 through a vacuum filter I12, the receiving tank I13 is provided with a vacuum pump I14, an outlet of the receiving tank I13 is connected with an inlet of a zinc removal tank 15, an outlet of the zinc removal tank 15 is connected with a plate-frame filter press 17 through a screw pump 16, a filtrate outlet of the plate-frame filter press 17 is connected with an inlet of an iron removal tank 18, an outlet of the iron removal tank 18 is connected with a concentration tank 20 through a slurry pump III 19, a supernatant outlet of the concentration tank 20 is connected with a sewage storage tank 25, a precipitation outlet of the concentration tank 20 is connected with a vacuum filter II 21, a filter residue outlet of the vacuum filter II 21 is connected with a dryer 24, a filtrate outlet of the vacuum filter II 21 is connected with an inlet of the receiving tank II 22, the receiving tank II 22 is provided with a vacuum pump II 23, and a filtrate outlet of the receiving tank II 22 is connected with the sewage storage tank 25;
the sewage storage tank 25 is connected with the liquid inlet of an ammonia-lime water distillation tower 27 through a sewage pump 26, and the air outlet of the ammonia-lime water distillation tower 27 is connected with an ammonia water tank 30 through a separator 28 and a condenser 29.
The working process of the device comprises the following steps: the flue gas is pressurized by a pressurizing blower 1 and sent into a first-stage desulfurizing tower 2 for first desulfurization, then enters a second-stage desulfurizing tower 3 for second desulfurization, and the flue gas after desulfurization purification reaches the standard is discharged after demisted by a demister 4;
copper extraction tailings and water are prepared into copper extraction tailings slurry in a slurry mixing tank 8, the copper extraction tailings slurry is sent into a secondary desulfurization tower 3 through a slurry pump I5, pressurized to 0.25MPa by a circulating pump II 7, sent to a tower top nozzle to be atomized and contacted with flue gas for secondary desulfurization, and the slurry after the secondary desulfurization enters a primary desulfurization tower 2 and passes through the circulating pump I6 pressurizing to 0.25MPa, and delivering to a tower top nozzle to spray mist and contact with the flue gas to absorb SO in the flue gas 2 Performing primary desulfurization, and then entering a desulfurization slurry storage tank 9 from the primary desulfurization tower 2 for subsequent procedures; a plurality of corrosion-resistant wear-resistant rotational flow solid spray heads are arranged in the two-stage desulfurizing towers; in the desulfurization process, the pH value of the copper extraction tailings slurry in the primary desulfurization tower 2 and the secondary desulfurization tower 3 is reduced, and when the pH value is less than 4.5, fresh copper extraction tailings slurry is supplemented from the slurry mixing tank 8, so that the pH value of the copper extraction tailings slurry in the desulfurization tower is kept at 4.5-5.
The desulfurization slurry in the desulfurization slurry storage tank 9 is sent into a slurry overhead tank 11 by a slurry pump II 10, flows into a vacuum filter 12 automatically for filtering, filter residues are discharged and can be used as building materials or cement raw materials, the filtered desulfurization slurry is sucked into a receiving tank I13 by a vacuum pump I14, the vacuum pump I14 works intermittently, when the receiving tank I13 is full of liquid, the vacuum pump I14 stops working, and after the receiving tank I13 is emptied, the vacuum pump I14 starts working; the filtered desulfurization slurry enters a zinc removal tank 15 from a receiving tank I13, ammonium sulfide is added into the zinc removal tank 15 to react to generate precipitates such as zinc sulfide, copper sulfide and the like, the mixture is pressed into a plate-and-frame filter press 17 by a screw pump 16, filter residues are zinc sulfide mud for zinc hydrometallurgy to extract zinc and copper, filtrate enters an iron removal tank 18, ammonium bicarbonate is added into the iron removal tank 18 to generate ferrous carbonate precipitation, the mixture is sent to a concentrating tank 20 to be precipitated and concentrated by a slurry pump III 19, supernatant fluid is decanted and used as sewage to enter a sewage storage tank 25, the ferrous carbonate precipitation is filtered by a vacuum filter 21, the filter cake is dried in a dryer 24 to obtain a ferrous carbonate product, and the filtrate is sucked into the receiving tank II 22 by a vacuum pump II 23 and then enters the sewage storage tank 25;
lime milk is added to a sewage tank 25 and mixed with sewage, and the mixture is sent to an ammonia-lime water distillation system 27 by a sewage pump 26 to be directly heated to 100 ℃ by steam (NH) 4 )HSO 4 Decomposing, allowing ammonia and water vapor to escape from the top of the distillation column, controlling the temperature to 90-95 ℃ through a separator 28, then condensing into ammonia water by a condenser 29, storing the ammonia water in an ammonia water tank 30, and adding water to adjust the concentration of the ammonia water to 8-10%.
The step of desulfurizing the copper extraction tailings slurry can be carried out according to SO in the flue gas 2 Content and discharge of flue gasAnd the standard requirement is that a primary or secondary desulfurization process flow is adopted.
The recovery of zinc ions and copper ions in the desulfurization slurry is completed through a zinc removal groove, zinc and copper ions are completely precipitated, and iron ions are not precipitated; the recovery of iron ions in the desulfurization slurry is completed through an iron removal tank, and the iron ions are completely precipitated.
Compared with the prior art, the invention has the beneficial effects that:
(1) The flue gas desulfurization is completed through a desulfurization tower, a plurality of corrosion-resistant wear-resistant rotational flow solid spray heads are arranged in the desulfurization tower, and the desulfurization tower has certain spray density, so that the whole desulfurization tower is filled with fog drops, the contact area is large, and the desulfurization efficiency is high;
(2) In order to ensure that the desulfurization solution has high oxidation speed and the requirement of subsequent procedures, the pH value of the desulfurization solution is controlled to be in the range of 4.5-5;
(3) The copper extraction tailings are used as desulfurizing agent, the desulfurizing efficiency reaches 85-95%, and SO in the flue gas is treated 2 The treatment is carried out, the secondary pollution of the flue gas is prevented, the purpose of treating pollution by waste is realized, and the method has important significance for environmental protection;
(4) In the desulfurization process, elements with recovery values such as iron, copper, zinc and the like in the copper extraction tailings are dissolved in the desulfurization slurry, the elements are recovered, waste is changed into products, the waste is utilized fully, and the purpose of recycling the copper extraction tailings is realized;
(5) Generally, environmental pollution treatment has great economic pressure on enterprises, the invention takes the copper extraction tailings as a desulfurizing agent, has low operation cost, simultaneously carries out copper and sulfur resource utilization, and has obvious economic benefit for enterprises. The environmental pollution treatment is not costly, and the economic benefit is a great innovation. The invention combines smelting flue gas desulfurization to realize the recycling of solid wastes, and has outstanding environmental benefit and economic benefit.
Drawings
FIG. 1 is a schematic flow chart of the present invention.
In the figure: the device comprises a 1-pressurizing blower, a 2-primary desulfurizing tower, a 3-secondary desulfurizing tower, a 4-demister, a 5-slurry pump I, a 6-circulating pump I, a 7-circulating pump II, an 8-slurry mixing tank, a 9-desulfurizing slurry storage tank, a 10-slurry pump II, a 11-desulfurizing slurry overhead tank, a 12-vacuum filter I, a 13-receiving tank I, a 14-vacuum pump I, a 15-dezincification tank, a 16-screw pump, a 17-plate-and-frame filter press, a 18-deironing tank, a 19-slurry pump III, a 20-concentrating tank, a 21-vacuum filter II, a 22-receiving tank II, a 23-vacuum pump II, a 24-dryer, a 25-sewage storage tank, a 26-sewage pump, a 27-ammonia-lime water distillation tower, a 28-separating device, a 29-condenser and a 30-ammonia tank.
Detailed Description
Example 1
The sulfur dioxide steel cylinder gas, the oxygen steel cylinder gas and the nitrogen steel cylinder gas are used for distribution in small experiments, the copper smelting flue gas is simulated, the mass flowmeter accurately controls the gas flow, after the distribution is stable, the gas is introduced into ore pulp for desulfurization reaction, a constant-temperature magnetic stirrer controls the temperature and stirring in the experimental process, and the concentration of sulfur dioxide at an inlet and an outlet is detected by using an HC-6 type micro sulfur and phosphorus analyzer.
SO 2 Inlet concentration 2856mg/m 3 At normal temperature, the solid-liquid ratio is 1:7 (16 g of ore tailings and 112g of distilled water), the oxygen content is 8%, the gas flow is 600-700 mL/min, and the desulfurization efficiency of ore pulp is maintained to be more than 90% in 43 hours of operation.
Example 2
30 ten thousand t/a sulfuric acid, sulfuric acid tail gas treatment capacity 100000Nm 3 /h, SO in the tail gas 2 The content is 2850mg/Nm 3 The tail gas outlet requires SO 2 The content was 100mg/Nm 3 . The flow is shown in figure 1 by adopting secondary desulfurization.
The sulfuric acid tail gas is pressurized to 0.2-0.3 kPa by a pressurizing blower 1, is sent into a first desulfurization tower 2 for first desulfurization, then enters a second desulfurization tower 3 for second desulfurization, the diameter phi of the desulfurization tower is 5m, the height of the desulfurization tower is 23.5m, the top of the desulfurization tower needs slurry to be pressurized to 0.25MPa by circulating pumps 6 and 7 respectively, and the circulation quantity is 1500m 3 And/h, spraying the flue gas into mist to contact the flue gas to absorb SO in the flue gas 2 The liquid-gas ratio is 8L/m 3 The purified smoke reaching the standard is discharged after demisted by a demister 4; the supplementing amount of the copper extraction tailings slurry with the solid content of 20 percent is 10m 3 And (3) delivering the slurry to a secondary desulfurization tower 3 by a slurry pump I5 for secondary desulfurization, and delivering the slurry after secondary desulfurization to a primary desulfurization tower 2Performing primary desulfurization, and then taking out 10m desulfurization solution from the primary desulfurization tower 2 3 And (3) entering a desulfurization slurry storage tank 9 for subsequent working procedures, wherein the pH value of slurry in the desulfurization tower is kept at 4.5-5.
The desulfurization slurry is sent to a slurry high-level tank 11 by a slurry pump II 10, flows into a vacuum filter 12 automatically for filtering, the filter cake is copper smelting residues, the stacked filter cake is still used as building materials, the filtrate enters a receiving tank I13 and then enters a dezincification tank 15, and the filtrate is 9m 3 And (3) adding 45-50 kg/h of ammonium sulfide to generate 60-65 kg/h of precipitates such as zinc sulfide and copper sulfide, pressing the precipitates into a plate-and-frame filter press 17 by a screw pump 16, and feeding about 100kg/h of obtained zinc sulfide mud to wet zinc hydrometallurgy to extract zinc and copper. The filtrate enters an iron removal tank 18, 280-290 kg/h of ammonium bicarbonate is added to generate 400-410 kg/h of ferrous carbonate precipitate, the mixture is sent to a concentration tank 20 for precipitation concentration by a slurry pump III 19, the supernatant fluid is decanted into a sewage storage tank 25, the ferrous carbonate precipitate is filtered by a vacuum filter 21, and the filter cake is dried in a dryer 24 to obtain 390-400 kg/h of ferrous carbonate product.
Adding 35kg/h of lime milk into a sewage storage tank 25, mixing sewage and lime milk, feeding the sewage and lime milk into an ammonia-lime water distillation system 27 by a sewage pump 26, heating the sewage to 100 ℃ by direct steam, enabling ammonia and water vapor to escape from the top of a distillation column, controlling the temperature to 90-95 ℃ by a contractor, then entering a condenser 29 to condense into ammonia water, storing the ammonia water in an ammonia water tank 30, and regulating the concentration of the ammonia water to 8-10% and 90-100 kg/h.
Example 3
80 ten thousand t/a sulfuric acid, sulfuric acid tail gas treatment capacity 200000Nm 3 And/h, converting SO in tail gas of two-rotation two-absorption sulfuric acid device 2 The content was 800mg/Nm 3 The tail gas outlet requires SO 2 The content was 100mg/Nm 3 The desulfurization efficiency was 87.5%. The primary desulfurization is adopted, and the process is finished by removing a secondary desulfurization tower according to the figure 1.
The sulfuric acid tail gas is pressurized to 0.15-0.2 kPa by a pressurizing blower 1 and is sent into a desulfurizing tower with the diameter phi of 6.2m and the height of 24.5m, the top of the desulfurizing tower needs slurry to be pressurized to 0.25Mpa by a circulating pump, and the circulating amount is 3000m 3 And/h, spraying the flue gas into mist to contact the flue gas to absorb SO in the flue gas 2 The liquid-gas ratio is 25L/m 3 The purified and qualified flue gas is discharged after demisted by a demister 4; the supplementing amount of the copper extraction tailings slurry with the solid content of 15 percent is 1.5m 3 Delivering the mixture to a desulfurizing tower by a slurry pump I5 for desulfurizing, and taking out desulfurizing liquid from the desulfurizing tower for 1.5m 3 And (3) entering a desulfurization slurry storage tank 9 for subsequent working procedures, wherein the pH value of slurry in the desulfurization tower is kept at 4.5-5.
The desulfurization slurry is sent to a slurry high-level tank 11 by a slurry pump II 10, flows into a vacuum filter 12 automatically for filtering, the filter cake is copper smelting residues, the stacked filter cake is still used as building materials, the filtrate enters a receiving tank I13 and then enters a dezincification tank 15, and the filtrate is 1.4m 3 And (3) adding 7-9 kg/h of ammonium sulfide to generate 9-10 kg/h of precipitates such as zinc sulfide and copper sulfide, pressing the precipitates into a plate-and-frame filter press 17 by a screw pump 16, and feeding about 15-18 kg/h of obtained zinc sulfide mud to wet zinc hydrometallurgy to extract zinc and copper. The filtrate enters an iron removal tank 18, ammonium bicarbonate is added into the iron removal tank 18 to generate ferrous carbonate sediment of 60-65 kg/h, a slurry pump III 19 is used for sending the mixture to a concentration tank 20 for sediment concentration, supernatant fluid is decanted into a sewage storage tank 25, the ferrous carbonate sediment is filtered by a vacuum filter 21, and a filter cake is dried in a fluidized bed dryer to obtain ferrous carbonate products of 55-60 kg/h.
Lime milk 5-6 kg/h is added into a sewage storage tank 25, sewage and lime milk are mixed, the sewage and lime milk are sent to an ammonia-lime water distillation system 27 by a sewage pump 26, direct steam is heated to 100 ℃, ammonia and water vapor escape from the top of a distillation column, the temperature is controlled to be 90-95 ℃ by a separator, then the ammonia water enters a condenser 29 to be condensed into ammonia water and stored in an ammonia water tank 30, and the concentration of the ammonia water is regulated to be 8-10% and 15-20 kg/h.

Claims (4)

1. SO in copper extraction tailings desorption flue gas 2 The recycling method is carried out according to the following steps:
(1) Preparing copper extraction tailings into slurry by using water, introducing flue gas to contact the copper extraction tailings slurry for desulfurization, discharging the desulfurized and purified flue gas after demisting, and filtering the desulfurized copper extraction tailings slurry to obtain desulfurized slurry, wherein filter residues can be used as building materials or cement raw materials;
the copper extraction tailings slurry containsThe solid content is 15-20wt%, and the ratio of the copper extraction tailings slurry to the smoke gas inlet is 8-25L/m 3 The pH value of the copper extraction tailings slurry in the desulfurization process is 4.5-5;
(2) Adding ammonium sulfide into the desulfurization slurry obtained in the step (1), reacting zinc, copper, manganese, mercury, arsenic ions in the desulfurization slurry with the ammonium sulfide to generate precipitate, filtering, and carrying out next treatment on the filtrate, wherein the filter residue is zinc sulfide sludge for extracting zinc and copper;
the addition amount of the ammonium sulfide is 5-6.5 kg/m 3
(3) Adding ammonium bicarbonate into the filtrate obtained in the step (2), reacting iron ions in the filtrate with the ammonium bicarbonate to generate precipitate, filtering, further treating the filtrate as sewage, wherein the filter residue is ferrous carbonate and is used for preparing ferric salt, magnetic ferric oxide and iron red pigment;
the addition amount of the ammonium bicarbonate is 25-35 kg/m 3
(4) Adding lime milk into the sewage obtained in the step (3) for reaction, and reacting ammonium sulfate in the sewage with the lime milk to generate ammonia water;
the mol ratio of the ammonium sulfate to the lime milk is 1:1-1.5, and water is added to adjust the concentration of the ammonia water to 8-10%.
2. The apparatus for use in the method of claim 1, comprising: the device comprises a pressurizing blower (1), a desulfurizing tower, a demister (4), a slurry pump I (5), a circulating pump, a slurry mixing tank (8), a desulfurizing slurry storage tank (9), a slurry pump II (10), a desulfurizing slurry overhead tank (11), a vacuum filter I (12), a receiving tank I (13), a vacuum pump I (14), a dezincification tank (15), a screw pump (16), a plate-frame filter press (17), an deironing tank (18), a slurry pump III (19), a concentration tank (20), a vacuum filter II (21), a receiving tank II (22), a vacuum pump II (23), a dryer (24), a sewage storage tank (25), a sewage pump (26), an ammonia-lime water distillation tower (27), a separator (28), a condenser (29) and an ammonia water tank (30);
the pressurizing blower (1) is connected with an air inlet of the desulfurizing tower, and an air outlet of the desulfurizing tower is communicated with the outside through a demister (4);
the slurry mixing tank (8) is connected with a liquid inlet of a desulfurizing tower through a slurry pump I (5), the desulfurizing tower is provided with a circulating pump for pressurizing slurry to the top of the tower, a liquid outlet of the desulfurizing tower is connected with a desulfurizing slurry storage tank (9), the desulfurizing slurry storage tank (9) is connected with an inlet of a desulfurizing slurry high-level tank (11) through a slurry pump II (10), an outlet of the desulfurizing slurry high-level tank (11) is connected with an inlet of a receiving tank I (13) through a vacuum filter I (12), the receiving tank I (13) is provided with a vacuum pump I (14), an outlet of the receiving tank I (13) is connected with an inlet of a zinc removing tank (15), an outlet of the zinc removing tank (15) is connected with a plate-frame filter press (17) through a screw pump (16), a filtrate outlet of the plate-frame filter press (17) is connected with an inlet of a deironing tank (18), a precipitation outlet of the deironing tank (18) is connected with a concentrating tank (20) through a slurry pump III (19), a precipitation outlet of the concentrating tank (20) is connected with a sewage (25), a precipitation outlet of the vacuum filter II (21) is connected with a vacuum filter II (21), an outlet of the vacuum filter II (21) is connected with a filtrate outlet of a dryer (21), and a filtrate outlet of the vacuum filter II (22) is connected with a filtrate tank (22) is connected with a filtrate outlet of the vacuum filter (22) through a vacuum filter (22);
the sewage storage tank (25) is connected with a liquid inlet of an ammonia-lime water distillation tower (27) through a sewage pump (26), and an air outlet of the ammonia-lime water distillation tower (27) is connected with an ammonia water tank (30) through a separator (28) and a condenser (29).
3. The device according to claim 2, wherein the number of the desulfurization towers is two, namely a first-stage desulfurization tower (2) and a second-stage desulfurization tower (3), the air inlet of the first-stage desulfurization tower (2) is connected with the pressurizing blower (1), the air outlet of the first-stage desulfurization tower (2) is connected with the air inlet of the second-stage desulfurization tower (3), and the air outlet of the second-stage desulfurization tower (3) is communicated with the outside through the demister (4); the liquid inlet of the secondary desulfurization tower (3) is connected with the slurry mixing tank (8) through a slurry pump I (5), the liquid outlet of the secondary desulfurization tower (3) is connected with the liquid inlet of the primary desulfurization tower (2), and the liquid outlet of the primary desulfurization tower (2) is connected with a desulfurization slurry storage tank (9).
4. The device of claim 2, wherein more than one corrosion-resistant and wear-resistant cyclone solid spray head is arranged in the desulfurizing tower.
CN201610716473.0A 2016-08-25 2016-08-25 SO in copper extraction tailings desorption flue gas 2 And resource method and device Active CN106422716B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610716473.0A CN106422716B (en) 2016-08-25 2016-08-25 SO in copper extraction tailings desorption flue gas 2 And resource method and device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610716473.0A CN106422716B (en) 2016-08-25 2016-08-25 SO in copper extraction tailings desorption flue gas 2 And resource method and device

Publications (2)

Publication Number Publication Date
CN106422716A CN106422716A (en) 2017-02-22
CN106422716B true CN106422716B (en) 2023-07-21

Family

ID=58182979

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610716473.0A Active CN106422716B (en) 2016-08-25 2016-08-25 SO in copper extraction tailings desorption flue gas 2 And resource method and device

Country Status (1)

Country Link
CN (1) CN106422716B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107213774B (en) * 2017-05-15 2020-09-25 昆明理工大学 Flue gas desulfurization and resource utilization method based on smelting tailing slag
CN107261799B (en) * 2017-07-20 2020-11-13 湖南辰州矿业有限责任公司 Device and method for preventing lime milk of smelting desulfurization system from scaling
CN109012109A (en) * 2018-06-26 2018-12-18 昆明理工大学 It is a kind of while removing the SO in flue gas2With the method and device of NO
CN109316945A (en) * 2018-11-26 2019-02-12 中国科学院过程工程研究所 A kind of device and method of integrated treatment slag and flue gas
CN109675425B (en) * 2018-12-06 2021-06-29 昆明理工大学 System and method for integrated treatment and resource utilization of red mud for flue gas desulfurization and denitrification
CN111214948B (en) * 2020-01-18 2021-03-12 昆明理工大学 Copper tailing recycling treatment coupling flue gas desulfurization method and system based on ammonioiarosite precipitation method
CN113860385B (en) * 2021-10-09 2023-11-17 四川天人能源科技有限公司 Recycling method of solid waste of ferro-manganese desulfurizing agent
CN114686632B (en) * 2022-04-08 2024-03-22 瀜矿环保科技(上海)有限公司 Copper slag recycling and CO based on industrial solid waste 2 Mineralization coupling method and mineralization coupling system

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101481806A (en) * 2009-01-06 2009-07-15 北京大学 Method for desulphurization of copper sulfur ore
CN101643857A (en) * 2009-08-25 2010-02-10 西部矿业股份有限公司 Comprehensive recovery method of complex polymetal sulphide ore containing copper, lead and zinc
JP2010180450A (en) * 2009-02-05 2010-08-19 Sumitomo Metal Mining Co Ltd Method for concentrating gold from copper-sulfide ore
CN101972704A (en) * 2010-11-10 2011-02-16 白银有色集团股份有限公司 Method for improving metal recovery rate during mineral dressing of copper-lead-zinc-sulfur-containing refractory ore
CN102952952A (en) * 2012-09-26 2013-03-06 东北大学 Method for directly restoring and recovering copper iron from smelting copper slag
JP2014205584A (en) * 2013-04-10 2014-10-30 Dowaメタルマイン株式会社 Method for manufacturing scorodite from flue cinder in nonferrous smelting
CN105435957A (en) * 2016-01-12 2016-03-30 云南华联锌铟股份有限公司 Mineral separation technology for recovering low-grade marmatite and cassiterite minerals from copper separation tailings

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2340763A1 (en) * 1976-02-12 1977-09-09 Hitachi Ltd PROCESS FOR TREATING AN EXHAUST GAS CONTAINING SULFUR OXIDES
JP4484993B2 (en) * 1999-12-24 2010-06-16 キレスト株式会社 Treatment of boron-containing water
CN1173077C (en) * 2002-03-11 2004-10-27 北京矿冶研究总院 Method for producing antimony by electrolyzing antimony-containing sulfide mineral pulp
US20070297960A1 (en) * 2004-12-30 2007-12-27 Krebs Damien G I Extraction of Nickel and Cobalt from a Resin Eluate Stream
CN100402676C (en) * 2006-03-24 2008-07-16 浙江工业大学 Method for recovering valuable metals from electroplating sludge
CN101328536B (en) * 2007-06-18 2010-06-02 中国恩菲工程技术有限公司 Process for comprehensive recovery of nickel, copper, cobalt, sulfur and magnesium from ore
CN101328537B (en) * 2007-06-18 2010-04-21 中国恩菲工程技术有限公司 Process for comprehensive recovery nickel, copper, cobalt, sulfur and magnesium from high magnesium and nickle ore concentrate
CN101643846B (en) * 2009-08-31 2011-04-13 江西理工大学 Complex copper sulphide ore thermal activating-pressure leaching technology
CN102051428B (en) * 2011-01-20 2012-02-08 西安建筑科技大学 Iron extracting and steelmaking process for comprehensively treating copper ore tailing and nickel molten slag
CN103861725B (en) * 2014-03-24 2016-01-13 西安建筑科技大学 The sorting process technique of gangue full resource utilization
CN104087971B (en) * 2014-07-11 2016-11-23 北京矿冶研究总院 Method for treating lead matte
CN206138987U (en) * 2016-08-25 2017-05-03 昆明理工大学 Carry in copper tailings desorption flue gas device of SO2 and resourceization

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101481806A (en) * 2009-01-06 2009-07-15 北京大学 Method for desulphurization of copper sulfur ore
JP2010180450A (en) * 2009-02-05 2010-08-19 Sumitomo Metal Mining Co Ltd Method for concentrating gold from copper-sulfide ore
CN101643857A (en) * 2009-08-25 2010-02-10 西部矿业股份有限公司 Comprehensive recovery method of complex polymetal sulphide ore containing copper, lead and zinc
CN101972704A (en) * 2010-11-10 2011-02-16 白银有色集团股份有限公司 Method for improving metal recovery rate during mineral dressing of copper-lead-zinc-sulfur-containing refractory ore
CN102952952A (en) * 2012-09-26 2013-03-06 东北大学 Method for directly restoring and recovering copper iron from smelting copper slag
JP2014205584A (en) * 2013-04-10 2014-10-30 Dowaメタルマイン株式会社 Method for manufacturing scorodite from flue cinder in nonferrous smelting
CN105435957A (en) * 2016-01-12 2016-03-30 云南华联锌铟股份有限公司 Mineral separation technology for recovering low-grade marmatite and cassiterite minerals from copper separation tailings

Also Published As

Publication number Publication date
CN106422716A (en) 2017-02-22

Similar Documents

Publication Publication Date Title
CN106422716B (en) SO in copper extraction tailings desorption flue gas 2 And resource method and device
CN107213774B (en) Flue gas desulfurization and resource utilization method based on smelting tailing slag
CN101314818B (en) Golden shifting process of biological oxidation-torrefaction-cyanidation
CN104404261B (en) The method of gold recovering, iron is synchronously reduced in the chloridizing roasting of a kind of refined gold ore cyaniding tailings
CN101234363B (en) Method for producing high-grade sulfur concentrate from low-grade pyrite mine ore
CN110090548B (en) Method for wet desulphurization and zinc sulfate recovery of copper slag tailings and zinc smelting fly ash
CN101343686B (en) Comprehensive utilization method for copper containing ferro-sulphur ore
CN111020175B (en) Method for comprehensively recycling zinc-rich gypsum slag resources
Tao et al. Removing sulfur dioxide from smelting flue and increasing resource utilization of copper tailing through the liquid catalytic oxidation
US20200332390A1 (en) Method for preparing iron ore concentrates by recycling copper slag tailings
AU2017402487B2 (en) Beneficiation method for mixed copper ore with low oxidation rate and high binding rate
CN106731629A (en) A kind of method of utilization copper smelting plant mine tailing dreg slurry desulfurization dearsenification mercury
CN109354149A (en) A kind of processing method of the waste water containing heavy metal-polluted acid
Conejeros et al. Novel treatment for mixed copper ores: Leaching ammonia–Precipitation–Flotation (LAPF)
CN206138987U (en) Carry in copper tailings desorption flue gas device of SO2 and resourceization
CN106269290B (en) The method for floating of decopperized lead zinc from highgrade pyrite concentrate
CN110408791A (en) A method of reduction autovulcanization roasting pretreatment iron vitriol slag
CN102363842B (en) Process for recovering arsenic comprehensively by two-section roasting of arsenic-containing and carbon-containing gold concentrates
Deng et al. Treatment of oxidized copper ores with emphasis on refractory ores
CN111876589A (en) Method and device for desulfurization and reduction of sulfur-containing iron ore
CN110075697B (en) Flue gas desulfurization and resource utilization method based on electrolytic manganese tailing slag
Gao et al. Innovative technology and mechanism for comprehensive recovery of copper, nickel, zinc and iron in electroplating sludge
RU2538791C2 (en) Method and device for production of direct iron and/or steelmaking pig iron from iron ores with high phosphorus content
CN109207720A (en) A kind of leaching method of extracting vanadium from stone coal
CN109231258A (en) A kind of method of integrated treatment copper ashes tailing and flue gas during smelting

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant