CN109650359A - A kind of the industrialization continuous producing apparatus and method of black phosphorus - Google Patents
A kind of the industrialization continuous producing apparatus and method of black phosphorus Download PDFInfo
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- CN109650359A CN109650359A CN201811631571.XA CN201811631571A CN109650359A CN 109650359 A CN109650359 A CN 109650359A CN 201811631571 A CN201811631571 A CN 201811631571A CN 109650359 A CN109650359 A CN 109650359A
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- resisting spiral
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 172
- 238000010438 heat treatment Methods 0.000 claims abstract description 110
- 239000011261 inert gas Substances 0.000 claims abstract description 29
- 239000000047 product Substances 0.000 claims description 80
- 239000002994 raw material Substances 0.000 claims description 75
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 45
- 229910052718 tin Inorganic materials 0.000 claims description 45
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 42
- 229910052740 iodine Inorganic materials 0.000 claims description 42
- 239000011630 iodine Substances 0.000 claims description 42
- 239000011135 tin Substances 0.000 claims description 40
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- 238000004806 packaging method and process Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000006227 byproduct Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 3
- 239000010962 carbon steel Substances 0.000 claims description 3
- 210000003298 dental enamel Anatomy 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 238000010924 continuous production Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 4
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 14
- 238000010586 diagram Methods 0.000 description 8
- 239000013589 supplement Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- 230000001502 supplementing effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000002196 Pyroceram Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- WGVVTQUSFDMILB-UHFFFAOYSA-J triiodyloxystannyl iodate Chemical compound I(=O)(=O)[O-].[Sn+4].I(=O)(=O)[O-].I(=O)(=O)[O-].I(=O)(=O)[O-] WGVVTQUSFDMILB-UHFFFAOYSA-J 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- -1 enamel Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 208000018875 hypoxemia Diseases 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Catalysts (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention discloses a kind of industrialization continuous producing apparatus of black phosphorus, including heat-resisting spiral conversion reactor, feed pipe, discharge nozzle, screw blade, motor, heating device；One end of heat-resisting spiral conversion reactor is arranged in the feed pipe, and the lower section of the other end is arranged in discharge nozzle；Screw blade spiral in the heat-resisting spiral conversion reactor is mounted in shaft, and the both ends of shaft are connect by axle sleeve with heat-resisting spiral conversion reactor；The motor is arranged in one end of heat-resisting spiral conversion reactor and is connected with shaft；It is provided with heating device outside the heat-resisting spiral conversion reactor and feed pipe, heating device is wrapped in outside heat-resisting spiral conversion reactor, and heat-resisting spiral conversion reactor is divided into several heating regions；Inert gas input pipe is provided on the discharge nozzle.The present invention optimizes the technological process of production, and production cost is low, easy to operate and safe, high degree of automation, can carry out continuous production under normal pressure.
Description
Technical field
The present invention relates to black phosphorus preparation technical fields, and in particular to a kind of industrialization continuous producing apparatus of black phosphorus and side
Method.
Background technique
Black phosphorus is the crystal that black has metallic luster, and reactivity is most weak in the allotrope of phosphorus, it is in air
In will not light, therefore black phosphorus is difficult to prepare, and is made generally by white phosphorus is heated under high pressure.Black phosphorus appearance,
Black, sheet all is presented like graphite in performance and structure, and can be conductive, link atom is in the sheet of fold.In stratiform black phosphorus
Phonon, photon and electronics in structure show the anisotropy of height, have on electric thin and infrared ray electronics technology
Great potential using value.
The difficulty of black phosphorus preparation is larger, and high-temperature and high-pressure conditions originally are harsh, and therefore, it is difficult to industrially raw on a large scale
It produces.Red phosphorus is transformed by black phosphorus by high-pressure process or high-energy ball milling method mostly at present, but temperature and pressure is not easy to control, energy consumption is very
Height, the success rate for synthesizing black phosphorus is low, and the black phosphorus being prepared is oxidized easily, while the above method can only be prepared intermittently
Black phosphorus, it is difficult to which large area is carried out using research and development and commercialization.
Summary of the invention
The object of the present invention is to provide a kind of optimizations of technological process of production, and production cost is low, easy to operate and safe, automation
Degree is high, can carry out the industrialization continuous producing apparatus and method of quantity-produced black phosphorus under normal pressure.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of industrialization continuous producing apparatus of black phosphorus, it is characterised in that: including heat-resisting spiral conversion reactor, charging
Pipe, discharge nozzle, screw blade, motor, heating device；One end of heat-resisting spiral conversion reactor is arranged in the feed pipe, out
The lower section of the other end is arranged in expects pipe；Screw blade is provided in the heat-resisting spiral conversion reactor；The screw blade spiral shell
Rotation is mounted in shaft, and shaft is arranged in heat-resisting spiral conversion reactor, and both ends are anti-by axle sleeve and the conversion of heat-resisting spiral
Device is answered to connect；The motor is arranged in one end of heat-resisting spiral conversion reactor and is connected with shaft；The heat-resisting spiral turns
Change and be provided with heating device outside reactor and feed pipe, heating device is wrapped in outside heat-resisting spiral conversion reactor, will be heat-resisting
Spiral conversion reactor is divided into several heating regions；Inert gas input pipe is provided on the discharge nozzle.
As a preferred option of the technical scheme, the heat-resisting spiral conversion reactor is double-layer structure, is divided into shell and liner,
Liner is detachable structure.
As a preferred option of the technical scheme, the heating method of the heating device is Resistant heating, is set in heating device
It is equipped with several segments resistance wire, and is connected with controller.
As a preferred option of the technical scheme, the heating method of the heating device is high-temperature gas heating, on the heating
Air inlet and air outlet are provided with, the middle part of heating device is arranged in air inlet, and gas outlet is arranged in heat-resisting spiral conversion reaction
Device both ends and feed inlet lower end.
Heating method of the present invention can also use infrared ray or microwave stove heating.
As a preferred option of the technical scheme, feed line and/or liquid charging stock input pipe, institute are provided on the feed pipe
It states and is provided with feeding port on feed line.
As a preferred option of the technical scheme, product delivery pipe is provided with below the discharge nozzle.
As a preferred option of the technical scheme, it is provided with outlet for product in the product delivery pipe, and passes through outlet for product
It is connected with product packaging systems.
As a preferred option of the technical scheme, the feed line or the feeding style of product delivery pipe are screw feeding.Spiral shell
The mode entry/exit material for revolving feeding is more uniform, more convenient control entry/exit doses, and the degree of automation is higher.
As a preferred option of the technical scheme, the heat-resisting spiral conversion reactor is using stainless steel, carbon steel, manganese, spraying carbonization
It is any in the metal of object to be made；The liner is made of pyroceram, enamel, graphite.Liner to pass using graphite
It is more preferable to lead performance, heating and heat insulation effect are good, more and so that the black phosphorus quality of production arrived is higher.
A method of it is produced, is included the following steps using the industrialization continuous producing apparatus of black phosphorus,
(1) raw material preparation: reaction raw materials are red phosphorus, tin, iodine；By reaction raw materials by red phosphorus: tin: iodine=6~40:0.7~
The ratio of 3:0.2~0.7 weighs, spare；
(2) raw material loads: raw material is transported in feed pipe after being uniformly mixed through feed line；
(3) calcination reaction: inert gas is passed through to heat-resisting spiral conversion reactor by inert gas input pipe and excludes it
Interior air；Heat-resisting spiral conversion reactor is divided into four regions, respectively one region of A medium temperature, B high-temperature area, C medium temperature
Two regions, D low-temperature region, are preheated by heating device, and the temperature for controlling four regions is followed successively by 400-550 DEG C, 550-
700℃,300-500℃,230-350℃；Enter heat-resisting spiral conversion reactor, raw material after raw material heating reaction in feed pipe
It successively to discharge nozzle movement and is reacted by this four regions under the drive of screw blade, passes through and control motor control propeller
The residence time 2-20h of the revolving speed control raw material of leaf；It comes out from discharge nozzle and is transported to by product delivery pipe after reaction
Product packaging systems are packaged into finished product.
A method of it is produced, is included the following steps using the industrialization continuous producing apparatus of black phosphorus,
(1) raw material preparation: reaction raw materials are yellow phosphorus, tin, iodine；By reaction raw materials by yellow phosphorus: tin: iodine=6~40:0.7~
The ratio of 3:0.2~0.7 weighs, spare；
(2) raw material loads: tin, iodine are transported in feed pipe after being uniformly mixed through feed line, and yellow phosphorus is through liquid charging stock
Feed pipe is added in input pipe；
(3) calcination reaction: inert gas is passed through to heat-resisting spiral conversion reactor by inert gas input pipe and excludes it
Interior air；Heat-resisting spiral conversion reactor is divided into four regions, respectively one region of A medium temperature, B high-temperature area, C medium temperature
Two regions, D low-temperature region, are preheated by heating device, and the temperature for controlling four regions is followed successively by 400-550 DEG C, 500-
700℃,300-500℃,230-350℃；Enter heat-resisting spiral conversion reactor after tin, iodine, yellow phosphorus heating in feed pipe, it is former
Material is successively mobile to discharge nozzle by this four regions under the drive of screw blade and reacts, by controlling motor control spiral
The residence time 2-20h of the revolving speed control raw material of blade；It comes out from discharge nozzle and is conveyed by product delivery pipe after reaction
Finished product is packaged into product packaging systems.
As a preferred option of the technical scheme, the red phosphorus/yellow phosphorus: tin: iodine=16~24:0.9~1.4:0.3~0.6；Raw material
It is respectively 0.5-5h, 0.5-5h, 0.5-5h, 0.5-5h in each region residence time.
As a preferred option of the technical scheme, the red phosphorus/yellow phosphorus: tin: iodine=16~24:0.9~1.4:0.3~0.6；Raw material
It is respectively 1-3h, 1-3h, 1-3h, 1-3h in each region residence time.
Working principle: after raw material (such as red phosphorus/yellow phosphorus, tin, iodine) enters feed pipe, that is, the medium temperature one of reaction system is entered
Region A, temperature are 400-550 DEG C, and iodine distils herein, and tin becomes liquid herein；Gaseous iodine and the tin of liquid are herein
Reaction generates iodate tin catalyst；Stannic iodide and red phosphorus (or yellow phosphorus of liquid) all endothermic gasifications herein, admixture of gas is all
Enter in heat-resisting spiral conversion reactor together, and enter the high-temperature area B of reaction system, temperature is 500-700 DEG C, in this area
Domain phosphorous vapor molecular structure further changes under stannic iodide effect；High-temperature region material continues to enter next medium temperature after moving ahead
Two region C, this regional temperature are 300-500 DEG C, and the phosphorous vapor of molecule structure change is main under stannic iodide catalyst action
Conversion forms black phosphorus solid herein；Black phosphorus solid enters next low-temperature region D, this region under the conveying of screw blade
Temperature is 230-350 DEG C, and black phosphorus is formed to obtain finished product in this region.
The invention has the following advantages:
1, compared with the black phosphorus production method such as existing high-pressure process, ball-milling method, the present invention overcomes previous clearance-types to produce institute
The problems such as production efficiency having is low, at high cost is able to achieve the large batch of large-scale production of black phosphorus, is conducive to improve yield, drop
Low cost improves production efficiency, can further promote the development of black phosphorus industry.
2, there is no limit for pressure when device and method of the invention are to production, can be produced in atmospheric conditions, if
Standby interior pressure and atmospheric pressure pressure difference are small, do not need control pressurer system, so that the operation of entire production system is more convenient,
Equipment is not easy to wear, and the service life is longer, thus further reduces the cost.
3, making for the auxiliary materials such as tin, iodine can be effectively reduced in present device and method during continuous production
Dosage, because tin and the iodine stannic iodide generated being added early period can largely be present in heat-resisting spiral conversion in liquid form
Reactor bottom can effectively reduce the consumption of auxiliary material, therefore can halve supplement every 5-10 days in continuous production
Iodine subtracts four/the tri- supplement auxiliary materials such as tin, further saves reaction raw materials and cost
4, multiple heating devices are provided in equipment of the invention, can according to need segmentally heating, reactor is divided
For multiple and different temperature regions, the reaction temperature of equipment, time are flexibly set.
5, product of the invention can continuously be packed in system, avoid and excessively contact with air, advantageously ensure that black
The degree of purity of phosphorus crystal product prevents from being oxidized, so that product is high-quality and stable.
5, traditional black phosphorus production method vacuumizes and the melting sealed anaerobic or low to guarantee production frequently with quartz ampoule
Oxygen condition, the present invention in equipment by being passed through a small amount of inert gas, so that whole equipment is in the environment of anaerobic or few oxygen, i.e.,
The working condition of black phosphorus can be met, technique more optimizes, and operates more convenient.
6, device and method of the invention can realize the dual production of solid material and liquid charging stock, be provided in equipment solid
The feeding port of body raw material and the feeding port of liquid charging stock can according to need using different production methods, more easily to setting
It is standby to be managed.
Detailed description of the invention
Fig. 1 is the equipment schematic diagram that the present invention uses Resistant heating mode.
Fig. 2 is the present invention using Resistant heating mode and the equipment schematic diagram of carrying liqs raw material input pipe.
Fig. 3 is the equipment schematic diagram that the present invention uses high-temperature gas heating method.
Fig. 4 is equipment schematic diagram of the present invention using high-temperature gas heating method and carrying liqs raw material input pipe.
Fig. 5 is the black phosphorus schematic diagram that present invention production obtains.
Fig. 6 is the black phosphorus schematic diagram that present invention production obtains.
Fig. 7 arrives black phosphorus schematic diagram for prepared by the embodiment of the present invention 3.
Fig. 8 arrives black phosphorus schematic diagram for prepared by the embodiment of the present invention 4.
Fig. 9 is the XRD standard spectrogram of black phosphorus.
Figure 10 is the XRD spectrum of black phosphorus prepared by the embodiment of the present invention 1.
Figure 11 is the XRD spectrum of black phosphorus prepared by the embodiment of the present invention 2.
Figure 12 is the XRD spectrum of black phosphorus prepared by the embodiment of the present invention 3.
Appended drawing reference: 1 heat-resisting spiral conversion reactor, 101 shells, 102 liners, 2 feed pipes, 3 discharge nozzles, 4 propellers
Leaf, 41 shafts, 42 axle sleeves, 5 motors, 6 heating devices, 61 resistance wires, 62 controllers, 63 air inlets, 64 gas outlet, 7 inert gas
Input pipe, 8 feed lines, 9 liquid charging stock input pipes, 10 product delivery pipes, 11 outlet for product, 12 product packaging systems,
13 feeding ports, one region of A medium temperature, B high-temperature area, two region of C medium temperature, D low-temperature region.
Specific embodiment
In order to make those skilled in the art better understand the technical solution in the application, come below in conjunction with embodiment
Technical solution of the present invention is clearly and completely described, it is clear that described embodiment is only a part of the application
Embodiment, based on the embodiment in the application, those of ordinary skill in the art are obtained without making creative work
The every other embodiment obtained, shall fall within the protection scope of the present application.As shown in Figs 1-4.
Embodiment 1
A kind of industrialization continuous producing apparatus of black phosphorus, including heat-resisting spiral conversion reactor 1, feed pipe 2, discharge nozzle 3,
Screw blade 4, motor 5, heating device 6；One end of heat-resisting spiral conversion reactor 1, discharge nozzle 3 is arranged in the feed pipe 2
The lower section of the other end is set；Screw blade 4 is provided in the heat-resisting spiral conversion reactor 1；4 spiral of screw blade
It is mounted in shaft 41, shaft 41 is arranged in heat-resisting spiral conversion reactor 1, and both ends are turned by axle sleeve 42 and heat-resisting spiral
Change reactor 1 to connect；The motor 5 is arranged in one end of heat-resisting spiral conversion reactor 1 and is connected with shaft 41；It is described resistance to
It is provided with heating device 6 outside hot spiral conversion reactor 1, heating device 6 is wrapped in outside heat-resisting spiral conversion reactor 1, will
Heat-resisting spiral conversion reactor 1 is divided into several heating regions；Inert gas input pipe 7 is provided on the discharge nozzle 3.
Heat-resisting spiral conversion reactor 1 is double-layer structure, is divided into shell 101 and liner 102, liner 102 is detachable
Structure.The heating method of the heating device 6 is Resistant heating, and several segments resistance wire 61 is provided in heating device 6, and
It is connected with controller 62.
It is provided with feed line 8 on feed pipe 2, feeding port 13 is provided on feed line 8.
Product delivery pipe 10 is provided with below discharge nozzle 3.
It is provided with outlet for product 11 in product delivery pipe 10, and passes through outlet for product 11 and 12 phase of product packaging systems
Connection.
Feed line 8 or the feeding style of product delivery pipe 10 are screw feeding.
Heat-resisting spiral conversion reactor 1 is made of stainless steel；Liner 12 is made of graphite.
A method of it is produced, is included the following steps using the industrialization continuous producing apparatus of black phosphorus,
(1) raw material preparation: reaction raw materials are red phosphorus, tin, iodine；Reaction raw materials are pressed into red phosphorus: tin: iodine=6:0.7:0.2
Ratio weighs, spare；
(2) raw material loads: raw material is transported in feed pipe 2 after being uniformly mixed through feed line 8；
(3) calcination reaction: inert gas is passed through to heat-resisting spiral conversion reactor 1 by inert gas input pipe 7 and is excluded
Air in it；Heat-resisting spiral conversion reactor 1 is divided into four regions, respectively one region of A medium temperature, B high-temperature area, C
Two region of medium temperature, D low-temperature region, are preheated by heating device 6, and the temperature for controlling four regions is followed successively by 400 DEG C, 500
℃,300℃,230℃；Enter heat-resisting spiral conversion reactor 1 after raw material heating reaction in feed pipe 2, raw material is in propeller
It successively to the movement of discharge nozzle 3 and is reacted by this four regions under the drive of leaf 4, passes through control motor 5 and control screw blade 4
The residence time 20h of revolving speed control raw material；It is come out from discharge nozzle 3 after reaction and product is transported to by product delivery pipe 10
Packaging system 12 is packaged into finished product.
Reactor is divided into four regions by the way of Resistant heating by heating device 6, to the temperature of inside reactor
Degree and heating time carry out flexible modulation；The product that reaction obtains is sent directly into product packaging systems and is packed, and avoids product
It is oxidized.In continuous production every 5 days, supplementing iodine can be halved, subtract four/the tri- supplement auxiliary materials such as tin.
The black phosphorus conversion ratio for using method described in the present embodiment to produce is 95%.
Embodiment 2
A kind of industrialization continuous producing apparatus of black phosphorus, it is characterised in that: including heat-resisting spiral conversion reactor 1, charging
Pipe 2, discharge nozzle 3, screw blade 4, motor 5, heating device 6；Heat-resisting spiral conversion reactor 1 is arranged in the feed pipe 2
The lower section of the other end is arranged in one end, discharge nozzle 3；Screw blade 4 is provided in the heat-resisting spiral conversion reactor 1；It is described
4 spiral of screw blade is mounted in shaft 41, and shaft 41 is arranged in heat-resisting spiral conversion reactor 1, and both ends pass through axle sleeve
42 connect with heat-resisting spiral conversion reactor 1；One end of heat-resisting spiral conversion reactor 1 and and shaft is arranged in the motor 5
41 are connected；Heating device 6 is provided with outside the heat-resisting spiral conversion reactor 1, heating device 6 is wrapped in heat-resisting spiral conversion
Outside reactor 1 and feed inlet 2, heat-resisting spiral conversion reactor 1 is divided into several heating regions；It is set on the discharge nozzle 3
It is equipped with inert gas input pipe 7.
Heat-resisting spiral conversion reactor 1 is double-layer structure, is divided into shell 101 and liner 102, liner 102 is detachable
Structure.
The heating method of the heating device 6 is the heating of person's high-temperature gas, and 63 He of air inlet is provided on heating device 6
The centre of heating device 6 is arranged in gas outlet 64, air inlet 63, and gas outlet 64 is arranged at heat-resisting 1 both ends of spiral conversion reactor
And 2 lower end of feed inlet.
It is provided with feed line 8 on feed pipe 2, feeding port 13 is provided on feed line 8.
Product delivery pipe 10 is provided with below discharge nozzle 3.
It is provided with outlet for product 11 in product delivery pipe 10, and passes through outlet for product 11 and 12 phase of product packaging systems
Connection.
Heat-resisting spiral conversion reactor 1 is made of carbon steel；Liner 12 is made of pyroceram.
A method of it is produced, is included the following steps using the industrialization continuous producing apparatus of black phosphorus,
(1) raw material preparation: reaction raw materials are red phosphorus, tin, iodine；Reaction raw materials are pressed into red phosphorus: tin: iodine=40:3:0.7 ratio
Example weighs, spare；
(2) raw material loads: raw material is transported in feed pipe 2 after being uniformly mixed through feed line 8；
(3) calcination reaction: inert gas is passed through to heat-resisting spiral conversion reactor 1 by inert gas input pipe 7 and is excluded
Air in it；Heat-resisting spiral conversion reactor 1 is divided into four regions, respectively one region of A medium temperature, B high-temperature area, C
Two region of medium temperature, D low-temperature region, are preheated by heating device 6, and the temperature for controlling four regions is followed successively by 550 DEG C, 700
℃,500℃,350℃；Enter heat-resisting spiral conversion reactor 1 after raw material heating reaction in feed pipe 2, raw material is in propeller
It successively to the movement of discharge nozzle 3 and is reacted by this four regions under the drive of leaf 4, passes through control motor 5 and control screw blade 4
The residence time 2h of revolving speed control raw material；It is come out from discharge nozzle 3 after reaction and product is transported to by product delivery pipe 10
Packaging system 12 is packaged into finished product.
Heating device 6 heats reactor using the heating method of high-temperature gas, and high-temperature gas is from reactor
Centre enters so that intermediate temperature highest, when gas is spread to both ends, since heat is consumed by reaction, the temperature at both ends by
Gradually reduce, so that the low temperature consecutive variations region of the high both ends temperature of a medium temperature is formed in reactor, it is defeated by controlling
The temperature and input quantity of the high-temperature gas entered carry out flexible modulation to the temperature and time of inside reactor；React obtained product
It is sent directly into product packaging systems to be packed, product is avoided to be oxidized.It, can be with a quarter in continuous production every 10 days
Supplementing iodine halves the auxiliary materials such as supplement tin.
The black phosphorus conversion ratio for using method described in the present embodiment to produce is 93%.
Embodiment 3
A kind of industrialization continuous producing apparatus of black phosphorus, including heat-resisting spiral conversion reactor 1, feed pipe 2, discharge nozzle 3,
Spiral
A kind of industrialization continuous producing apparatus of black phosphorus, it is characterised in that: including heat-resisting spiral conversion reactor 1, charging
Pipe 2, discharge nozzle 3, screw blade 4, motor 5, heating device 6；Heat-resisting spiral conversion reactor 1 is arranged in the feed pipe 2
The lower section of the other end is arranged in one end, discharge nozzle 3；Screw blade 4 is provided in the heat-resisting spiral conversion reactor 1；It is described
4 spiral of screw blade is mounted in shaft 41, and shaft 41 is arranged in heat-resisting spiral conversion reactor 1, and both ends pass through axle sleeve
42 connect with heat-resisting spiral conversion reactor 1；One end of heat-resisting spiral conversion reactor 1 and and shaft is arranged in the motor 5
41 are connected；Heating device 6 is provided with outside the heat-resisting spiral conversion reactor 1, heating device 6 is wrapped in heat-resisting spiral conversion
Outside reactor 1 and feed inlet 2, heat-resisting spiral conversion reactor 1 is divided into several heating regions；It is set on the discharge nozzle 3
It is equipped with inert gas input pipe 7.
The heating method of heating device 6 is Resistant heating, and several segments resistance wire 61 is provided in heating device 6, and
It is connected with controller 62.
It is provided with feed line 8 and liquid charging stock input pipe 9 on feed pipe 2, is provided with feeding port on feed line 8
13。
It is provided with outlet for product 11 in product delivery pipe 10, and passes through outlet for product 11 and 12 phase of product packaging systems
Connection.
Feed line 8 or the feeding style of product delivery pipe 10 are screw feeding.
Heat-resisting spiral conversion reactor 1 is made of manganese.
A method of it is produced, is included the following steps using the industrialization continuous producing apparatus of black phosphorus,
(1) raw material preparation: reaction raw materials are yellow phosphorus, tin, iodine；Reaction raw materials are pressed into yellow phosphorus: tin: iodine=30:2:0.4 ratio
Example weighs, spare；
(2) raw material loads: tin, iodine are transported in feed pipe 2 after being uniformly mixed through feed line 8, and yellow phosphorus is through liquid original
Expect that feed pipe 2 is added in input pipe 9；
(3) calcination reaction: inert gas is passed through to heat-resisting spiral conversion reactor 1 by inert gas input pipe 7 and is excluded
Air in it；Heat-resisting spiral conversion reactor 1 is divided into four regions, respectively one region of A medium temperature, B high-temperature area, C
Two region of medium temperature, D low-temperature region, are preheated by heating device 6, and the temperature for controlling four regions is followed successively by 500 DEG C, 650
℃,400℃,300℃；Enter heat-resisting spiral conversion reactor 1 after tin, iodine, yellow phosphorus heating in feed pipe 2, raw material is in spiral
It successively to the movement of discharge nozzle 3 and is reacted by this four regions under the drive of blade 4, passes through control motor 5 and control screw blade 4
Revolving speed control raw material residence time；Reactant is respectively 1h, 1h, 1h, 1h in each region residence time；Reaction terminates
Product packaging systems 12 are transported to by product delivery pipe 10 out from discharge nozzle 3 afterwards and are packaged into finished product.
Industrial yellow phosphorus is mostly liquid charging stock, and the holding vessel of yellow phosphorus is connect with raw material input pipe 9, passes through liquid charging stock
Input pipe 9 is added in feed pipe 2, and tin and iodine are added in feed pipe 2 by feed line 8；Heating device 6 is to inside reactor
Temperature and time carry out flexible modulation；The product that reaction obtains is sent directly into product packaging systems and is packed, and avoids product
It is oxidized.In continuous production every 7 days, supplementing iodine can be halved, subtract four/the tri- supplement auxiliary materials such as tin.
The black phosphorus conversion ratio for using method described in the present embodiment to produce is 90%.It is carried out using the equipment of no liner
Production, since heating and heat insulation effect are poor, so lower compared to using the equipment production conversion ratio for having liner.
Embodiment 4
A kind of industrialization continuous producing apparatus of black phosphorus, it is characterised in that: including heat-resisting spiral conversion reactor 1, charging
Pipe 2, discharge nozzle 3, screw blade 4, motor 5, heating device 6；Heat-resisting spiral conversion reactor 1 is arranged in the feed pipe 2
The lower section of the other end is arranged in one end, discharge nozzle 3；Screw blade 4 is provided in the heat-resisting spiral conversion reactor 1；It is described
4 spiral of screw blade is mounted in shaft 41, and shaft 41 is arranged in heat-resisting spiral conversion reactor 1, and both ends pass through axle sleeve
42 connect with heat-resisting spiral conversion reactor 1；One end of heat-resisting spiral conversion reactor 1 and and shaft is arranged in the motor 5
41 are connected；Heating device 6 is provided with outside the heat-resisting spiral conversion reactor 1, heating device 6 is wrapped in heat-resisting spiral conversion
Outside reactor 1 and feed inlet 2, heat-resisting spiral conversion reactor 1 is divided into several heating regions；It is set on the discharge nozzle 3
It is equipped with inert gas input pipe 7.
Heat-resisting spiral conversion reactor 1 is double-layer structure, is divided into shell 101 and liner 102, liner 102 is detachable
Structure.
The heating method of the heating device 6 is Resistant heating, and several segments resistance wire is provided in heating device 6
61, and be connected with controller 62；
It is provided with feed line 8 and liquid charging stock input pipe 9 on feed pipe 2, is provided with feeding port on feed line 8
13。
Product delivery pipe 10 is provided with below discharge nozzle 3.
It is provided with outlet for product 11 in product delivery pipe 10, and passes through outlet for product 11 and 12 phase of product packaging systems
Connection.
Feed line 8 or the feeding style of product delivery pipe 10 are screw feeding.
Heat-resisting spiral conversion reactor 1 is made of the metal of spraying carbide；Liner 12 is made of enamel.
A method of it is produced, is included the following steps using the industrialization continuous producing apparatus of black phosphorus,
(1) raw material preparation: reaction raw materials are yellow phosphorus, tin, iodine；Reaction raw materials are pressed into yellow phosphorus: tin: iodine=16:1.4:0.6
Ratio weighs, spare；
(2) raw material loads: tin, iodine are transported in feed pipe 2 after being uniformly mixed through feed line 8, and yellow phosphorus is through liquid original
Heat-resisting spiral conversion reactor 1 is added in material input pipe 9；
(3) calcination reaction: inert gas is passed through to heat-resisting spiral conversion reactor 1 by inert gas input pipe 7 and is excluded
Air in it；Heat-resisting spiral conversion reactor 1 is divided into four regions, respectively one region of A medium temperature, B high-temperature area, C
Two region of medium temperature, D low-temperature region, are preheated by heating device 6, and the temperature for controlling four regions is followed successively by 450 DEG C, 600
℃,360℃,250℃；Enter heat-resisting spiral conversion reactor 1 after tin, iodine, yellow phosphorus heating in feed pipe 2, raw material is in spiral
It successively to the movement of discharge nozzle 3 and is reacted by this four regions under the drive of blade 4, passes through control motor 5 and control screw blade 4
Revolving speed control raw material residence time；Reactant is respectively 5h, 5h, 3h, 3h in each region residence time；Reaction terminates
Product packaging systems 12 are transported to by product delivery pipe 10 out from discharge nozzle 3 afterwards and are packaged into finished product.
Industrial yellow phosphorus is mostly liquid charging stock, and the holding vessel of yellow phosphorus is connect with raw material input pipe 9, and yellow phosphorus passes through liquid
Raw material input pipe 9 is added in feed pipe 2, and tin and iodine are added in feed pipe 2 by feed line 8；Pass through discharging in production
Pipe 3 is isolated air by inert gas, guarantees the environment of anaerobic or hypoxemia；And by heating device 6 to reactor
Internal temperature and time carries out flexible modulation；The product that reaction obtains is sent directly into product packaging systems and is packed, and avoids
Product is oxidized.In continuous production every 7 days, supplementing iodine can be halved, subtract four/the tri- supplement auxiliary materials such as tin.
The black phosphorus conversion ratio for using method described in the present embodiment to produce is 98.5%.
Embodiment 5
A kind of industrialization continuous producing apparatus of black phosphorus, it is characterised in that: including heat-resisting spiral conversion reactor 1, charging
Pipe 2, discharge nozzle 3, screw blade 4, motor 5, heating device 6；Heat-resisting spiral conversion reactor 1 is arranged in the feed pipe 2
The lower section of the other end is arranged in one end, discharge nozzle 3；Screw blade 4 is provided in the heat-resisting spiral conversion reactor 1；It is described
4 spiral of screw blade is mounted in shaft 41, and shaft 41 is arranged in heat-resisting spiral conversion reactor 1, and both ends pass through axle sleeve
42 connect with heat-resisting spiral conversion reactor 1；One end of heat-resisting spiral conversion reactor 1 and and shaft is arranged in the motor 5
41 are connected；Heating device 6 is provided with outside the heat-resisting spiral conversion reactor 1, heating device 6 is wrapped in heat-resisting spiral conversion
Outside reactor 1 and feed inlet 2, heat-resisting spiral conversion reactor 1 is divided into several heating regions；It is set on the discharge nozzle 3
It is equipped with inert gas input pipe 7.
Heat-resisting spiral conversion reactor 1 is double-layer structure, is divided into shell 101 and liner 102, liner 102 is detachable
Structure.
The heating method of the heating device 6 is the heating of person's high-temperature gas, and 63 He of air inlet is provided on heating device 6
The centre of heating device 6 is arranged in gas outlet 64, air inlet 63, and gas outlet 64 is arranged at heat-resisting 1 both ends of spiral conversion reactor
And 2 lower end of feed inlet.
Product delivery pipe 10 is provided with below discharge nozzle 3.
It is provided with outlet for product 11 in product delivery pipe 10, and passes through outlet for product 11 and 12 phase of product packaging systems
Connection.
Feed line 8 or the feeding style of product delivery pipe 10 are screw feeding.
A method of it is produced, is included the following steps using the industrialization continuous producing apparatus of black phosphorus,
(1) raw material preparation: reaction raw materials are red phosphorus, tin, iodine；Reaction raw materials are pressed into red phosphorus: tin: iodine=24:0.9:0.3
Ratio weighs, spare；
(2) raw material loads: raw material is transported in feed pipe 2 after being uniformly mixed through feed line 8；
(3) calcination reaction: inert gas is passed through to heat-resisting spiral conversion reactor 1 by inert gas input pipe 7 and is excluded
Air in it；Heat-resisting spiral conversion reactor 1 is divided into four regions, respectively one region of A medium temperature, B high-temperature area, C
Two region of medium temperature, D low-temperature region, are preheated by heating device 6, and the temperature for controlling four regions is followed successively by 420 DEG C, 550
℃,440℃,290℃；Enter heat-resisting spiral conversion reactor 1 after raw material heating reaction in feed pipe 2, raw material is in propeller
It successively to the movement of discharge nozzle 3 and is reacted by this four regions under the drive of leaf 4, passes through control motor 5 and control screw blade 4
Revolving speed controls the residence time of raw material, and reactant is respectively 3h, 3h, 5h, 5h in each region residence time；After reaction
Product packaging systems 12 are transported to by product delivery pipe 10 out from discharge nozzle 3 and are packaged into finished product.
Heating device 6 heats reactor using the heating method of high-temperature gas, and high-temperature gas is from reactor
Centre enters so that intermediate temperature highest, when gas is spread to both ends, since heat is consumed by reaction, the temperature at both ends by
Gradually reduce, so that the low temperature consecutive variations region of the high both ends temperature of a medium temperature is formed in reactor, it is defeated by controlling
The temperature and input quantity of the high-temperature gas entered carry out flexible modulation to the temperature and time of inside reactor；React obtained product
It is sent directly into product packaging systems to be packed, product is avoided to be oxidized.In continuous production every 5 days, supplement can be halved
Iodine subtracts four/the tri- supplement auxiliary materials such as tin.
The black phosphorus conversion ratio for using method described in the present embodiment to produce is 95.7%.
The working principle of above-described embodiment: after raw material (such as red phosphorus/yellow phosphorus, tin, iodine) enters feed pipe, that is, reaction is entered
The one region A of medium temperature of system, temperature are 400-550 DEG C, and iodine distils herein, and tin becomes liquid herein；Gaseous iodine and liquid
The tin of state reacts herein generates iodate tin catalyst；Stannic iodide and red phosphorus (or yellow phosphorus of liquid) all endothermic gasifications herein,
Admixture of gas all enters in heat-resisting spiral conversion reactor together, and enters the high-temperature area B, temperature 500- of reaction system
It 700 DEG C, is further changed under stannic iodide effect in this region phosphorous vapor molecular structure；High-temperature region material continues to enter after moving ahead
To next two region C of medium temperature, this regional temperature is 300-500 DEG C, the molecule structure change under stannic iodide catalyst action
Phosphorous vapor mainly herein conversion form black phosphorus solid；Black phosphorus solid enters next low temperature under the conveying of screw blade
Region D, this regional temperature are 230-350 DEG C, and black phosphorus is formed to obtain finished product in this region.
As shown in Fig. 5 to 8, Figure 10-12 present invention is prepared the black phosphorus product that the embodiment of the present invention is produced
Black phosphorus XDR spectrogram, You Tuzhong can see that product dodges the bulk flat crystal of the metallic luster of black, be high-quality black phosphorus.
Claims (10)
1. a kind of industrialization continuous producing apparatus of black phosphorus, it is characterised in that: including heat-resisting spiral conversion reactor (1), charging
Manage (2), discharge nozzle (3), screw blade (4), motor (5), heating device (6)；Feed pipe (2) setting turns in heat-resisting spiral
Change the one end of reactor (1), the lower section of the other end is arranged in discharge nozzle (3)；Setting in the heat-resisting spiral conversion reactor (1)
There are screw blade (4)；Screw blade (4) spiral is mounted on shaft (41), and shaft (41) setting is converted in heat-resisting spiral
In reactor (1), both ends are connect by axle sleeve (42) with heat-resisting spiral conversion reactor (1)；The motor (5) is arranged resistance to
One end of hot spiral conversion reactor (1) is simultaneously connected with shaft (41)；The heat-resisting spiral conversion reactor (1) and feed pipe
(2) it is provided with heating device (6) outside, heating device (6) is wrapped in heat-resisting spiral conversion reactor (1) outside, by heat-resisting spiral
Conversion reactor (1) is divided into several heating regions；Inert gas input pipe (7) are provided on the discharge nozzle (3).
2. the industrialization continuous producing apparatus of black phosphorus according to claim 1, it is characterised in that: the heat-resisting spiral conversion
Reactor (1) is double-layer structure, is divided into shell (101) and liner (102), and liner (102) is detachable structure.
3. the industrialization continuous producing apparatus of black phosphorus according to claim 1, it is characterised in that: the heating device (6)
Heating method be Resistant heating；Be provided with several segments resistance wire (61) in the heating device (6), and with controller (62) phase
Connection.
4. the industrialization continuous producing apparatus of black phosphorus according to claim 1, it is characterised in that: the heating device (6)
Heating method be high-temperature gas heating；Air inlet (63) and gas outlet (64), air inlet are provided on heating device (6)
(63) middle front part in heating device (6) is set, and gas outlet (64) are arranged in heat-resisting spiral conversion reactor (1) both ends and charging
Mouth (2) lower end.
5. the industrialization continuous producing apparatus of black phosphorus according to claim 3 or 4, it is characterised in that: the feed pipe (2)
On be provided with feed line (8) and/or liquid charging stock input pipe (9), be provided with feeding port on the feed line (8)
(13)。
6. the industrialization continuous producing apparatus of black phosphorus according to claim 5, it is characterised in that: under the discharge nozzle (3)
Side is provided with product delivery pipe (10), is provided with outlet for product (11) on the product delivery pipe (10), and go out by product
Material mouth (11) is connected with product packaging systems (12)；The feeding style of the feed line (8) or product delivery pipe (10)
For screw feeding.
7. the industrialization continuous producing apparatus of black phosphorus according to claim 1, it is characterised in that: the heat-resisting spiral conversion
Reactor (1) uses stainless steel, carbon steel, manganese, sprays any in the metal of carbide be made；The liner (102) is using resistance to
High temp glass, graphite any in enamel are made.
8. a kind of method that the industrialization continuous producing apparatus using black phosphorus as claimed in claim 1 to 7 is produced,
It is characterized in that: including the following steps,
(1) raw material preparation: reaction raw materials are red phosphorus, tin, iodine；Reaction raw materials are pressed into red phosphorus: tin: iodine=6~40:0.7~3:0.2
~0.7 ratio weighs, spare；
(2) raw material loads: raw material is transported in feed pipe (2) after being uniformly mixed through feed line (8)；
(3) calcination reaction: inert gas is passed through by inert gas input pipe (7) Xiang Naire spiral conversion reactor (1) and is excluded
Air in it；Heat-resisting spiral conversion reactor (1) is divided into four regions, respectively one region of A medium temperature, B high-temperature area,
Two region of C medium temperature, D low-temperature region are preheated by heating device (6), and the temperature for controlling four regions is followed successively by 400-550
℃,500-700℃,300-500℃,230-350℃；Enter heat-resisting spiral after raw material heating reaction in feed pipe (2) to convert
Reactor (1), raw material is successively mobile to discharge nozzle (3) by this four regions under the drive of screw blade (4) and reacts, and leads to
Cross the residence time 2-20h of the revolving speed control raw material of control motor (5) control screw blade (4)；After reaction from discharge nozzle
(3) product packaging systems (12) are transported to by product delivery pipe (10) out in and are packaged into finished product.
9. a kind of method that the industrialization continuous producing apparatus using black phosphorus as claimed in claim 1 to 7 is produced,
It is characterized in that: including the following steps,
(1) raw material preparation: reaction raw materials are yellow phosphorus, tin, iodine；Reaction raw materials are pressed into yellow phosphorus: tin: iodine=6~40:0.7~3:0.2
~0.7 ratio weighs, spare；
(2) raw material loads: tin, iodine are transported in feed pipe (2) after being uniformly mixed through feed line (8), and yellow phosphorus is through liquid original
Expect that feed pipe (2) are added in input pipe (9)；
(3) calcination reaction: inert gas is passed through by inert gas input pipe (7) Xiang Naire spiral conversion reactor (1) and is excluded
Air in it；Heat-resisting spiral conversion reactor (1) is divided into four regions, respectively one region of A medium temperature, B high-temperature area,
Two region of C medium temperature, D low-temperature region are preheated by heating device (6), and the temperature for controlling four regions is followed successively by 400-550
℃,500-700℃,300-500℃,230-350℃；Enter heat-resisting spiral after tin, iodine and yellow phosphorus heating in feed pipe (2) to turn
To change reactor (1), raw material is successively mobile to discharge nozzle (3) by this four regions under the drive of screw blade (4) and reacts,
The residence time 2-20h of raw material is controlled by the revolving speed of control motor (5) control screw blade (4)；After reaction from discharging
Product packaging systems (12), which are transported to, by product delivery pipe (10) out in pipe (3) is packaged into finished product.
10. the method produced according to claim 8 or claim 9 using the industrialization continuous producing apparatus of black phosphorus, feature
It is: the red phosphorus/yellow phosphorus: tin: iodine=16~24:0.9~1.4:0.3~0.6；Raw material is in each region residence time point
It Wei not 0.5-5h, 0.5-5h, 0.5-5h, 0.5-5h.
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