CN104312899A - An aerobiotic-anaerobic intermittent aeration reactor for preparing nano selenium and a method thereof for preparing the nano selenium - Google Patents
An aerobiotic-anaerobic intermittent aeration reactor for preparing nano selenium and a method thereof for preparing the nano selenium Download PDFInfo
- Publication number
- CN104312899A CN104312899A CN201410502881.7A CN201410502881A CN104312899A CN 104312899 A CN104312899 A CN 104312899A CN 201410502881 A CN201410502881 A CN 201410502881A CN 104312899 A CN104312899 A CN 104312899A
- Authority
- CN
- China
- Prior art keywords
- water
- aerobic
- anaerobism
- reactor
- water inlet
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M23/00—Constructional details, e.g. recesses, hinges
- C12M23/34—Internal compartments or partitions
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M29/00—Means for introduction, extraction or recirculation of materials, e.g. pumps
- C12M29/06—Nozzles; Sprayers; Spargers; Diffusers
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Zoology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Genetics & Genomics (AREA)
- Microbiology (AREA)
- Biotechnology (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Sustainable Development (AREA)
- Biomedical Technology (AREA)
- Clinical Laboratory Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Biological Treatment Of Waste Water (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention relates to an aerobiotic-anaerobic intermittent aeration reactor for preparing nano selenium. The reactor comprises a reactor main body. The upper part of the reactor main body is provided with a three-phase separator. The side wall of the reactor main body is provided with a first gas outlet, a water outlet and a sludge discharging port. A water distribution system and a gas distribution system are disposed at the bottom of the reactor main body. The water distribution system comprises an anaerobic water distribution branch and an aerobiotic water distribution branch. A microcomputer is disposed outside the reactor main body and controls water feeding of the anaerobic water distribution branch and the aerobiotic water distribution branch, gas feeding of an air compressor and water discharging of a water discharging pipe. The reactor integrates an aerobiotic stage and an anaerobic stage, reduces energy consumption, is simple, convenient, feasible and simplified in process, largely shortens time for microbe culturing and preparation of the nano selenium, and increases the production efficiency.
Description
Technical field
The present invention relates to and a kind ofly prepare the Aerobic-anaerobic intermittent aeration reactor of nanometer selenium and prepare the method for nanometer selenium.
Background technology
The scope of nano particle diameter from 0.1 to 1000 nanometer not etc., determines nano material and has obvious physical chemistry advantage relative to traditional material: good non-linear character, saturated absorption and optical bistability characteristics.Selenium because its special physical properties is as higher photoconductivity, thermal response and nonlinear optical response, because of but a kind of important semiconductor functional material.Therefore, selenium is widely used in a lot of instrument, such as store battery, photoexposure rice, sun power and cell semiconductor rectifier.In addition, selenium is one of necessary nutritional trace element of human body, result of study shows, the activity that selenium can improve glutathione peroxidase reduces the damage to biological cells and tissues, and selenium nano particle has higher biological activity, play an important role in anti-cancer, anticancer, prevention and therapy cardiovascular and cerebrovascular diseases.
Existing more research at present reports the method preparing nanometer selenium, and wherein Biological preparation nanometer selenium is a kind of nontoxic, and environmentally friendly method, therefore more and more by extensive concern.As high flat interest with a pseudomonas aerobic reduction synthesis nanometer selenium, Mausumi Mukhopadhyay utilizes dynamic glue bacterium to synthesize nanometer selenium under aerobic condition, under aerobic environment, microorganism can by electron transmission to selenite, and selenite is reduced to nanometer selenium.In addition, there are some researches show again, utilize amphimicrobe Saccharomycodes also can prepare nanometer selenium, the advantage of this method can prepare nanometer selenium under anaerobic state, reduce the consumption needed for aerobic aeration, shortcoming is culturing yeast Pseudomonas under aerobic condition, under anaerobic state, then reduce selenite, preparation nanometer selenium.The cultivation of microorganism is separated with the preparation process of nanometer selenium, needs to carry out in two reactors, and process is more loaded down with trivial details.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of Aerobic-anaerobic intermittent aeration reactor preparing nanometer selenium, the present invention also provides a kind of method utilizing this device to prepare nanometer selenium.
Technical scheme of the present invention is as follows:
A kind of Aerobic-anaerobic intermittent aeration reactor preparing nanometer selenium, comprise reactor body and top cover, described reactor body is that cylinder is barrel-shaped, reactor body inside is divided into thalline bed district and suspension zone from bottom to top, suspension zone central upper is provided with triphase separator, triphase separator is made up of two pieces of sloping baffles, the top of two sloping baffles is fixed on top cover, the reactor body sidewall on top, suspension zone is provided with the first air outlet, the reactor body sidewall on top, suspension zone is provided with water outlet, water outlet is connected with water tank by rising pipe, first air outlet and water outlet are positioned at relative both sides, the reactor body sidewall being positioned at thalline bed district is provided with mud discharging mouth, the bottom of reactor body is provided with water distribution system and gas distribution system, described water distribution system is divided into anaerobic water branch road and aerobic water distribution branch road, anaerobic water branch road comprises anaerobism water inlet manifold, anaerobism water inlet pipe and anaerobism inlet chest, water inlet manifold is connected with anaerobism water inlet pipe, anaerobism water inlet pipe is communicated with the anaerobism water-in bottom reactor body, and anaerobism water inlet manifold is connected with anaerobism inlet chest, aerobic water distribution branch road comprises aerobic water inlet manifold, aerobic water inlet pipe and aerobic inlet chest, aerobic water inlet manifold is connected with aerobic water inlet pipe, aerobic oxygen water inlet pipe is communicated with the aerobic water-in bottom reactor body, and aerobic water inlet manifold is connected with aerobic inlet chest, described gas distribution system comprises aeration head, aeration head is arranged on the bottom of reactor body, aeration head is connected with air compressor by pipeline, micro computer is outside equipped with at reactor body, the water inlet of microcomputerized control anaerobic water branch road, aerobic water distribution branch road, the air inlet of air compressor and the work of rising pipe water outlet.
The present invention is preferred, the thalline nutritive water that thalli growth needs is contained in described aerobic inlet chest, the aqueous solution containing selenite is contained in anaerobism inlet chest, the composition of thalline nutritive water is as follows: Tryptones 10.0-15.0g/L, yeast extract 5.0-10.0g/L, sodium-chlor 5.0-10.0g/L, KNO
31.0-2.0g/L, MgSO
41.0-2.0g/L, KH
2pO
42.0-3.0g/L, Trisodium Citrate 5.2g/L.Be 36-40mol/L containing the mass concentration of selenite in the aqueous solution of selenite.
The present invention is preferred, two pieces of sloping baffles of triphase separator are positioned at top, suspension zone and top, suspension zone are divided into left part exhaust area, exhaust area, middle part and region, three, right part drained zone, two pieces of sloping baffles are butt V-arrangement, angle between two sloping baffles is 20 ~ 40 °, angle between every block sloping baffle and the plane at top cover place is 60 ° ~ 80 °, and the first air outlet is arranged on the reactor body sidewall of left part exhaust area.
The present invention is preferred, and the side of top cover is provided with the second air outlet, and the second air outlet is communicated with exhaust area, middle part, and the first air outlet is connected collection chamber jointly with the second air outlet.
The present invention is preferred, and the top of top cover is provided with syphon trap, and syphon trap is communicated with exhaust area, middle part, and syphon trap is connected with water-sealed tank, and water-sealed tank is cylindric.
The present invention is preferred, mud discharging mouth is positioned at 3 ~ 10cm place bottom reactor body, mud discharging mouth is connected with spoil disposal pond by shore pipe, spoil disposal pond is connected with circulation tube, the end of circulation tube extends to the suspension zone in reactor body through the top cover of reactor body, the pipeline of circulation tube is provided with recycle pump.
The present invention is preferred, and described aerobic water-in is 3 ~ 6, and quantity and the aerobic water-in of aerobic water inlet pipe match, and aerobic water inlet pipe connects aerobic water inlet manifold jointly; Described anaerobism water-in is 3 ~ 6, and quantity and the anaerobism water-in of anaerobism water inlet pipe match, and anaerobism water inlet pipe connects anaerobism water inlet manifold jointly; Aeration head is arranged on the central position bottom reactor body.
Preferred further, described aerobic water-in is 4, and anaerobism water-in is 4, and 4 aerobic water-ins are rectangle and are distributed in around aeration head centered by aeration head; 4 anaerobism water-ins assume diamond in shape and are distributed in around aeration head centered by aeration head, and anaerobism water-in is arranged between two adjacent aerobic water-ins.
The present invention is preferred, rising pipe is provided with magnetic valve, the opening and closing of solenoid control water outlet, the pipeline of aerobic water inlet manifold is provided with aerobic intake pump, the pipeline of aerobic water inlet manifold is provided with aerobic intake pump, the pipeline of anaerobism water inlet manifold is provided with anaerobism intake pump, and the switch of micro computer to magnetic valve, aerobic intake pump, anaerobism intake pump and air compressor controls.
The present invention is preferred, and water outlet is positioned at distance top cover 10 ~ 20cm position.
The present invention is preferred, and reactor body is synthetic glass housing, and the useful volume of reactor body is 1-10L, is highly 0.5-5m.
The present invention is by controlling gas distribution system, anaerobic water branch road and aerobic water distribution branch road, make gas distribution system synchronous with aerobic water distribution branch road, by aerobic water distribution branch road for Saccharomycodes growth provides the required energy, the aerobic condition of culturing yeast Pseudomonas is provided by gas distribution system, make Saccharomycodes that the nutritive substance in water inlet can be utilized constantly to grow to cultivate, and keep its biological activity, after Saccharomycodes cultivation stage terminates, open anaerobic water branch road, by passing into the aqueous solution containing selenite in anaerobic water Zhi Luxiang reactor body, under anaerobic state, utilize the Saccharomycodes of cultivation reduction selenite to be prepared nanometer selenium.
Thalline bed district of the present invention refers to the region that thalline and charcoal powder mix, and cell concentration is higher, adds charcoal to make the better sedimentation of thalline in thalline bed district, prevents the Saccharomycodes cultivated from discharging reactor with water outlet.The degraded of water inlet and the sedimentation of thalline mainly occur in this region, and suspension zone refers to the region that cell concentration is lower, and the separation of three-phase mainly occurs in this region.
The bottom of reactor body of the present invention arranges aerobic water-in 3 ~ 6, anaerobism water-in 3 ~ 6, be respectively used to the water inlet that aerobic stage is different with anaerobic stages, aerobic water-in is rectangle and is distributed in around aeration head centered by aeration head, anaerobism water-in assumes diamond in shape and is distributed in around aeration head centered by aeration head, anaerobism water-in is arranged between two adjacent aerobic water-ins, make the inlet distribution of aerobic stage and anaerobic stages more even, aerobic water-in is rectangle and is distributed in around aeration head centered by aeration head, water inlet is rectangle into water, in addition the aeration of central position, what Saccharomycodes was contacted with thalline nutritive water is more even, make Saccharomycodes evenly be dispersed in water body, cultivation for Saccharomycodes provides good condition, anaerobism water-in assumes diamond in shape and is distributed in around aeration head centered by aeration head, water inlet assumes diamond in shape into water, make that Saccharomycodes contacts with selenite evenly fully, improve the production efficiency of nanometer selenium.
Utilize the Aerobic-anaerobic intermittent aeration reactor of above-mentioned preparation nanometer selenium to be prepared the method for nanometer selenium, comprise step as follows:
1) Saccharomycodes growth phase: before reactor runs, Saccharomycodes liquid bacterial agent is joined thalline bed district in reactor body, add charcoal powder simultaneously, open the aerobic intake pump on gas distribution system and aerobic water distribution branch road, by thalline nutritive water in reactor, thalline nutritive water passes through aerobic water inlet manifold in aerobic inlet chest, aerobic water inlet pipe enters in reactor from the bottom of reactor body, the water inlet flow velocity controlling thalline nutritive water is 3-6L/h, flooding time: 5-10 minute, after water inlet end, containing 9-10mL microbial inoculum in often liter of thalline nutritive water, containing 1000-1500mg charcoal in often liter of thalline nutritive water, the composition of thalline nutritive water is as follows: Tryptones 10.0-15.0g/L, yeast extract 5.0-10.0g/L, sodium-chlor 5.0-10.0g/L, KNO
31.0-2.0g/L, MgSO
41.0-2.0g/L, KH
2pO
42.0-3.0g/L, Trisodium Citrate 5.2g/L, aeration 5-5.5 hour simultaneously, aeration rate is 40-80L/h, and aeration starts rear Saccharomycodes and starts to decompose the organic substance in thalline nutritive water, and this organic substance provides the required energy for Saccharomycodes growth, produces CO in degradation process
2, CH
4and the oxygen that do not utilize completely in aeration process rises and enters triphase separator, from the first air outlet, the second air outlet discharges, and Saccharomycodes growth phase temperature remains on 25 ± 3 DEG C,
2) after aeration terminates, close the aerobic intake pump on gas distribution system and aerobic water distribution branch road, leave standstill the sedimentation carrying out Saccharomycodes flock for 8-10 minute, after sedimentation terminates, the magnetic valve opened on rising pipe carries out water outlet 5-10 minute, the clear liquid on top, suspension zone flow in water tank by water outlet, controls Water discharge flow speed flow velocity 3-6L/h;
3) after water outlet terminates, close the magnetic valve on rising pipe, leave standstill the oxygen that idle discharge in 24-60 minute is unnecessary, open the anaerobism intake pump on anaerobic water branch road, in reactor, pass into the aqueous solution containing selenite, the aqueous solution containing selenite enters reactor in by anaerobism water inlet manifold, anaerobism water inlet pipe from the bottom of reactor body in anaerobism inlet chest, and the water inlet flow velocity controlled containing the aqueous solution of selenite is 3-6L/h, flooding time 5-10 minute
4) containing after the aqueous solution water inlet end of selenite, close the anaerobism intake pump on anaerobic water branch road, start the preparation carrying out nanometer selenium for anaerobism 5-5.5 hour, the closedown of venting port valve is kept during the preparation of nanometer selenium, prevent oxygen from entering, temperature remains on 25 ± 3 DEG C
5) after the preparatory phase of nanometer selenium terminates, leave standstill the sedimentation carrying out nanometer selenium for 8-10 minute, after sedimentation terminates, the magnetic valve opened on rising pipe carries out water outlet 5-10 minute, and discharge the waste water of anaerobic stages, the clear liquid on top, suspension zone flow in water tank by water outlet, control Water discharge flow speed flow velocity 3-6L/h, open the thalline that mud discharging mouth discharges precipitation, then centrifugal, with distilled water and absolute ethanol washing, obtain red elemental nano-selenium.
The present invention is preferred, is 36-40mol/L containing the mass concentration of selenite in the aqueous solution of selenite.
Preferred further, described selenite is Sodium Selenite or potassium selenite.
The present invention is preferred, step 5) product of removing red elemental nano-selenium after washing pumped in reactor body by recycle pump and carries out recycle.
The present invention is preferred, and Saccharomycodes is prior art, can buy in market.
Saccharomycodes growth phase of the present invention is aerobic stage, and in thalline nutritive water, organic substance provides the required energy for yeast saccharomyces cerevisiae bacteria growing, produces CO in the process that is degraded
2, CH
4deng gas, thalline mixed solution containing the oxygen do not utilized completely in this gas and aeration process continues rising and enters triphase separator, gas is separated with thalline mixed solution by triphase separator, the process water of clarification is produced on the top of suspension zone, S. cervisiae can utilize the nutritive substance in water inlet constantly to grow in this process, and keeps its biological activity.Then sedimentation, water outlet, for discharging the waste water after yeast process, be beneficial to the water inlet of anaerobic stages, the preparatory phase in nanometer selenium: be anaerobic stages, input is containing the selenite aqueous solution, then the preparation of nanometer selenium is started, anaerobic stages is similar to aerobic stage, but only containing the gas that degradation of organic substances produces, this gas and thalline mixed solution rise and enter triphase separator, gas is separated with thalline mixed solution by triphase separator, produces the process water of clarification on the top of suspension zone.
Beneficial effect of the present invention
1, the Aerobic-anaerobic intermittent aeration reactor of preparation nanometer selenium of the present invention integrates aerobic stage and anaerobic stages, by the cultivation of Saccharomycodes, the preparation of growth phase and nanometer selenium gathers together, the cultivation of microorganism and the preparation process of nanometer selenium are gathered together, disposable injection Saccharomycodes is only needed to carry out incubation growth, do not need to prepare nanometer selenium all will cultivate at every turn, and its biological activity can be kept, reduce the consumption of the energy, and it is simple and easy to do, process simplification, substantially reduce the time of the cultivation of microorganism and the preparation of nanometer selenium, improve production efficiency.
2, device of the present invention can carry out the cultivation of Saccharomycodes, the preparation of nanometer selenium can be carried out again, structure is simple, simplify device, more function can be realized, only need the cultured Saccharomycodes of disposable injection, do not need to prepare nanometer selenium all will cultivate at every turn, and its biological activity can be kept, reduce the consumption of the energy, and simple and easy to do.
3, the layout of anaerobism water-in of the present invention and aerobic water-in, be respectively used to the water inlet that aerobic stage is different with anaerobic stages, aerobic water-in is rectangle and is distributed in around aeration head centered by aeration head, anaerobism water-in assumes diamond in shape and is distributed in around aeration head centered by aeration head, anaerobism water-in is arranged between two adjacent aerobic water-ins, make the inlet distribution of aerobic stage and anaerobic stages more even, aerobic water-in is rectangle and is distributed in around aeration head centered by aeration head, water inlet is rectangle into water, in addition the aeration of central position, what Saccharomycodes was contacted with thalline nutritive water is more even, make Saccharomycodes evenly be dispersed in water body, cultivation for Saccharomycodes provides good condition, anaerobism water-in assumes diamond in shape and is distributed in around aeration head centered by aeration head, water inlet assumes diamond in shape into water, make that Saccharomycodes contacts with selenite evenly fully, improve the production efficiency of nanometer selenium.
4, the present invention can also collect reaction process produce inflammable gas recycle.
Accompanying drawing explanation
Fig. 1 is the structural representation that the present invention prepares the Aerobic-anaerobic intermittent aeration reactor of nanometer selenium
Wherein, 1, collection chamber, 2, water-sealed tank, 3, water tank, 4, mud discharging mouth, 5, aerobic inlet chest, 6, aerobic intake pump, 7, anaerobism inlet chest, 8, anaerobism intake pump, 9, air compressor, 10, micro computer, 11, magnetic valve, 12, suspension zone, 13, thalline bed district, the 14, first air outlet, 15, the second air outlet, 16, syphon trap.
Fig. 2 is the structural representation of Aerobic-anaerobic intermittent aeration reactor bottom
Wherein, 1,3,7,9 is aerobic water-in, and 2,4,6,8 is anaerobism water-in, 5, aeration head.
Embodiment:
Embodiment 1
A kind of Aerobic-anaerobic intermittent aeration reactor preparing nanometer selenium, structure as shown in Figure 1, comprise reactor body and top cover, reactor body is that cylinder is barrel-shaped, reactor body inside is divided into thalline bed district 13 and suspension zone 12 from bottom to top, suspension zone 12 central upper is provided with triphase separator, triphase separator is made up of two pieces of sloping baffles, the top of two sloping baffles is fixed on top cover, two pieces of sloping baffles of triphase separator are positioned at top, suspension zone and top, suspension zone are divided into left part exhaust area, exhaust area, middle part and region, three, right part drained zone, two pieces of sloping baffles are butt V-arrangement, angle between two sloping baffles is 60 °, angle between every block sloping baffle and the plane at top cover place is 60 °, the reactor body sidewall on top, suspension zone is provided with the first air outlet 14, first air outlet 14 is arranged on the reactor body sidewall of left part exhaust area.Be provided with the second air outlet 15, air outlet 15, second to be communicated with exhaust area, middle part in the side of top cover, the first air outlet 14 is connected collection chamber 1 jointly with the second air outlet 15.The reactor body sidewall on top, suspension zone is provided with water outlet, and water outlet is connected with water tank 3 by rising pipe, and the first air outlet 14 is positioned at relative both sides with water outlet; The top of top cover is provided with syphon trap 16, and syphon trap 16 is communicated with exhaust area, middle part, and syphon trap is connected with water-sealed tank 2, and water-sealed tank 2 is in cylindric.
The reactor body sidewall being positioned at thalline bed district is provided with mud discharging mouth 4, and mud discharging mouth 4 is positioned at 3cm place bottom reactor body, and mud discharging mouth 4 is connected with spoil disposal pond by shore pipe.
The bottom of reactor body is provided with water distribution system and gas distribution system, described water distribution system is divided into anaerobic water branch road and aerobic water distribution branch road, anaerobic water branch road comprises anaerobism water inlet manifold, anaerobism water inlet pipe and anaerobism inlet chest 7, water inlet manifold is connected with anaerobism water inlet pipe, anaerobism water inlet pipe is communicated with the anaerobism water-in (2,4,6,8) bottom reactor body, and anaerobism water inlet manifold is connected with anaerobism inlet chest; Aerobic water distribution branch road comprises aerobic water inlet manifold, aerobic water inlet pipe and aerobic inlet chest 5, aerobic water inlet manifold is connected with aerobic water inlet pipe, aerobic oxygen water inlet pipe is communicated with the aerobic water-in (1,3,7,9) bottom reactor body, and aerobic water inlet manifold is connected with aerobic inlet chest 5; Aerobic water-in is 4, and anaerobism water-in is 4, and 4 aerobic water-ins are rectangle and are distributed in around aeration head centered by aeration head; 4 anaerobism water-ins assume diamond in shape and are distributed in around aeration head centered by aeration head, and anaerobism water-in is arranged between two adjacent aerobic water-ins.Quantity and the aerobic water-in of aerobic water inlet pipe match, and aerobic water inlet pipe connects aerobic water inlet manifold jointly; Quantity and the anaerobism water-in of anaerobism water inlet pipe match, and anaerobism water inlet pipe connects anaerobism water inlet manifold jointly; Contain the thalline nutritive water that thalli growth needs in aerobic inlet chest, contain the aqueous solution containing selenite in anaerobism inlet chest, the composition of thalline nutritive water is as follows: Tryptones 10.0g/L, yeast extract 5.0g/L, sodium-chlor 5.0g/L, KNO
31.0g/L, MgSO
41.0-g/L, KH
2pO
42.0g/L, Trisodium Citrate 5.2g/L.Be 36-40mol/L containing the mass concentration of selenite in the aqueous solution of selenite.
Described gas distribution system comprises aeration head 5, aeration head 5 is arranged on the central position bottom reactor body, aeration head is connected with air compressor 9 by pipeline, rising pipe is provided with magnetic valve 11, magnetic valve 11 controls the opening and closing of water outlet, the pipeline of aerobic water inlet manifold is provided with aerobic intake pump 6, the pipeline of anaerobism water inlet manifold is provided with anaerobism intake pump 8, and the switch of micro computer to magnetic valve 11, aerobic intake pump 6, anaerobism intake pump 8 and air compressor 9 controls.Water outlet is positioned at distance top cover 10m position.Reactor body is synthetic glass housing, and the useful volume of reactor body is 5L, is highly 3m.
Embodiment 2
The Aerobic-anaerobic intermittent aeration reactor of preparation nanometer selenium as described in Example 1, difference is,
Spoil disposal pond is connected with circulation tube, and the end of circulation tube extends to the suspension zone in reactor body through the top cover of reactor body, the pipeline of circulation tube is provided with recycle pump.
Embodiment 3
The Aerobic-anaerobic intermittent aeration reactor of preparation nanometer selenium as described in Example 1, difference is,
Angle between two sloping baffles is 20 °, and the angle between every block sloping baffle and the plane at top cover place is 80 °, and mud discharging mouth 4 is positioned at 8cm place bottom reactor body, and water outlet is positioned at distance top cover 15m position.
Embodiment 4
Utilize the Aerobic-anaerobic intermittent aeration reactor of the preparation nanometer selenium described in embodiment 1 to be prepared the method for nanometer selenium, comprise step as follows:
1) Saccharomycodes growth phase: before reactor runs, Saccharomycodes liquid bacterial agent is joined thalline bed district in reactor body, add charcoal powder simultaneously, the addition of charcoal powder? open the aerobic intake pump on gas distribution system and aerobic water distribution branch road, by thalline nutritive water in reactor, thalline nutritive water passes through aerobic water inlet manifold in aerobic inlet chest, aerobic water inlet pipe enters in reactor from the bottom of reactor body, the water inlet flow velocity controlling thalline nutritive water is 3L/h, flooding time: 5 minutes, after water inlet end, containing 9mL microbial inoculum in often liter of thalline nutritive water, containing 1000mg charcoal in often liter of thalline nutritive water, the composition of thalline nutritive water is as follows: Tryptones 12.0g/L, yeast extract 8.0g/L, sodium-chlor 8.0g/L, KNO
31.5g/L, MgSO
41.5g/L, KH
2pO
42.5g/L, Trisodium Citrate 5.2g/L, aeration 5 hours simultaneously, aeration rate is 40L/h, aeration starts rear Saccharomycodes and starts to decompose the organic substance in thalline nutritive water, this organic substance provides the required energy for Saccharomycodes grows, CO2 is produced in degradation process, the oxygen do not utilized completely in CH4 and aeration process rises and enters triphase separator, and from the first air outlet, the second air outlet discharges, and Saccharomycodes growth phase temperature remains on 25 DEG C,
2) after aeration terminates, close the aerobic intake pump on gas distribution system and aerobic water distribution branch road, leave standstill the sedimentation carrying out Saccharomycodes flock for 8 minutes, after sedimentation terminates, the magnetic valve opened on rising pipe carries out water outlet 5 minutes, the clear liquid on top, suspension zone flow in water tank by water outlet, controls Water discharge flow speed flow velocity 3L/h;
3) after water outlet terminates, close the magnetic valve on rising pipe, leave standstill the oxygen that idle discharge in 24 minutes is unnecessary, open the anaerobism intake pump on anaerobic water branch road, in reactor, pass into the aqueous solution containing selenite, the aqueous solution containing selenite enters reactor in by anaerobism water inlet manifold, anaerobism water inlet pipe from the bottom of reactor body in anaerobism inlet chest, and the water inlet flow velocity controlled containing the aqueous solution of selenite is 3L/h, flooding time 5 minutes
4) containing after the aqueous solution water inlet end of selenite, close the anaerobism intake pump on anaerobic water branch road, start the preparation that anaerobism carries out nanometer selenium for 5 hours, the closedown of venting port valve is kept during the preparation of nanometer selenium, prevent oxygen from entering, temperature remains on 25 ± 3 DEG C
5) after the preparatory phase of nanometer selenium terminates, leave standstill the sedimentation carrying out nanometer selenium for 8 minutes, after sedimentation terminates, the magnetic valve opened on rising pipe carries out water outlet 5 minutes, and discharge the waste water of anaerobic stages, the clear liquid on top, suspension zone flow in water tank by water outlet, control Water discharge flow speed flow velocity 3L/h, open the thalline that mud discharging mouth discharges precipitation, then centrifugal, with distilled water and absolute ethanol washing, obtain red elemental nano-selenium.Be 36mol/L containing the mass concentration of selenite in the aqueous solution of selenite.Described selenite is Sodium Selenite.
Embodiment 5
Utilize the Aerobic-anaerobic intermittent aeration reactor of the preparation nanometer selenium described in embodiment 1 to be prepared the method for nanometer selenium, comprise step as follows:
1) Saccharomycodes growth phase: before reactor runs, Saccharomycodes liquid bacterial agent is joined thalline bed district in reactor body, add charcoal powder simultaneously, the addition of charcoal powder? open the aerobic intake pump on gas distribution system and aerobic water distribution branch road, by thalline nutritive water in reactor, thalline nutritive water passes through aerobic water inlet manifold in aerobic inlet chest, aerobic water inlet pipe enters in reactor from the bottom of reactor body, the water inlet flow velocity controlling thalline nutritive water is 6L/h, flooding time: 10 minutes, after water inlet end, containing 10mL microbial inoculum in often liter of thalline nutritive water, composition containing 1500mg charcoal thalline nutritive water in often liter of thalline nutritive water is as follows: Tryptones 15.0g/L, yeast extract 10.0g/L, sodium-chlor 10.0g/L, KNO
32.0g/L, MgSO
42.0g/L, KH
2pO
43.0g/L, Trisodium Citrate 5.2g/L, aeration 5.5 hours simultaneously, aeration rate is 80L/h, aeration starts rear Saccharomycodes and starts to decompose the organic substance in thalline nutritive water, this organic substance provides the required energy for Saccharomycodes grows, CO2 is produced in degradation process, the oxygen do not utilized completely in CH4 and aeration process rises and enters triphase separator, and from the first air outlet, the second air outlet discharges, and Saccharomycodes growth phase temperature remains on 28 DEG C,
2) after aeration terminates, close the aerobic intake pump on gas distribution system and aerobic water distribution branch road, leave standstill the sedimentation carrying out Saccharomycodes flock for 10 minutes, after sedimentation terminates, the magnetic valve opened on rising pipe carries out water outlet 10 minutes, the clear liquid on top, suspension zone flow in water tank by water outlet, controls Water discharge flow speed flow velocity 6L/h;
3) after water outlet terminates, close the magnetic valve on rising pipe, leave standstill the oxygen that idle discharge in 60 minutes is unnecessary, open the anaerobism intake pump on anaerobic water branch road, in reactor, pass into the aqueous solution containing selenite, the aqueous solution containing selenite enters reactor in by anaerobism water inlet manifold, anaerobism water inlet pipe from the bottom of reactor body in anaerobism inlet chest, and the water inlet flow velocity controlled containing the aqueous solution of selenite is 6L/h, flooding time 10 minutes
4) containing after the aqueous solution water inlet end of selenite, close the anaerobism intake pump on anaerobic water branch road, start the preparation that anaerobism carries out nanometer selenium for 5.5 hours, the closedown of venting port valve is kept during the preparation of nanometer selenium, prevent oxygen from entering, temperature remains on 28 DEG C
5) after the preparatory phase of nanometer selenium terminates, leave standstill the sedimentation carrying out nanometer selenium for 10 minutes, after sedimentation terminates, the magnetic valve opened on rising pipe carries out water outlet 10 minutes, and discharge the waste water of anaerobic stages, the clear liquid on top, suspension zone flow in water tank by water outlet, control Water discharge flow speed flow velocity 6L/h, open the thalline that mud discharging mouth discharges precipitation, then centrifugal, with distilled water and absolute ethanol washing, obtain red elemental nano-selenium.Be 40mol/L containing the mass concentration of selenite in the aqueous solution of selenite.Described selenite is potassium selenite.
Claims (10)
1. prepare the Aerobic-anaerobic intermittent aeration reactor of nanometer selenium for one kind, comprise reactor body and top cover, described reactor body is that cylinder is barrel-shaped, reactor body inside is divided into thalline bed district and suspension zone from bottom to top, suspension zone central upper is provided with triphase separator, triphase separator is made up of two pieces of sloping baffles, the top of two sloping baffles is fixed on top cover, the reactor body sidewall on top, suspension zone is provided with the first air outlet, the reactor body sidewall on top, suspension zone is provided with water outlet, water outlet is connected with water tank by rising pipe, first air outlet and water outlet are positioned at relative both sides, the reactor body sidewall being positioned at thalline bed district is provided with mud discharging mouth, the bottom of reactor body is provided with water distribution system and gas distribution system, described water distribution system is divided into anaerobic water branch road and aerobic water distribution branch road, anaerobic water branch road comprises anaerobism water inlet manifold, anaerobism water inlet pipe and anaerobism inlet chest, water inlet manifold is connected with anaerobism water inlet pipe, anaerobism water inlet pipe is communicated with the anaerobism water-in bottom reactor body, and anaerobism water inlet manifold is connected with anaerobism inlet chest, aerobic water distribution branch road comprises aerobic water inlet manifold, aerobic water inlet pipe and aerobic inlet chest, aerobic water inlet manifold is connected with aerobic water inlet pipe, aerobic oxygen water inlet pipe is communicated with the aerobic water-in bottom reactor body, and aerobic water inlet manifold is connected with aerobic inlet chest, described gas distribution system comprises aeration head, aeration head is arranged on the bottom of reactor body, aeration head is connected with air compressor by pipeline, micro computer is outside equipped with at reactor body, the water inlet of microcomputerized control anaerobic water branch road, aerobic water distribution branch road, the air inlet of air compressor and the work of rising pipe water outlet.
2. the Aerobic-anaerobic intermittent aeration reactor of preparation nanometer selenium according to claim 1, it is characterized in that, the thalline nutritive water that thalli growth needs is contained in described aerobic inlet chest, the aqueous solution containing selenite is contained in anaerobism inlet chest, the composition of thalline nutritive water is as follows: Tryptones 10.0-15.0g/L, yeast extract 5.0-10.0g/L, sodium-chlor 5.0-10.0g/L, KNO
31.0-2.0g/L, MgSO
41.0-2.0g/L, KH
2pO
42.0-3.0g/L, Trisodium Citrate 5.2g/L.Be 36-40mol/L containing the mass concentration of selenite in the aqueous solution of selenite.
3. the Aerobic-anaerobic intermittent aeration reactor of preparation nanometer selenium according to claim 1, it is characterized in that, two pieces of sloping baffles of triphase separator are positioned at top, suspension zone and top, suspension zone are divided into left part exhaust area, exhaust area, middle part and region, three, right part drained zone, two pieces of sloping baffles are butt V-arrangement, angle between two sloping baffles is 30 ~ 60 °, angle between every block sloping baffle and the plane at top cover place is 60 ° ~ 80 °, first air outlet is arranged on the reactor body sidewall of left part exhaust area, the side of top cover is provided with the second air outlet, second air outlet is communicated with exhaust area, middle part, first air outlet is connected collection chamber jointly with the second air outlet, the top of top cover is provided with escape pipe, escape pipe is communicated with exhaust area, middle part, escape pipe is connected with water-sealed tank, water-sealed tank is cylindric.
4. the Aerobic-anaerobic intermittent aeration reactor of preparation nanometer selenium according to claim 1, it is characterized in that, mud discharging mouth is positioned at 3 ~ 10cm place bottom reactor body, mud discharging mouth is connected with spoil disposal pond by shore pipe, spoil disposal pond is connected with circulation tube, the end of circulation tube extends to the suspension zone in reactor body through the top cover of reactor body, the pipeline of circulation tube is provided with recycle pump.
5. the Aerobic-anaerobic intermittent aeration reactor of preparation nanometer selenium according to claim 1, it is characterized in that, described aerobic water-in is 3 ~ 6, and quantity and the aerobic water-in of aerobic water inlet pipe match, and aerobic water inlet pipe connects aerobic water inlet manifold jointly; Described anaerobism water-in is 3 ~ 6, and quantity and the anaerobism water-in of anaerobism water inlet pipe match, and anaerobism water inlet pipe connects anaerobism water inlet manifold jointly; Aeration head is arranged on the central position bottom reactor body.
6. the Aerobic-anaerobic intermittent aeration reactor of preparation nanometer selenium according to claim 1, is characterized in that, described aerobic water-in is 4, and anaerobism water-in is 4, and 4 aerobic water-ins are rectangle and are distributed in around aeration head centered by aeration head; 4 anaerobism water-ins assume diamond in shape and are distributed in around aeration head centered by aeration head, and anaerobism water-in is arranged between two adjacent aerobic water-ins.
7. the Aerobic-anaerobic intermittent aeration reactor of preparation nanometer selenium according to claim 1, it is characterized in that, rising pipe is provided with magnetic valve, the opening and closing of solenoid control water outlet, the pipeline of aerobic water inlet manifold is provided with aerobic intake pump, the pipeline of aerobic water inlet manifold is provided with aerobic intake pump, the pipeline of anaerobism water inlet manifold is provided with anaerobism intake pump, and the switch of micro computer to magnetic valve, aerobic intake pump, anaerobism intake pump and air compressor controls.
8. the Aerobic-anaerobic intermittent aeration reactor of preparation nanometer selenium according to claim 1, it is characterized in that, water outlet is positioned at distance top cover 10 ~ 20cm position, and reactor body is synthetic glass housing, the useful volume of reactor body is 1-10L, is highly 0.5-5m.
9. utilize the Aerobic-anaerobic intermittent aeration reactor of the preparation nanometer selenium described in claim 1 to be prepared the method for nanometer selenium, comprise step as follows:
1) Saccharomycodes growth phase: before reactor runs, Saccharomycodes liquid bacterial agent is joined thalline bed district in reactor body, add charcoal powder simultaneously, open the aerobic intake pump on gas distribution system and aerobic water distribution branch road, by thalline nutritive water in reactor, thalline nutritive water passes through aerobic water inlet manifold in aerobic inlet chest, aerobic water inlet pipe enters in reactor from the bottom of reactor body, the water inlet flow velocity controlling thalline nutritive water is 3-6L/h, flooding time: 5-10 minute, after water inlet end, containing 9-10mL microbial inoculum in often liter of thalline nutritive water, containing 1000-1500mg charcoal in often liter of thalline nutritive water, the composition of thalline nutritive water is as follows: Tryptones 10.0-15.0g/L, yeast extract 5.0-10.0g/L, sodium-chlor 5.0-10.0g/L, KNO
31.0-2.0g/L, MgSO
41.0-2.0g/L, KH
2pO
42.0-3.0g/L, Trisodium Citrate 5.2g/L, aeration 5-5.5 hour simultaneously, aeration rate is 40-80L/h, aeration starts rear Saccharomycodes and starts to decompose the organic substance in thalline nutritive water, this organic substance provides the required energy for Saccharomycodes grows, CO2 is produced in degradation process, the oxygen do not utilized completely in CH4 and aeration process rises and enters triphase separator, and from the first air outlet, the second air outlet discharges, and Saccharomycodes growth phase temperature remains on 25 ± 3 DEG C,
2) after aeration terminates, close the aerobic intake pump on gas distribution system and aerobic water distribution branch road, leave standstill the sedimentation carrying out Saccharomycodes flock for 8-10 minute, after sedimentation terminates, the magnetic valve opened on rising pipe carries out water outlet 5-10 minute, the clear liquid on top, suspension zone flow in water tank by water outlet, controls Water discharge flow speed flow velocity 3-6L/h;
3) after water outlet terminates, close the magnetic valve on rising pipe, leave standstill the oxygen that idle discharge in 24-60 minute is unnecessary, open the anaerobism intake pump on anaerobic water branch road, in reactor, pass into the aqueous solution containing selenite, the aqueous solution containing selenite enters reactor in by anaerobism water inlet manifold, anaerobism water inlet pipe from the bottom of reactor body in anaerobism inlet chest, and the water inlet flow velocity controlled containing the aqueous solution of selenite is 3-6L/h, flooding time 5-10 minute
4) containing after the aqueous solution water inlet end of selenite, close the anaerobism intake pump on anaerobic water branch road, start the preparation carrying out nanometer selenium for anaerobism 5-5.5 hour, the closedown of venting port valve is kept during the preparation of nanometer selenium, prevent oxygen from entering, temperature remains on 25 ± 3 DEG C
5) after the preparatory phase of nanometer selenium terminates, leave standstill the sedimentation carrying out nanometer selenium for 8-10 minute, after sedimentation terminates, the magnetic valve opened on rising pipe carries out water outlet 5-10 minute, and discharge the waste water of anaerobic stages, the clear liquid on top, suspension zone flow in water tank by water outlet, control Water discharge flow speed flow velocity 3-6L/h, open the thalline that mud discharging mouth discharges precipitation, then centrifugal, with distilled water and absolute ethanol washing, obtain red elemental nano-selenium.
10. the method preparing nanometer selenium according to claim 9, is characterized in that, be 36-40mol/L containing the mass concentration of selenite in the aqueous solution of selenite, described selenite is Sodium Selenite or potassium selenite.Step 5) remove the product of red elemental nano-selenium after washing and pumped in reactor body by recycle pump and carry out recycle.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410502881.7A CN104312899B (en) | 2014-09-26 | 2014-09-26 | A kind of aerobic-anaerobic intermittent aerating reactor for preparing nanometer selenium and its method for preparing nanometer selenium |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410502881.7A CN104312899B (en) | 2014-09-26 | 2014-09-26 | A kind of aerobic-anaerobic intermittent aerating reactor for preparing nanometer selenium and its method for preparing nanometer selenium |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104312899A true CN104312899A (en) | 2015-01-28 |
CN104312899B CN104312899B (en) | 2017-07-28 |
Family
ID=52368218
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410502881.7A Active CN104312899B (en) | 2014-09-26 | 2014-09-26 | A kind of aerobic-anaerobic intermittent aerating reactor for preparing nanometer selenium and its method for preparing nanometer selenium |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104312899B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106582516A (en) * | 2016-11-08 | 2017-04-26 | 浙江工业大学 | Nano-selenium -adsorbed activated carbon and biosynthesis and application thereof |
CN107539963A (en) * | 2016-11-11 | 2018-01-05 | 王鲁宁 | Utilize the method for aerobic microbiological particle preparation nanometer selenium |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN201883042U (en) * | 2010-11-30 | 2011-06-29 | 中国环境科学研究院 | Column-type anaerobic-aerobic integrated fermentation device |
CN202499762U (en) * | 2012-03-26 | 2012-10-24 | 山东北辰集团水务工程有限公司 | Anaerobic-aerobic integration bioreactor |
CN103204587A (en) * | 2013-04-18 | 2013-07-17 | 天津清华德人环境工程有限公司 | Anaerobic-aerobic alternative type granule sludge treatment sewage device and method |
CN103756922A (en) * | 2013-12-31 | 2014-04-30 | 广州市博仕奥生物科技有限公司 | Production method and application for organic yeast protein selenium product with life combined state |
CN103876158A (en) * | 2013-11-18 | 2014-06-25 | 国家***第三海洋研究所 | Elemental selenium and sugar compound and preparation method thereof |
-
2014
- 2014-09-26 CN CN201410502881.7A patent/CN104312899B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN201883042U (en) * | 2010-11-30 | 2011-06-29 | 中国环境科学研究院 | Column-type anaerobic-aerobic integrated fermentation device |
CN202499762U (en) * | 2012-03-26 | 2012-10-24 | 山东北辰集团水务工程有限公司 | Anaerobic-aerobic integration bioreactor |
CN103204587A (en) * | 2013-04-18 | 2013-07-17 | 天津清华德人环境工程有限公司 | Anaerobic-aerobic alternative type granule sludge treatment sewage device and method |
CN103876158A (en) * | 2013-11-18 | 2014-06-25 | 国家***第三海洋研究所 | Elemental selenium and sugar compound and preparation method thereof |
CN103756922A (en) * | 2013-12-31 | 2014-04-30 | 广州市博仕奥生物科技有限公司 | Production method and application for organic yeast protein selenium product with life combined state |
Non-Patent Citations (1)
Title |
---|
车云波等: "《功能食品加工技术》", 31 January 2013 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106582516A (en) * | 2016-11-08 | 2017-04-26 | 浙江工业大学 | Nano-selenium -adsorbed activated carbon and biosynthesis and application thereof |
CN107539963A (en) * | 2016-11-11 | 2018-01-05 | 王鲁宁 | Utilize the method for aerobic microbiological particle preparation nanometer selenium |
Also Published As
Publication number | Publication date |
---|---|
CN104312899B (en) | 2017-07-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103910434B (en) | To exceed standard the membrane type bioreactor of nitrogen phosphorus and treatment process thereof for the treatment of natural pond liquid | |
CN106219871A (en) | A kind of livestock breeding wastewater processing method | |
CN105733930A (en) | Rotating disc type photobioreactor for microalgae large-scale culture | |
CN103789195A (en) | Membrane microalgae photobioreactor for realizing in-situ solid-liquid separation and culture method thereof | |
CN105018336A (en) | Apparatus for culturing microalgae by using waste water | |
CN102311924B (en) | Method for open-type culture of microalgae | |
CN103103128A (en) | Method for high efficiency enrichment culture of microalgae | |
CN109136082A (en) | A kind of membrane bioreactor and helotism system of microalgae and methane-oxidizing bacteria symbiosis reinforcing methane producing bio-oil | |
CN103074231B (en) | Method for producing microalgae by utilizing industrial waste water and waste gas of biobutanol, and application of method | |
CN103103130A (en) | Production method for lipid through mixed culture of microbes | |
CN105543314A (en) | Method for producing polymyxin E through fermentation and foam separation coupling | |
CN112028414B (en) | Biomass hydrothermal energy production process and device | |
CN104745639B (en) | A kind of united two-stage anaerobic fermentation methane production technique of wet method-dry method | |
CN102311922B (en) | Method for high-efficiency culture of microalgae | |
WO2020134688A1 (en) | Method for preparing high-purity hericium erinaceus polysaccharide by fermenting hericium erinaceus, and fermentation medium thereof | |
CN106865935A (en) | Using anthraquinone 2,6 disulfonic acid salt(AQDS)The method for promoting excess sludge methane phase | |
CN104031834B (en) | A kind of photosynthetic bacterium successive reaction hydrogen production process | |
CN104312899A (en) | An aerobiotic-anaerobic intermittent aeration reactor for preparing nano selenium and a method thereof for preparing the nano selenium | |
CN107475090B (en) | A kind of tidal type bioreactor | |
CN101306879A (en) | System for treating high concentrated organic wastewater by three-phase fluidized algae photobioreactor | |
CN203065486U (en) | Device for rapid enrichment-proliferation and purification-cultivation for anaerobic ammonium oxidation bacteria | |
CN103773691A (en) | Enclosed rapid culture method of microalgae | |
CN101275117B (en) | Method for fast algae proliferation directly used for bio-hydrogen production by using CO2 | |
CN103103125B (en) | A kind of microalgae recovery method that microbial flocculation and air supporting are coupled | |
CN102304463B (en) | Spirulina culture system and method based on silica white production system |
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 |