CN108998833A - A kind of calcium sulfate crystal whiskers preparation system - Google Patents
A kind of calcium sulfate crystal whiskers preparation system Download PDFInfo
- Publication number
- CN108998833A CN108998833A CN201811008707.1A CN201811008707A CN108998833A CN 108998833 A CN108998833 A CN 108998833A CN 201811008707 A CN201811008707 A CN 201811008707A CN 108998833 A CN108998833 A CN 108998833A
- Authority
- CN
- China
- Prior art keywords
- electromagnet
- desulphurization
- iron powder
- calcium sulfate
- sulfate crystal
- 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.)
- Granted
Links
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 157
- 239000013078 crystal Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 189
- 239000007789 gas Substances 0.000 claims abstract description 49
- 238000004064 recycling Methods 0.000 claims abstract description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000967 suction filtration Methods 0.000 claims abstract description 14
- 229920000742 Cotton Polymers 0.000 claims description 31
- 238000001914 filtration Methods 0.000 claims description 16
- 230000009471 action Effects 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 230000000740 bleeding effect Effects 0.000 claims description 12
- 229920001971 elastomer Polymers 0.000 claims description 9
- 239000005060 rubber Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000010985 leather Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 34
- 230000023556 desulfurization Effects 0.000 abstract description 34
- 239000003546 flue gas Substances 0.000 abstract description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 17
- 238000007254 oxidation reaction Methods 0.000 abstract description 15
- 230000003647 oxidation Effects 0.000 abstract description 13
- 238000005245 sintering Methods 0.000 abstract description 12
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 21
- 239000002002 slurry Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 230000008602 contraction Effects 0.000 description 13
- 238000002425 crystallisation Methods 0.000 description 12
- 230000008025 crystallization Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000011010 flushing procedure Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 229910052602 gypsum Inorganic materials 0.000 description 9
- 230000005484 gravity Effects 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 239000010440 gypsum Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 229910052925 anhydrite Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000009527 percussion Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D29/00—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor
- B01D29/085—Funnel filters; Holders therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D29/00—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor
- B01D29/50—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor with multiple filtering elements, characterised by their mutual disposition
- B01D29/56—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor with multiple filtering elements, characterised by their mutual disposition in series connection
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
- B03C1/30—Combinations with other devices, not otherwise provided for
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a kind of calcium sulfate crystal whiskers preparation systems, belong to metallurgical solid wastes recycling and utilize technical field.The present invention includes: iron powder recyclable device, for separating the iron powder in Desulphurization comprising blast pipe, iron powder recycling cavity, top cover and blowback gas tank;Suction filtration device, for the bulky grain insoluble matter in Desulphurization will to be removed comprising filter, vacuum pump using circulatory water and suction filtration unit;Reaction unit, for the Desulphurization after separation iron powder to be prepared calcium sulfate crystal whiskers comprising oxygen cylinder and autoclave.The present invention is using sintering flue gas desulfurization ash as raw material, using hydrothermal system oxidation coordinate system for calcium sulfate crystal whiskers, realizes that sintering flue gas desulfurization ash oxidation coordinate system for calcium sulfate crystal whiskers, solves CaSO3It is difficult to quickly oxidation and the longer problem of calcium sulfate crystal whiskers preparation process flow, the recovery utilization rate of Desulphurization is improved, improves the quality of calcium sulfate crystal whiskers.
Description
Technical field
The present invention relates to the utilizations of metallurgical solid wastes recycling, more specifically to a kind of calcium sulfate crystal whiskers preparation system.
Background technique
Sintering process is as the important link and the main pollutant emission of steel and iron industry in Production Processes In Steel Industry
Source, the wherein SO of 70% or more steel and iron industry2From sintering process.As country is to SO2The reinforcement of contamination control and China's ring
The reinforcement of border protective awareness reduces SO in sintering process2Discharge have become the emphasis of steel industry reducing discharge of waste gases, sinter
Research in terms of the comprehensive utilization of flue gas desulfurization ash is gradually concerned by people, therefore existing iron and steel enterprise is mating builds
If the desulphurization system of different process, and the utilization of sinter flue gas desulfurization ash can reduce because fund consumed by stacking,
Land occupation and environmental pollution reduce the dosage of the natural gypsum, and then reduce the yield of the natural gypsum, preserve the ecological environment.
Therefore, many colleges and universities and enterprise have carried out a large amount of research to sinter flue gas desulfurization ash comprehensive utilization aspect, such as utilize sintering
Flue gas desulfurization ash prepares sulfuric acid, cement retarder, gypsum building material and calcium sulfate crystal whiskers etc..Wherein, de- using sintering flue gas
Sulphur ash prepares calcium sulfate crystal whiskers added value with higher, and calcium sulfate crystal whiskers are a kind of staple fibers grown with single crystal form,
It has uniform cross section, complete shape and highly perfect internal structure, and compared with glass fibre, advantage is that it has
There is high intensity, subtle size is easier in conjunction with the organic high molecular compounds such as resin, rubber, plastics, and product
Presentation quality is excellent.Pollution of the desulfurized gypsum to environment can be reduced by preparing calcium sulfate crystal whiskers not only as raw material using desulfurized gypsum,
Natural gypsum resource can also be saved, and opened up a new way for the high value added utilization of desulfurized gypsum, but it is existing de-
The method that sulphur ash prepares calcium sulfate crystal whiskers is not perfect, so that calcium sulfate crystal whiskers is second-rate, seriously limits Desulphurization
High efficient resourcing application.
Through patent retrieval, the Shi Peiyang of Northeastern University has also carried out correlative study, and has applied for related patents, utilizes sintering
Mine flue gas desulfurization byproduct prepares the method (application number: 201010545829.1 of calcium sulfate crystal whiskers;The applying date: 2010.11.16)
With the method (application number: 200810011193.5 for preparing calcium sulfate crystal whiskers using desulfurized gesso of flue gas;The applying date:
2008.04.25), the recycling application for being similarly desulfurizing byproduct provides a kind of approach.But existing method produces
The calcium sulfate crystal whiskers arrived are second-rate, limit the value added applications of desulfurizing byproduct.In addition, the title of innovation and creation are as follows:
Processing unit (the number of patent application: CN 201610076883.3 of semi-dry desulphurization ash;Data of publication of application: 2016.05.04), it should
Processing unit is by being arranged adsorption tower, the flue gas that heating semi-dry desulphurization ash generates quilt in inlet air stack in the top of heating furnace
It is entered back into lower adsorption chamber after the cold wind cooling of air-introduced machine blowout, the activated coke in lower adsorption chamber is to the SO in flue gas2It carries out
It adsorbs for the first time, then flue gas is entered in upper adsorption chamber by transition flue duct, and the activated coke in upper adsorption chamber is in flue gas
SO2It carries out second to adsorb, then flue gas enters after outlet flue by being discharged in chimney.It has been achieved rapidly to semidry method
Desulphurization carries out desulfurization process, solves the problems, such as the secondary pollution of semi-dry desulphurization ash, but still without solving to Desulphurization
The technical issues of utilizing again.In addition, the title of innovation and creation are as follows: a kind of processing unit and processing method (patent of Desulphurization
Application number: CN 201610344246.X;Data of publication of application: 2016.10.12), the processing by the way that a kind of Desulphurization is arranged fills
It sets, comprising: Vertical Mill, dust-precipitator, hot-blast stove, a hot air pipe and second heat air hose;The slag of slag entrance is offered on Vertical Mill
Entrance;Dust-precipitator is connect with the Vertical Mill;The junction of hot air pipe and second heat air hose offers mixed wind entrance.Passing through will
Desulphurization oxidation modification in hot wind so that the slag powders product setting time formed greatly shortens, and has been saved low temperature and has been forged
Equipment investment and process cost are burnt, efficiently solving Desulphurization processing mode in the prior art causes processing cost to increase and formed
The technical issues of new pollution sources.But still the recycling without solving the problems, such as iron powder in Desulphurization.
Summary of the invention
1. technical problems to be solved by the inivention
It is an object of the invention to overcome in the prior art, sintering flue gas desulfurization ash prepares the system of calcium sulfate crystal whiskers still not
Maturation, so that the second-rate deficiency of calcium sulfate crystal whiskers, provides a kind of calcium sulfate crystal whiskers preparation system, it is possible to further
Solve the problems, such as the resource waste and pollution of Desulphurization in production process.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention are as follows:
A kind of calcium sulfate crystal whiskers preparation system of the invention, including iron powder recyclable device, for by the iron powder in Desulphurization
It is separated comprising blast pipe, iron powder recycling cavity, top cover and blowback gas tank;Electromagnet is provided in iron powder reclaiming chamber body
With cotton sleeve, the cotton sleeve is wrapped in the outside of electromagnet, and electromagnet includes conducting wire and iron core, and wherein conducting wire is wound in
The surface of the outside of iron core, iron core offers venthole, which is connected with the cylinder heart of iron core;Top cover is set to iron powder and returns
The top of cavity is received, which is internally provided with filter layer;Blast pipe is set to the bottom of iron powder recycling cavity, and Desulphurization is logical
Blast pipe is crossed to enter in iron powder reclaiming chamber body;Above-mentioned blowback gas tank is connected by gas pipeline with the cylinder heart of iron core, blast pipe bottom
Portion is provided with accumulator tank;Suction filtration device, for the bulky grain insoluble matter in Desulphurization will to be removed comprising filter, recirculated water
Vacuum pump and suction filtration unit, vacuum pump using circulatory water are connected by rubber leather hose with the bleeding point for filtering unit;Reaction unit is used for
By separate iron powder after Desulphurization prepare calcium sulfate crystal whiskers comprising oxygen cylinder and autoclave, oxygen cylinder by pipeline with
Air inlet at the top of autoclave is connected.
Preferably, it is provided with oxygen valve on the air inlet at the top of autoclave, between air inlet and autoclave
It is provided with relief valve on pipeline, air gauge is provided on the autoclave, is provided with stirring blade in autoclave.
Preferably, filtering unit includes Buchner funnel, bleeding point and vacuum suction bottle, and wherein Buchner funnel is arranged in vacuum
The top of suction bottle, the side of vacuum suction bottle are provided with bleeding point, and bleeding point passes through rubber leather hose and vacuum pump using circulatory water phase
Even, the top of Buchner funnel is arranged in the filter.
Preferably, electromagnet includes the first electromagnet, the second electromagnet and third electromagnet, wherein the first electromagnet and the
Two electromagnet are set side by side, and gap is provided between the first electromagnet and the second electromagnet, and third electromagnet is set to the first electricity
The top of magnet and the second electromagnet, and third electromagnet is correspondingly arranged with above-mentioned gap.
Preferably, it is connected with air-flow supervisor on blowback gas tank, is connected with the first airflow manifold and the second gas on air-flow supervisor
Branch pipe is flowed, the first airflow manifold is connected with the iron core both ends of third electromagnet;Second airflow manifold respectively with the first electromagnet
It is connected with the iron core of the second electromagnet.
Preferably, Desulphurization is blown to iron powder reclaiming chamber body by the blast pass of blast pipe, in the effect of blast pass
Lower Desulphurization is blowed to around electromagnet, and the iron powder in Desulphurization is adsorbed in the surface of cotton sleeve by electromagnet, with this
Blowback air stream is overflowed outward by the venthole on electromagnet core surface simultaneously, and Desulphurization is avoided to penetrate into cotton sleeve.
Preferably, strainer is provided in the middle part of the filter, the pore size filter of strainer is less than the straight of bulky grain insoluble matter
Diameter is simultaneously greater than the diameter of Desulphurization, and the bottom of filter is provided with filtering outlet, and the upper of Buchner funnel is arranged in filtering outlet
Portion.
Preferably, third electromagnet includes left electromagnet and right electromagnet, the junction position of left electromagnet and right electromagnet
In the surface in gap;Left electromagnet and the angle of right electromagnet junction are β, and β value range is 120~150 °.
Preferably, it is connected with air-flow supervisor on blowback gas tank, is connected with the first airflow manifold and the second gas on air-flow supervisor
Branch pipe is flowed, the first airflow manifold is connected with the iron core both ends of third electromagnet;Second airflow manifold respectively with the first electromagnet
It is connected with the iron core of the second electromagnet.
3. beneficial effect
Using technical solution provided by the invention, compared with existing well-known technique, there is following remarkable result:
(1) a kind of calcium sulfate crystal whiskers preparation system of the invention, the iron powder in Desulphurization is separated with Desulphurization, is weeded out de-
Bulky grain insoluble matter in sulphur ash, obtains pretreated Desulphurization, by pretreated Desulphurization and MgCl2Solution is sufficiently stirred
It is even to obtain slurries, then slurries are transferred to progress hydrothermal synthesis in the autoclave of reaction unit and obtain calcium sulfate crystal whiskers, make
It, can be to avoid the iron powder being entrained in Desulphurization in hydro-thermal body during Desulphurization synthesis calcium sulfate crystal whiskers with separation iron powder
The oxygen dissolved in slurries is fought for the calcium sulfite in Desulphurization in system, and the iron powder in Desulphurization is prevented to become new life
The crystallization attachment point of calcium sulfate causes a large amount of forming cores of calcium sulfate crystal whiskers, hinders the growth course of calcium sulfate crystal whiskers;
(2) Desulphurization is blown to iron powder by a kind of calcium sulfate crystal whiskers preparation system of the invention, the blast pass of blast pipe
In reclaiming chamber body, electromagnet generates magnetic force for the iron powder adsorption in Desulphurization in the surface of cotton sleeve, and cotton sleeve improves
Iron powder and the ironing surface frictional force of electromagnetism, avoid the iron powder of electromagnet adsorption from being blown off, and promote electromagnet to Desulphurization
In iron powder separation;Open electromagnet, open simultaneously the air valve of blowback gas tank, the blowback air in blowback gas tank flow through pipeline into
The cylinder for entering electromagnet core is intracardiac, and then blowback air-flow is overflowed from the venthole on iron core surface to electromagnet exterior, prevents desulfurization
Ash is penetrated under the action of blast pass in the gap of cotton sleeve, and then is promoted the separation of Desulphurization and iron powder and improved
The rate of recovery of Desulphurization;
(3) a kind of calcium sulfate crystal whiskers preparation system of the invention, the Desulphurization for removing iron power removing that will be taken out from accumulator tank
It is uniformly mixed to obtain Desulphurization aqueous solution with water, Desulphurization aqueous solution is then moved into Suction filtration device, desulfurization is weeded out by strainer
Bulky grain insoluble matter in ash, Desulphurization aqueous solution enter the filtering outlet of filter bottom, and edge through the hole on filter screen
Filtering outlet flows into Buchner funnel, and vacuum pump using circulatory water carries out vacuumizing operation at this time, obtains pretreated Desulphurization, will be pre-
The Desulphurization of processing, which moves into progress hydrothermal synthesis in reaction unit, can be obtained calcium sulfate crystal whiskers;It can be removed using vacuum pump suction filtration
Bulky grain insoluble matter in Desulphurization improves the quality of the calcium sulfate crystal whiskers using Desulphurization preparation.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the device of iron powder in the separation Desulphurization of embodiment 1;
Fig. 2 is the schematic top plan view of the top cover of embodiment 1;
Fig. 3 is the structural schematic diagram of the Suction filtration device of embodiment 1;
Fig. 4 is the structural schematic diagram of the filter of embodiment 1;
Fig. 5 is the structural schematic diagram of the reaction unit of embodiment 1;
Fig. 6 is the structural schematic diagram of the device of iron powder in the separation Desulphurization of embodiment 2;
Fig. 7 is the structural schematic diagram of the device of iron powder in the separation Desulphurization of embodiment 2;
Fig. 8 is the SEM figure of the calcium sulfate crystal whiskers of embodiment 4;
Fig. 9 is embodiment 4 not except the SEM figure of the calcium sulfate crystal whiskers of iron;
Figure 10 is a kind of structural schematic diagram of calcium sulfate crystal whiskers preparation system of the invention.
Label declaration in schematic diagram:
100, blast pipe;110, the first blast pipe;120, the second blast pipe;130, air hose junction;131, bellows;
140, accumulator tank;150, air blast blower;101, desulfurization ash-pit;102, delivery pipe;103, pressurized gas;104, Material valve;
200, iron powder recycles cavity;201, energization head;202, conducting wire;203, cotton sleeve;204, venthole;205, iron
Core;210, the first electromagnet;220, the second electromagnet;230, third electromagnet;231, left electromagnet;232, right electromagnet;
240, cavity contraction section;
310, top cover;320, filter layer;
410, blowback gas tank;420, air-flow is responsible for;421, the first airflow manifold;422, the second airflow manifold;423, first
Back-flushing valve;424, the second back-flushing valve;
520, autoclave;521, relief valve;522, air gauge;523, air inlet;524, gas heater;525, it stirs
Mix blade;526, insulating layer;527, thermometer;528, oxygen valve;
601, unit is filtered;602, filter;610, Buchner funnel;620, bleeding point;630, vacuum suction bottle;640, rubber
Hose;650, vacuum pump using circulatory water;
710, strainer;720, filtering outlet.
Specific embodiment
Hereafter detailed description of the present invention and example embodiment are more fully understood in combination with attached drawing, wherein of the invention
Element and feature are identified by appended drawing reference.
Embodiment 1
As shown in Figure 10, a kind of calcium sulfate crystal whiskers preparation system of the invention, including iron powder recyclable device, Suction filtration device and
Reaction unit;Wherein iron powder recyclable device is for separating the iron powder in Desulphurization, and Suction filtration device will be for that will remove desulfurization
Bulky grain insoluble matter in ash, reaction unit are used to the Desulphurization after separation iron powder preparing calcium sulfate crystal whiskers.In the present embodiment,
As shown in Figure 1, iron powder recyclable device includes blast pipe 100, iron powder recycling cavity 200, top cover 310 and blowback gas tank 410;Iron powder
It is provided with electromagnet and cotton sleeve 203 in recycling cavity 200, cotton sleeve 203 is wrapped in the outside of electromagnet, blast pipe
Desulphurization is blown to iron powder recycling cavity 200 by 100 blast pass, and electromagnet generates magnetic force and inhales the iron powder in Desulphurization
The surface of cotton sleeve 203 is invested, cotton sleeve 203 improves the frictional force of electromagnetism iron surface and iron powder, avoids electromagnet table
The iron powder of face absorption is blowed air-flow and blows off;Electromagnet includes conducting wire 202 and iron core 205, and wherein conducting wire 202 is wound in iron core
205 outside, electromagnet include the first electromagnet 210, the second electromagnet 220 and third electromagnet 230, and Desulphurization moves to the
Around one electromagnet 210 and the second electromagnet 220, the iron powder in Desulphurization is by the first electromagnet 210 and the second electromagnet 220
It is adsorbed in the surface of cotton sleeve 203;Then Desulphurization continues up under the action of blast pass, when Desulphurization moves
When to third 230 surrounding of electromagnet, the iron powder adsorption in Desulphurization is in the surface of third electromagnet 230.
Further, the first electromagnet 210 and the second electromagnet 220 are set side by side, the first electromagnet 210 and the second electromagnetism
Gap is provided between iron 220, third electromagnet 230 is set to the top of the first electromagnet 210 and the second electromagnet 220, and
Third electromagnet 230 is correspondingly arranged with above-mentioned gap, and the mode of being arranged above and below of electromagnet makes different location, different levels
Electromagnet can come into full contact with Desulphurization, to make the iron powder of different location in electromagnet adsorption recovery cavity 200, Jin Erti
The separative efficiency of iron powder in the high unit time.Third electromagnet 230 includes left electromagnet 231 and right electromagnet 232, left electromagnetism
The junction of iron 231 and right electromagnet 232 is located at the surface in gap;The folder of 232 junction of left electromagnet 231 and right electromagnet
Angle is β, and β value range is 120~150 °, and the preferred β value of the present embodiment is 120 °, and the setting of above-mentioned angle β increases
Third electromagnet 230 enhances the electromagnetic force of junction, and then third electromagnet 230 to the adsorption area of iron powder
Generate the iron powder in stronger magnetic-adsorption Desulphurization, reach preferable separating effect, Desulphurization under the action of blast pass,
Through the gap between the first electromagnet 210 and the second electromagnet 220, move between left electromagnet 231 and right electromagnet 232
Junction, and it is adsorbed on the surface of junction, convenient for improving the separating effect of iron powder in Desulphurization.
It is worth noting that blowback gas tank 410 is connected by gas pipeline with the cylinder heart of iron core 205, on blowback gas tank 410
It is connected with air-flow supervisor 420, is connected with the first airflow manifold 421 and the second airflow manifold 422, the first gas on air-flow supervisor 420
Stream branch pipe 421 is connected with 205 both ends of iron core of third electromagnet 230;Second airflow manifold 422 respectively with the first electromagnet
210 are connected with the iron core 205 of the second electromagnet 220, and the surface of iron core 205 offers venthole 204, the venthole 204 with
The cylinder heart of iron core 205 is connected, and then blowback gas tank 410 can convey blowback air to the cylinder heart of iron core 205 by gas pipeline
Stream;In addition, the diameter of venthole 204 is greater than the diameter of conducting wire 202, when so that conducting wire 202 passing through the outer surface of venthole 204,
Blowback air-flow into iron core 205 can also be flowed out from the gap of 204 surrounding of venthole, then by cotton sleeve 203 to
Outside diffusion can avoid Desulphurization from entering in cotton sleeve 203 under the action of blast pass to the blowback air-flow of external diffusion,
To achieve the effect that separate iron powder in Desulphurization.
As shown in Fig. 2, top cover 310 is set to the top of iron powder recycling cavity 200, which was internally provided with
Filtering layer 320, blast pipe 100 are set to the bottom of iron powder recycling cavity 200, and the blast pass in blast pipe 100 is used for desulfurization
In ash blowing to iron powder recycling cavity 200, recycled in cavity 200 so that Desulphurization enters iron powder by blast pipe 100;From air inlet
Pipe 100 enters the blast pass that iron powder receives cavity 200, flows out iron powder by filter layer 320 and receives cavity 200, balance iron powder recycling
Pressure and extraneous pressure in cavity 200, guarantee going on smoothly for separation process.The top interior of iron powder recycling cavity 200
It is provided with internal screw thread, is provided on 310 lateral wall of top cover and is matched with the internal screw thread of the top interior of iron powder recycling cavity 200
External screw thread, so that being connected between iron powder recycling cavity 200 and top cover 310 by screw thread, the mode of threaded connection be can be improved
Installation effectiveness;In addition, the top cover 310 is internally provided with filter layer 320, be provided with through-hole on filter layer 320, the through-hole with it is upper
The energization head 201 stated matches, and energization head 201 is disposed through on filter layer 320 by through-hole, and energization head 201 passes through filtering
Layer 320 extends to the outside of top cover 310, and energization head 201 is electrically connected to a power source.Above-mentioned filter layer 320 is gauze or has
The filled layer or dust-removal cloth-bag in gap, gas can be flowed out by filter layer 320 in iron powder removal process, and filter layer
320 can will be in treated Desulphurization is limited in iron powder recycling cavity 200, so that the Desulphurization after processed concentrates on iron powder
It recycles in cavity 200, to avoid Desulphurization while carrying out safe and efficient separation to the iron powder in Desulphurization and overflow
Out outside iron powder reclaiming chamber body 200.
Further, blast pipe 100 is set to the bottom of iron powder recycling cavity 200, and Desulphurization is entered by blast pipe 100
Iron powder recycles in cavity 200;100 bottom of blast pipe is provided with accumulator tank 140, and the blast pass of blast pipe 100 sprays Desulphurization
It is blown in iron powder recycling cavity 200, Desulphurization is blowed to around electromagnet under the action of blast pass, in Desulphurization
Iron powder is adsorbed in the surface of cotton sleeve 203 by electromagnet, and blowback air stream passes through the logical of 205 surface of electromagnet core at the same time
Stomata 204 overflows outward, and Desulphurization is avoided to penetrate into cotton sleeve 203.
As shown in Figures 3 and 4, Suction filtration device includes filter 602, vacuum pump using circulatory water 650 and filters unit 601, is filtered
The top of Buchner funnel 610 is arranged in device 602, and the middle part of filter 602 is provided with strainer 710, and the pore size filter of strainer 710 is small
It is simultaneously greater than the diameter of Desulphurization in the diameter of bulky grain insoluble matter, the bottom of filter 602 is provided with filtering outlet 720, mistake
The top that Buchner funnel 610 is arranged in mouth 720 is filtered out, after Desulphurization removes iron power removing, it is moved into after mixing evenly with distilled water
In filter 602, in the case where the strainer 710 of filter 602 acts on, the bulky grain insoluble matter in Desulphurization aqueous solution is blocked on filter
The upper surface of net 710 can remove the bulky grain insoluble matter in Desulphurization, and the Desulphurization aqueous solution of remainder is along strainer 710
In hole flow to the bottom of filter 602, flow into the Desulphurization aqueous solution of 602 bottom of filter under gravity, after
Continue and flowed to the filtering outlet 720 that 602 bottom of filter is arranged in, then flows into the suction filtration being arranged in below filtering outlet 720
Unit 601.
It is worth noting that filtering unit 601 includes Buchner funnel 610, bleeding point 620 and vacuum suction bottle 630, vacuum
The side of suction bottle 630 is provided with bleeding point 620, and bleeding point 620 is connected by rubber leather hose 640 with vacuum pump using circulatory water 650,
The top of vacuum suction bottle 630 is arranged in Buchner funnel 610, the desulfurization filtered in unit 601 convenient for 650 Duis of vacuum pump using circulatory water
Grey aqueous solution carries out suction filtration work, and then removes moisture extra in Desulphurization, filters unit 601 and carries out to Desulphurization aqueous solution
It filters, first opens the power supply of vacuum pump using circulatory water 650, Desulphurization aqueous solution flows into Buchner funnel 610 under the effect of gravity, follows
Ring water vacuum pump 650 is connected by rubber leather hose 640 with the bleeding point 620 that 630 side of vacuum suction bottle is arranged in, and rubber is passed through
The Desulphurization aqueous solution that leather hose 640 acts in Buchner funnel 610 starts to vacuumize operation, obtains after vacuum filtration pretreated
Desulphurization weeds out the bulky grain insoluble matter in Desulphurization, and then the degree of purity of Desulphurization can be improved.
As shown in figure 5, reaction unit includes oxygen cylinder 510 and autoclave 520 in the present embodiment, oxygen cylinder 510 is logical
Piping is connected with the air inlet 523 at 520 top of autoclave, is provided on the air inlet 523 at 520 top of autoclave
Oxygen valve 528 is provided with relief valve 521, the autoclave on the pipeline between air inlet 523 and autoclave 520
It is provided with air gauge 522 on 520, stirring blade 525 is provided in autoclave 520.By pretreated Desulphurization and MgCl2
Solution mixing, which stirs, is made slurries, adjusts the range of the pH value of slurries between 8~9, is then added to reaction under high pressure
In kettle 520, oxygen is filled with into autoclave 520 after closing 520 top cover of autoclave, and control autoclave 520
Interior stirring intensity is 400-600r/min, and the reaction time is 2~3h, carries out hydrothermal synthesis and obtains calcium sulfate crystal whiskers.Control is high
The stirring intensity in reaction kettle 520 and reaction time are pressed, hydrothermal system temperature and pressure with higher can be made, it can
Promote the CaSO in Desulphurization3·0.5H2The continuous dissolution of O, the SO generated after dissolution3 2-Rapid oxidation is at SO4 2-, so that solution
Middle Ca2+、SO4 2-Always it is in hypersaturated state, it is the crystallization and life of calcium sulfate crystal whiskers that simultaneous oxidation reaction carries out incessantly
It is long that power is provided, sintering flue gas desulfurization ash oxidation coordinate system is realized for calcium sulfate crystal whiskers, further, solves CaSO3It is difficult
Quickly to aoxidize and the longer problem of calcium sulfate crystal whiskers preparation process flow.
Embodiment 2
As shown in fig. 6-7, a kind of calcium sulfate crystal whiskers preparation system of the present embodiment, basic content with embodiment 1, difference
Be in: be connected with air-flow supervisor 420 on blowback gas tank 410, be connected with the first airflow manifold 421 and the on air-flow supervisor 420
Two airflow manifolds 422, the first airflow manifold 421 are connected with 205 both ends of iron core of third electromagnet 230, it should be noted that:
First airflow manifold 421 is connected with the cylinder heart of iron core 205, and the cylinder heart is hollow passageway, the venthole of the cylinder heart and 205 surface of iron core
204 are connected, and the position that the first airflow manifold 421 is connect with the cylinder heart is equipped with sealing ring, avoid blowback air-flow from 205 hearts of iron core
Both ends reveal;Second airflow manifold 422 is connected with the iron core 205 of the first electromagnet 210 and the second electromagnet 220 respectively
Logical, i.e., the second airflow manifold 422 is connected with the cylinder heart in iron core 205, same second airflow manifold 422 and cylinder heart link position
Equipped with sealing ring.The air inlet of second airflow manifold 422 includes left port and right output port, wherein left port and the first electromagnet
The left end of 210 iron core 205 is connected, and right output port is connected with the right end of the iron core 205 of the second electromagnet 220.Blowback gas tank 410 produces
Raw air-flow respectively enters the first airflow manifold 421 and the second airflow manifold 422 by gas pipeline;First airflow manifold 421
On be provided with the first back-flushing valve 423, the second back-flushing valve 424 is provided in the second airflow manifold 422;First back-flushing valve 423 is used for
The gas flow in the first airflow manifold 421 is controlled, the second back-flushing valve 424 is used to control the gas in the second airflow manifold 422
Flow.First electromagnet 210 and the second electromagnet 220 are located proximate to blast pipe 100, and power supply is by energization head 201 to electromagnetism
Iron provides electric energy, and then electromagnet generates magnetic force by electromagnetic induction, on the one hand, because of the first electromagnet 210 and the at this
The probability that two electromagnet 220 are contacted with iron powder in Desulphurization is larger, can suitably increase the first electromagnet 210 and the second electromagnet
The number of turns of conducting wire 202 on 220, and then the electromagnetism intensity at the first electromagnet 210 and the second electromagnet 220 can be enhanced;Separately
On the one hand, third electromagnet 230 is compared to the first electromagnet 210 and the second electromagnet 220, positional distance blast pipe 100
Farther out, so the probability that contacts with iron powder in Desulphurization of third electromagnet 230 is lower, it is appropriate in the identical situation of electric current to need
Increase the number of turns of the conducting wire 202 on third electromagnet 230, enhances the electromagnetism intensity at third electromagnet 230, to improve third
Absorption of the electromagnet 230 to the iron powder for blasting iron powder recycling 200 top of cavity iron powder, and then can be to avoid adsorption cotton matter sleeve
The iron powder on 203 surfaces is blown off and fallen into Desulphurization again by blowback air-flow, reduces the purity of Desulphurization separation.
It should be noted that Desulphurization can penetrate into cotton sleeve 203 under the action of 100 blast pass of blast pipe, make
Obtaining in cotton sleeve 203 has Desulphurization residual, causes the separating effect of iron powder poor, at this time can be by adjusting the second back-flushing valve
424 control the gas flow in the second airflow manifold 422, so that blowback air-flow is from the inner surface of cotton sleeve 203 to appearance
Surface current is dynamic, and Desulphurization is avoided to be attached in the fiber holes of cotton sleeve 203.Iron powder in Desulphurization is inhaled under the action of electromagnetic force
It is attached to 203 surface of cotton sleeve, moves to the Desulphurization near electromagnet under the action of the blowback air-flow of venthole 204, instead
It to cotton sleeve 203 is moved away from, promotes Desulphurization and is separated with iron powder, improve the separating effect of iron powder in Desulphurization.Third
Electromagnet 230 is far from blast pipe 100, when Desulphurization moves near third electromagnet 230, suffered by gas impact compared with
It is small at first electromagnet 210 and the second electromagnet 220, so in the present embodiment first can be controlled by the first back-flushing valve 423
Gas flow in airflow manifold 421, so that the gas flow of the first airflow manifold 421 is less than in the second airflow manifold 422
Gas flow.
Further, since blast pass in blast pipe 100 has certain air pressure, Desulphurization is by cannot be by itself weight
Power is entered in blast pipe 100 by delivery pipe 102, therefore seal closure, pressurization is arranged at the top of desulfurization ash-pit 101 in the present embodiment
Gas tank 103 is connected by pipeline with desulfurization ash-pit 101;Pressurized gas 103 be sealing desulfurization ash-pit 101 air pressure is provided, thus
Stream pressure in balance air inlet pipe 100, so that the effect of air pressure and self gravity that Desulphurization is provided in pressurized gas 103
Under, it is delivered in blast pipe 100 by delivery pipe 102, blast pass is by Desulphurization along the pipe of blast pipe 100 in blast pipe 100
Road direction is blown upward in iron powder recycling cavity 200, and then the progress in iron powder recycling cavity 200 to the iron powder in Desulphurization
Separation.
Embodiment 3
A kind of calcium sulfate crystal whiskers preparation system of the present embodiment, basic content with embodiment 1, the difference is that: air inlet
Pipe 100 includes the first blast pipe 110 and the second blast pipe 120, and the first blast pipe 110 and the second blast pipe 120 are correspondingly arranged,
Angle between first blast pipe 110 and the second blast pipe 120 is a, 90~120 ° of the range of a, the first blast pipe 110 and second
Blast pipe 120 can be generated in the bottom that iron powder recycles cavity 200 to the blast pass blown, so that Desulphurization better disperses out
Come, and Desulphurization is blowed by the bottom of iron powder recycling cavity 200 to top under the action of blast pass, and Desulphurization is avoided to exist
It falls under the action of self gravity and is piled up in iron powder recycling 200 bottom of cavity, and then promote iron-containing Desulphurization and electromagnetism
Iron comes into full contact with, and improves electromagnet to the separative efficiency of iron powder.
First blast pipe 110 is provided with desulfurization ash-pit 101 far from the side of the second blast pipe 120;The desulfurization ash-pit 101
Bottom is connected by delivery pipe 102 with the first blast pipe 110;Second blast pipe 120 is arranged far from the side of the first blast pipe 110
There is desulfurization ash-pit 101;The bottom of the desulfurization ash-pit 101 is connected by delivery pipe 102 with the second blast pipe 120;Desulfurization ash-pit 101
In Desulphurization be added separately in the first blast pipe 110 and the second blast pipe 120 by delivery pipe 102, convenient for by Desulphurization
It is added directly into blast pipe 100 along delivery pipe 102, realizes the online separation of iron powder in Desulphurization, improve actual life
Produce efficiency.Blast pipe 100 is provided with air blast blower 150 far from one end of iron powder recycling cavity 200, air blast blower 150 be used for
Blast pipe 100 blasts air-flow.Since the air-flow in blast pipe 100 has certain air pressure, when air pressure is larger, Desulphurization cannot
Enter in blast pipe 100 along delivery pipe 102 from desulfurization ash-pit 101 by the gravity of itself, therefore the present embodiment is in desulfurization ash-pit
101 top is provided with seal closure, and pressurized gas 103 is connected by pipeline with desulfurization ash-pit 101.Pressurized gas 103 is sealing
Desulfurization ash-pit 101 air pressure is provided, thus the stream pressure in balance air inlet pipe 100, so that Desulphurization is mentioned in pressurized gas 103
It under the action of the air pressure and self gravity of confession, is delivered in blast pipe 100 by delivery pipe 102, is constantly blasted in blast pipe 100
Air-flow by Desulphurization along the duct orientation of blast pipe 100 be blown upward iron powder recycling cavity 200 in, and iron powder recycle cavity
Iron powder in 200 in separation Desulphurization.
Further, the bottom of iron powder recycling cavity 200 is provided with cavity contraction section 240, and blast pipe 100 and cavity are shunk
The bottom of section 240 is connected;Blast pipe 100 is connected by the bottom of cavity contraction section 240 and iron powder recycling cavity 200, first into
Be provided between air hose 110 and the second blast pipe 120 air hose junction 130, air hose junction 130 and the first electromagnet 210 and
Gap between second electromagnet 220 is correspondingly arranged, and air hose junction 130 extends to above chamber into cavity contraction section 240
The bottom of body contraction section 240.The blast pass that blast pipe 100 generates is respectively along the first blast pipe 110 and the second blast pipe 120
Direction moves upwards, and blast pass collects in air hose junction 130 and enters cavity contraction section 240, the bottom of cavity contraction section 240
Design is shunk in portion, is moved upwards so that blast pass is gathered, so that the blast pass that blast pipe 100 is blown into is in cavity contraction section
240 opposite aggregations are conducive to Desulphurization and are blowed by the bottom of iron powder recycling cavity 200 to top under the action of blast pass,
It avoids Desulphurization from being deposited on iron powder recycling 200 bottom of cavity because unbalance stress falls under the effect of gravity, and then leads
Cause the separating effect of Desulphurization poor.It is provided with Material valve 104 in delivery pipe 102, can according to need and be turned on or off object
Expect valve 104;The bottom sidewall of first blast pipe 110 and the second blast pipe 120 is connected by pipeline with air blast blower 150, the pipe
Road is provided with air blast valve, and air blast valve is used to control the gas flow of the pipeline;First blast pipe 110 and the second blast pipe 120
It is provided with accumulator tank 140 immediately below bottom, which is used to collect the Desulphurization after separation iron powder.
Further, 240 upper end of cavity contraction section is connected by bellows 131 with the bottom that iron powder recycles cavity 200, chamber
240 lower end of body contraction section is connected by bellows 131 with the top of blast pipe 100, is provided with jarring machine on cavity contraction section 240
Structure, the percussion mechanism is for driving cavity contraction section 240 to be vibrated, so that the Desulphurization accumulated on cavity contraction section 240 is logical
It crosses the first blast pipe 110 and the second blast pipe 120 falls to accumulator tank 140, convenient for sufficiently collecting the Desulphurization of separated iron powder,
The yield of the calcium sulfate crystal whiskers using Desulphurization preparation can be improved.
Embodiment 4
A kind of calcium sulfate crystal whiskers preparation system of the present embodiment, basic content with embodiment 1, the difference is that: use
Calcium sulfate crystal whiskers preparation system prepares calcium sulfate crystal whiskers,
Step 1: Desulphurization pretreatment
Iron powder in Desulphurization is separated with Desulphurization, the bulky grain insoluble matter in Desulphurization is removed, obtains pretreated
Desulphurization;Detailed step are as follows:
(1) Desulphurization is added in Desulphurization iron powder separator, opens electromagnet, opens simultaneously blowback gas tank 410
Air valve, the blowback air in blowback gas tank 410 flow through pipeline enter electromagnet core 205 cylinder it is intracardiac, then blowback air-flow by
The venthole 204 on 205 surface of iron core is overflowed to electromagnet exterior;
Blowback air stream in blowback gas tank 410 respectively enters the first airflow manifold 421 and the second gas by air-flow supervisor 420
Branch pipe 422 is flowed, and controls the flow of the first back-flushing valve 423 and the second back-flushing valve 424 simultaneously;
(2) air blast blower 150, penetrating of the blast pass that air blast blower 150 generates through blast pipe 100 from bottom to top are opened
Iron powder recycles in cavity 200;
(3) Desulphurization is delivered in blast pipe 100 by desulfurization ash-pit 101;
Desulphurization is added to desulfurization ash-pit 101, opens the air valve of pressurized gas 103, pressurized gas 103 is to desulfurization ash-pit
101 pressurize, and then open Material valve 104, Desulphurization is delivered to blast pipe 100 through delivery pipe 102 in desulfurization ash-pit 101
It is interior;
(4) Desulphurization is blown to iron powder recycling cavity 200 by the blast pass of blast pipe 100, the iron powder in Desulphurization
It is adsorbed on the surface of cotton sleeve 203;
Desulphurization is blown to iron powder recycling cavity 200 by the blast pass of blast pipe 100, under the action of blast pass
Desulphurization is blowed to around electromagnet, and the iron powder in Desulphurization is adsorbed in the surface of cotton sleeve 203 by electromagnet, with this
Blowback air stream is overflowed outward by the venthole 204 on 205 surface of electromagnet core simultaneously, and Desulphurization is avoided to penetrate into cotton sleeve
In 203;
(5) Desulphurization after separating iron powder after the blast pass of closing blast pipe 100 drop to recycling under the effect of gravity
In slot 140;
(6) it goes the Desulphurization of iron power removing to mix with water from the taking-up of accumulator tank 140, weeds out bulky grain insoluble matter, then will weed out
The Desulphurization of bulky grain insoluble matter is placed in Buchner funnel 610 and is filtered by vacuum, and obtains pretreated Desulphurization;
Step 2: calcium sulfate crystal whiskers are prepared
By pretreated Desulphurization and MgCl2Solution is mixed to get slurries, then slurries are transferred to the high pressure of reaction unit
In reaction kettle 520, and oxygen is passed through into autoclave 520, adjusting the pressure in autoclave 520 is 1~2MPA, temperature
Degree is 120~180 DEG C, and the temperature of the present embodiment is 180 DEG C;To the hydrothermal synthesis calcium sulfate crystal whiskers in autoclave 520;
Specific steps are as follows:
(1) MgCl that compound concentration is 2%2Solution serves as medium crystallization agent, to MgCl2Pretreated Desulphurization is added in solution
Slurries are uniformly mixing to obtain, the solid-to-liquid ratio for controlling slurries is 1/15~1/20;
(2) Ca (OH) of saturation is added dropwise into slurries2Solution, the pH for adjusting slurries is 8~9;
(3) slurries are added in autoclave 520, to autoclave 520 after closing 520 top cover of autoclave
In be filled with oxygen, and the slurries in autoclave 520 are stirred, stirring intensity is 400~600r/min, reaction time
For 2~3h, thus the hydrothermal synthesis calcium sulfate crystal whiskers in autoclave 520;High pressure oxygen is the oxidant of oxidation stage, chlorine
Change magnesium as medium crystallization agent, in conjunction with crystallization theory, three processes are protected in specific crystallization:
1) oxidation process is dissolved
Thinner granularity makes Desulphurization have large specific surface area, while hydrothermal system temperature with higher and pressure
Power can promote CaSO3·0.5H2The dissolution of O.The SO generated after dissolution3 2-Rapid oxidation is at SO4 2-, oxidation reaction is incessantly
It carries out, CaSO in Desulphurization3·0.5H2O constantly dissolves.
2) crystallization process
As dissolution oxidation process persistently carries out, the Ca in solution2+、SO4 2-Concentration be continuously increased, as the Ca in solution2 +、SO4 2-When reaching hypersaturated state at this temperature, the phenomenon that crystallization is precipitated just is had.Experiment shows reaction condition difference,
Corresponding reaction product also can difference, specific reaction equation it is as follows:
Ca2++SO4 2-=CaSO4(threadiness)
Ca2++SO4 2-+1/2H2O=CaSO4·1/2H2O (threadiness)
Ca2++SO4 2-+2H2O=CaSO4·2H2O (threadiness)
3) whisker growth process
Ca after crystal nucleation, in solution2+、SO4 2-It is still in hypersaturated state, is still constantly precipitated in the form of crystal.
Under the conditions of 180 DEG C, CaSO4Solubility is lower than CaSO4·0.5H2O and CaSO4·2H2O, CaSO4It will be fast centered on nucleus
Rapid hardening is poly-;Simultaneously according to the oriented growth characteristic of calcium sulfate crystal whiskers and under the action of medium crystallization agent, crystal meeting sustainable growth, finally
Form acicular calcium sulfate crystal whiskers.It is as shown in Figure 2 using the SEM picture of calcium sulfate crystal whiskers manufactured in the present embodiment.
Comparative example 1
The basic content of this comparative example 1 with embodiment 4, the difference is that: in step 1: Desulphurization pretreatment in, do not have
Have the iron powder separation in Desulphurization, but directlys adopt the Desulphurization with iron powder and prepare whisker.It is prepared using this comparative example
Calcium sulfate crystal whiskers SEM picture it is as shown in Figure 3.
Shown in comparison diagram 8 and Fig. 9, the calcium sulfate crystal whiskers production prepared using embodiment 4 is relatively orderly, and calcium sulfate crystal whiskers
What is prepared is relatively fast.Its reason may be: comparative example 1 contains in Desulphurization during using calcium sulfate crystal whiskers are prepared
A large amount of CaSO3, it is not available strong acid and cleans, therefore the present embodiment introduces physical dedoping step, is removed using electromagnet
Iron powder in Desulphurization, if directly carrying out hydro-thermal reaction synthesis calcium sulfate crystal whiskers, iron powder using the Desulphurization for not separating iron powder
Meeting and CaSO in hydrothermal system3The oxygen dissolved in contention slurries, while iron powder becomes the crystallization attachment point of newborn calcium sulfate,
Cause a large amount of forming cores of calcium sulfate crystal whiskers, but slow growth, therefore remove the life that the iron powder in Desulphurization is conducive to calcium sulfate crystal whiskers
Growth process.And the iron powder in Desulphurization is carried out physical removal of impurities during preparing calcium sulfate crystal whiskers by embodiment 1, effectively
Ground removes the iron powder in Desulphurization, to improve the preparation quality of calcium sulfate crystal whiskers.
It is worth noting that the MgCl that compound concentration is 2%2Solution serves as medium crystallization agent, to MgCl2Pretreatment is added in solution
Desulphurization afterwards is uniformly mixing to obtain slurries, and the solid-to-liquid ratio for controlling slurries is 1/15~1/20, can be to avoid Desulphurization in slurries
Agglomeration, while thinner granularity is but also Desulphurization obtains specific surface area with larger;The slurries stirred are added to
In autoclave 520, oxygen is filled with into autoclave 520 after closing 520 top cover of autoclave, and it is anti-to control high pressure
Answering the stirring intensity in kettle 520 is 400~600r/min, and the reaction time is 2~3h, so that hydrothermal system temperature with higher
And pressure, the CaSO in Desulphurization can be promoted3·0.5H2The dissolution of O, the SO generated after dissolution3 2-Rapid oxidation is at SO4 2-, oxygen
Change reaction to carry out incessantly, CaSO in Desulphurization3·0.5H2O constantly dissolves, Ca in solution2+、SO4 2-Always in supersaturation
State provides power for the crystallization and growth of calcium sulfate crystal whiskers, realizes sintering flue gas desulfurization ash oxidation coordinate system for calcium sulfate crystalline substance
Must, solve CaSO3It is difficult to quickly oxidation and the longer problem of calcium sulfate crystal whiskers preparation process flow, is that sintering flue gas desulfurization ash is high
Added value resource utilization provides theoretical foundation.
The present invention is described in detail above in conjunction with specific exemplary embodiment.It is understood, however, that can not take off
It is carry out various modifications in the case where from the scope of the present invention being defined by the following claims and modification.Detailed description and drawings
Should be to be considered only as it is illustrative and not restrictive, if there is any such modifications and variations, then they all will
It falls into the scope of the present invention described herein.In addition, Development Status and meaning that background technique is intended in order to illustrate this technology,
It is not intended to limit the present invention or the application and application field of the invention.
Claims (9)
1. a kind of calcium sulfate crystal whiskers preparation system, it is characterised in that: including
Iron powder recyclable device, for separating the iron powder in Desulphurization comprising blast pipe (100), iron powder recycle cavity
(200), top cover (310) and blowback gas tank (410);Electromagnet and cotton sleeve are provided in iron powder recycling cavity (200)
(203), the cotton sleeve (203) is wrapped in the outside of electromagnet, and electromagnet includes conducting wire (202) and iron core (205), wherein
Conducting wire (202) is wound in the outside of iron core (205), and the surface of iron core (205) offers venthole (204), the venthole (204)
It is connected with the cylinder heart of iron core (205);Top cover (310) is set to the top of iron powder recycling cavity (200), the top cover (310)
It is internally provided with filter layer (320);Blast pipe (100) is set to the bottom of iron powder recycling cavity (200), and Desulphurization passes through air inlet
(100) are managed to enter in iron powder recycling cavity (200);Above-mentioned blowback gas tank (410) passes through the cylinder heart of gas pipeline and iron core (205)
It is connected, blast pipe (100) bottom is provided with accumulator tank (140);
Suction filtration device, for the bulky grain insoluble matter in Desulphurization will to be removed comprising filter (602), vacuum pump using circulatory water
(650) and unit (601) are filtered, the pumping that vacuum pump using circulatory water (650) passes through rubber leather hose (640) and suction filtration unit (601)
Mouth (620) is connected;
Reaction unit, for the Desulphurization after separation iron powder to be prepared calcium sulfate crystal whiskers comprising oxygen cylinder (510) and high pressure are anti-
It answers kettle (520), oxygen cylinder (510) is connected by pipeline with the air inlet (523) at the top of autoclave (520).
2. a kind of calcium sulfate crystal whiskers preparation system according to claim 1, it is characterised in that: autoclave (520) top
It is provided with oxygen valve (528) on the air inlet (523) in portion, is set on the pipeline between air inlet (523) and autoclave (520)
It is equipped with relief valve (521), is provided with air gauge (522) on the autoclave (520), setting in autoclave (520)
There are stirring blade (525).
3. a kind of calcium sulfate crystal whiskers preparation system according to claim 1, it is characterised in that: filtering unit (601) includes
Buchner funnel (610), bleeding point (620) and vacuum suction bottle (630), the Buchner funnel (610) are arranged in vacuum suction bottle
(630) top, the side of vacuum suction bottle (630) are provided with bleeding point (620), and bleeding point (620) passes through rubber leather hose
(640) it is connected with vacuum pump using circulatory water (650), top of filter (602) setting in Buchner funnel (610).
4. a kind of calcium sulfate crystal whiskers preparation system according to claim 1, it is characterised in that: electromagnet includes the first electromagnetism
Iron (210), the second electromagnet (220) and third electromagnet (230), wherein the first electromagnet (210) and the second electromagnet (220)
It is set side by side, gap is provided between the first electromagnet (210) and the second electromagnet (220), third electromagnet (230) is set to
The top of first electromagnet (210) and the second electromagnet (220), and third electromagnet (230) is correspondingly arranged with above-mentioned gap.
5. a kind of calcium sulfate crystal whiskers preparation system according to claim 1, it is characterised in that: blowback gas tank connects on (410)
It is connected to air-flow supervisor (420), is connected with the first airflow manifold (421) and the second airflow manifold (422) on air-flow supervisor (420),
First airflow manifold (421) is connected with iron core (205) both ends of third electromagnet (230);Second airflow manifold (422) is respectively
It is connected with the iron core (205) of the first electromagnet (210) and the second electromagnet (220).
6. a kind of calcium sulfate crystal whiskers preparation system according to claim 1, it is characterised in that: the blowing of blast pipe (100)
Desulphurization is blown to iron powder recycling cavity (200) by air-flow, and Desulphurization is blowed to electromagnet under the action of blast pass
Around, the iron powder in Desulphurization is adsorbed in the surface of cotton sleeve (203) by electromagnet, and blowback air stream passes through electricity at the same time
The venthole (204) on pole core (205) surface overflows outward, and Desulphurization is avoided to penetrate into cotton sleeve (203).
7. a kind of calcium sulfate crystal whiskers preparation system according to claim 3, it is characterised in that: the filter (602)
Middle part is provided with strainer (710), and the diameter that the pore size filter of strainer (710) is less than bulky grain insoluble matter is simultaneously greater than Desulphurization
Diameter, the bottom of filter (602) are provided with filtering outlet (720), and filtering outlet (720) is arranged in Buchner funnel (610)
Top.
8. a kind of calcium sulfate crystal whiskers preparation system according to claim 4, it is characterised in that: third electromagnet (230) packet
Include left electromagnet (231) and right electromagnet (232), the junction of left electromagnet (231) and right electromagnet (232) is located at gap
Surface;The angle of left electromagnet (231) and right electromagnet (232) junction is β, and β value range is 120~150 °.
9. a kind of calcium sulfate crystal whiskers preparation system according to claim 1-8, it is characterised in that: blowback gas tank
(410) it is connected with air-flow supervisor (420) on, is connected with the first airflow manifold (421) and the second air-flow branch on air-flow supervisor (420)
It manages (422), the first airflow manifold (421) is connected with iron core (205) both ends of third electromagnet (230);Second airflow manifold
(422) it is connected respectively with the iron core (205) of the first electromagnet (210) and the second electromagnet (220).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811008707.1A CN108998833B (en) | 2018-08-31 | 2018-08-31 | Calcium sulfate whisker preparation system |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811008707.1A CN108998833B (en) | 2018-08-31 | 2018-08-31 | Calcium sulfate whisker preparation system |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108998833A true CN108998833A (en) | 2018-12-14 |
CN108998833B CN108998833B (en) | 2020-07-03 |
Family
ID=64591168
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811008707.1A Active CN108998833B (en) | 2018-08-31 | 2018-08-31 | Calcium sulfate whisker preparation system |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108998833B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111977678A (en) * | 2019-05-24 | 2020-11-24 | 新疆天富环保科技有限公司 | Slurry treatment system and method for wet desulphurization by using semidry desulphurization ash |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN201791675U (en) * | 2010-09-21 | 2011-04-13 | 山东泓奥电力科技有限公司 | High-field intensity magnetic separation coal-desulfurization device |
CN102912445A (en) * | 2012-10-22 | 2013-02-06 | 浙江天蓝环保技术股份有限公司 | Process and device for preparing gypsum whisker by semi-dry desulfurized fly ash and waste acid |
CN106757363A (en) * | 2016-11-29 | 2017-05-31 | 安徽工业大学 | A kind of method that utilization sintering flue gas desulfurization accessory substance prepares calcium sulfate crystal whiskers |
CN107400929A (en) * | 2017-03-03 | 2017-11-28 | 安徽工业大学 | A kind of method that sintering flue gas semi-dry desulphurization ash based on acid oxidation prepares calcium sulfate crystal whiskers |
-
2018
- 2018-08-31 CN CN201811008707.1A patent/CN108998833B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN201791675U (en) * | 2010-09-21 | 2011-04-13 | 山东泓奥电力科技有限公司 | High-field intensity magnetic separation coal-desulfurization device |
CN102912445A (en) * | 2012-10-22 | 2013-02-06 | 浙江天蓝环保技术股份有限公司 | Process and device for preparing gypsum whisker by semi-dry desulfurized fly ash and waste acid |
CN106757363A (en) * | 2016-11-29 | 2017-05-31 | 安徽工业大学 | A kind of method that utilization sintering flue gas desulfurization accessory substance prepares calcium sulfate crystal whiskers |
CN107400929A (en) * | 2017-03-03 | 2017-11-28 | 安徽工业大学 | A kind of method that sintering flue gas semi-dry desulphurization ash based on acid oxidation prepares calcium sulfate crystal whiskers |
Non-Patent Citations (1)
Title |
---|
编辑委员会编: "《钢铁工业节能减排新技术5000问 上 钢铁系统分册》", 31 July 2009, 中国科学技术出版社 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111977678A (en) * | 2019-05-24 | 2020-11-24 | 新疆天富环保科技有限公司 | Slurry treatment system and method for wet desulphurization by using semidry desulphurization ash |
Also Published As
Publication number | Publication date |
---|---|
CN108998833B (en) | 2020-07-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105473504B (en) | Caustic solution is reclaimed by calcium carbonate crystal group | |
CN105821214B (en) | Reviver high-purity energy-conserving and environment-protective smelting process | |
CN109987638A (en) | Red mud produces ferric phosphate lithium cell pigment composite plate | |
CN104762478B (en) | The method reclaiming metal is produced based on pickling mud | |
CN107570723B (en) | Method for producing superfine cobalt powder for hard alloy by fluidized reduction of cobalt carbonate and production system thereof | |
CN110950338A (en) | Method for capturing carbon dioxide and co-producing NPCC (nitrogen phosphorus CC) in converter flue gas by closed cycle of converter steel slag-steelmaking wastewater | |
CN108998833A (en) | A kind of calcium sulfate crystal whiskers preparation system | |
CN108546826A (en) | A kind of closed method stacked from thermal maturation pretreatment extraction vanadium from vanadium slag | |
CN206069961U (en) | The sintering machine that a kind of convulsion and air blast combine | |
CN109082709B (en) | Method for synthesizing calcium sulfate whiskers by using sintered flue gas desulfurization ash through one-step method | |
CN110935422B (en) | Process for enriching heavy metals in desulfurization wastewater based on high-stability adsorbent | |
CN209459440U (en) | A kind of multi-functional smelting furnace exhaust emission device | |
CN106337115A (en) | Super-thick material layer sintering method combining air draft and air blowing, and sintering machine | |
CN105967232A (en) | Method for leaching and simultaneously stabilizing arsenic sulfide slag | |
CN108706622A (en) | A kind of alkali circulation regeneration method | |
CN109355497A (en) | Leach serpentine Mg simultaneously in situ using membrane electrochemical2+Seal CO up for safekeeping2Device and method | |
CN110465176A (en) | Flue-gas dust-removing and desulfurization tower and flue gas desulfurization and wastewater treatment method | |
CN203498140U (en) | Device for treating tungsten smelting exhaust gas and ionic exchange wastewater | |
CN205127629U (en) | Tail gas processing apparatus and be used for buffer tube of tail gas treatment | |
CN109136551B (en) | Method for extracting vanadium from high-calcium stone coal | |
CN207745671U (en) | A kind of limekiln exit gas purifying processing device | |
CN207108834U (en) | For producing the quartz sand red mud processing unit and system of architectural pottery base substrate | |
CN106039863A (en) | Equipment system for treating lead, nitrogen and sulfur with electrolytic manganese anode slag | |
CN102503131B (en) | Method for preparing red mud reduced slag hollow glass beads and iron reduction furnace | |
CN202226898U (en) | Lead-containing material smelting device |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |