CN107159066A - A kind of spouted fluidized bed fluid bed compound reactor for producing hydrogen fluoride - Google Patents
A kind of spouted fluidized bed fluid bed compound reactor for producing hydrogen fluoride Download PDFInfo
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- CN107159066A CN107159066A CN201710334856.6A CN201710334856A CN107159066A CN 107159066 A CN107159066 A CN 107159066A CN 201710334856 A CN201710334856 A CN 201710334856A CN 107159066 A CN107159066 A CN 107159066A
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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
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/192—Preparation from fluorspar
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1818—Feeding of the fluidising gas
- B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1836—Heating and cooling the reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
- B01J8/38—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it
- B01J8/384—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it being subject to a circulatory movement only
- B01J8/388—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it being subject to a circulatory movement only externally, i.e. the particles leaving the vessel and subsequently re-entering it
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
- B01J2208/00256—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles in a heat exchanger for the heat exchange medium separate from the reactor
Abstract
The invention discloses a kind of spouted fluidized bed fluid bed compound reactor for producing hydrogen fluoride.Reactor includes：Gas distribution grid and solid tremie pipe are set between spouted fluidized bed and fluid bed two reaction zones domain, two conversion zones；Reactor lower part is the undergauge section part below spouted fluidized bed, including direct tube section and the direct tube section.Because in spouted fluidized bed conversion zone, the spouted throughput in center is sufficiently large, the percussion to agglomerate is strong enough, and particle motion intense herein is not likely to produce agglomerate.One aspect of the present invention flows the ratio of stock by increasing annular space area fluidisation stream stock and spouted area, that is, controls general gas flow to the fluidisation stream stock transfer of annular space area.On the other hand by increasing circulating air total flow, maintain fluidisation stream stock to have higher flow rate ratio, strengthen the particle motion in annular space area to regulate and control and eliminate agglomerate.
Description
Technical field
The present invention relates to a kind of spouted fluidized bed reactor and its technique for being used to continuously produce anhydrous hydrogen fluoride.
Background technology
Anhydrous hydrogen fluoride is a kind of important basic chemical industry raw material, and the organic fluoride produced, inorganic fluorine salt dissolving etc. is produced
Product are widely used in fluorination work, petrochemical industry, atomic energy industry etc..The fluorine resource of China is main in the form of fluorite ore and phosphorus ore
In the presence of wherein fluorite basic unit price occupies the 1st, the world, and fluorite is the primary raw material that China produces hydrogen fluoride.
For a long time, with fluorite (Ca2F) rotary kiln technology for raw material is the prevailing technology for producing anhydrous hydrofluoric acid.
It is main in reacting in rotary kiln to occur following react：
CaF2+H2SO4→CaSO4+2HF
The technique at home and abroad commercial Application comparative maturity.But there is complex technical process, equipment heaviness, corrosion in the process
Efficiency low problem when seriously, investing big, the low thermal efficiency, high energy consumption and processing low-grade fluorite ore deposit.
In addition, the technique for hydrogen fluoride being produced by raw material of fluorite also has slurry process and vapor phase method.
CN201210489798.1 discloses a kind of slurry process of gas-solid-liquid three-phase Joint Production hydrogen fluoride, and Fluorspar Powder is in fluidisation shape
With after high-temperature fluorination hydrogen and sulfuric acid vapor reaction and heat exchange, continuously entering the liquid phase stirring of excess sulfuric acid formation instead under state
Answer in device and react.Liquid phase can also be other liquid phases in the technique, but the technique common problem is that liquid phase solvent loss is big,
Reclaim difficult, cost is higher.It is excellent that gas-phase process has that flow is simple, it is low to consume energy and is swift in response etc. compared with other two kinds of techniques
Point, with some superiority.The technique can be realized by reactors such as fluid bed and moving beds.Proposed in US3278265
It is a kind of it is gas-phase fluidized bed prepares hydrogen fluoride technique, use multicompartment fluidized bed reactor in the technique, fluorite is from reactor head
Add, fluidizing gas (vapor, sulfur trioxide, the mixture of sulfuric acid) enters from reactor bottom, both counter current contactings, fluorite
Particle and calcium sulfate particle in the presence of fluidizing gas be in bubbling fluidization state, and under gravity along down-comer successively
Move down, finally discharged from fluidized-bed bottom.But because the particle diameter of reactant fluorite particle is smaller, strong Van der Waals force is easily led between particle
The fluidisation of Fluorspar Powder and all extremely difficult realization of interlayer transmission in caking of reuniting, reactor are caused, this also causes the technique not yet to have at present
Industrial applications example.A kind of vapor phase method moving bed is proposed in US4120939 and prepares hydrogen fluoride technique.Fluorite is from reactor top
Portion is added, and fluidizing gas (vapor, sulfur trioxide, sulfuric acid, the mixture of hydrogen fluoride) enters from reactor bottom, both adverse currents
Contact.By controlling grain diameter and fluidizing gas velocity, make fluorite particle with certain speed decline and step-reaction becomes sulfuric acid
Calcium, finally discharges from reactor bottom.Residence time of the fluorite particle in reactor is about 5~30s.But moving bed reaction
Device requires high to the sphericity and mobility of fluorite particle and calcium sulfate/fluorite composite particles, otherwise easily causes to reunite
Caking, ditch flow short-circuit, and then cause conversion ratio reduction even system crash.So if can be carried out to bonding, clustering phenomena
Effectively regulate and control and prevent, vital effect is played into the progress to vapor phase method fluorite production technology.
With reference to the fluidization characteristic of fluorite particle, it is layering fluidization in fluid bed, and upper strata can be fluidized well, and
Lower floor's fluorite particle forms fixed bed due to bonding not energy fluidizing of reuniting；And with the progressively progress of reaction, solid particle can be by
Product calcium sulfate is gradually changed into by calcirm-fluoride, viscous force between vapor, particle is passed through in course of reaction in addition and dramatically increases, is gathered
Group becomes readily apparent from.The present invention can effectively improve fluorite using spouted bed and fluid bed combined reactor as reaction unit
The problem of layered fluidized middle lower floor's particle agglomeration of particle lumps.In spouted bed, the powerful shearing force of spouted area's stream stock can be crushed
Bed bottom agglomerate, while also can control and eliminate agglomerate by increasing fluidizing gas stream stock in annular space area.
In summary, spouted fluidized bed reactor can effectively suppress particle agglomeration, and the fluidisation for improving fluorite particle is formed, special
Shi Yongyu not vapor phase method production hydrogen fluoride technology.
The content of the invention
It is an object of the invention to provide a kind of spouted bed-fluid bed compound reactor and use for being used to produce hydrogen fluoride
The technique that the reactor produces anhydrous hydrogen fluoride.The reaction unit and production technology can form spouted stream in a reactor
Change bed and fluid bed two reaction zones domain, reach regulation and control and (or) eliminate caking, the purpose of agglomerate.
The reactor that a kind of spouted fluidized bed-fluid bed that the present invention is provided is combined, including：The spouted stream of reactor lower part
Change the undergauge section part below bed, including straight tube cylindrical section and the cylinder, undergauge section has the internal diameter being gradually reduced downwards, and
There is air admission hole in its bottom and multiple apertures of undergauge section are passed through from outside to inside, and spouted bed bottom is sealed by closure
Close and separated with the external world, air admission hole described herein is spouted gas entrance, and the aperture of undergauge section is fluidized gas entrance；On reactor
The fluid bed in portion, including fluid bed direct tube section and the expanding reach on direct tube section top, direct tube section part is as main reaction zone
Domain, and expanding reach is prevented set by particle entrainment；Spouted fluidized bed is provided with outlet for product, and fluid bed is fed provided with solid fluorite
Mouthful；Reactor external heat stove.
According to spouted fluidized bed of the present invention-fluid bed compound reactor, mainly by spouted fluidized bed and fluid bed
Two reaction zones domain is formed by connecting, and gas distribution grid is provided between two reaction zones domain, so, is ensured that between two conversion zones
Gas flowing be continuous.According to the present invention, described spouted fluidized bed conversion zone and the height in fluidized-bed reaction region
Than 1:5-5:Change in the range of 1, preferably 1:4-4:1, more preferably 1：2-2:1.
Exchange between solid particle, is realized by the tremie pipe that is set between two regions, tremie pipe from wall with a distance from
With from the ratio with a distance from bed center 1:50-50:Change between 1, preferably 1:20-20:1, more preferably 1:10-10:1.According to
Reaction rate and required conveying capacity set tremie pipe, at least provided with 1, preferably 2-4.The internal diameter of tremie pipe is at least
6 times of particle diameter of grain, preferably more than the 10 of grain diameter times.Tremie pipe can be arranged on more than spouted fluidized bed region material position,
It can be arranged on below material position.
At least one is provided with above the spouted air-flow of spouted fluidized bed conversion zone conical baffled, the baffle plate has downward
Gradually increased external diameter and in its top closure, and its bottom and the inwall of the cylinder are separated, conical baffled one side stops
The particle of spouted air-flow entrainment blocks gas distribution grid, on the other hand plays a part of gas pre-distributor.
According to the present invention, the undergauge section bottom vertical range of the liquid ejection outlet position and the spouted fluidized bed region
Account for the 20-90% of spouted fluidized bed region total length, more preferably preferably 30-80%, 60-70%.
According to the present invention, described fluorite particulate charge position and the undergauge section bottom vertical range of the reactor accounts for institute
State the 80-95% of spouted fluidized bed region total length, preferably 85-90%.
According to the present invention, heating furnace is provided with outside described spouted fluidized bed-fluid bed compound reactor, makes the reaction
Device internal temperature maintains 200 DEG C -500 DEG C, preferably 200 DEG C -400 DEG C.
Spouted fluidized bed-fluid bed the compound reactor provided using the present invention, produces hydrogen fluoride.In conversion zone, firefly
Stone particle is issued with admixture of gas (sulfuric acid vapor, vapor, sulfur trioxide vapor and hydrogen fluoride steam) in dew point
Raw reaction.In this course, being approximately equal to of sulfuric acid amount reacted with fluorite particle is condensed out from admixture of gas
Learn the amount of metering or the sulfuric acid being slightly in excess in needed for fluorite particle reaction.In addition to reactor, technique is mainly also followed comprising gas
The equipment such as cyclone separator, condenser, gas-liquid separator, current divider after ring element, including gas reactor outlet.Circulation
The fluid sulphuric acid that unit gas-liquid separator comes out, the nozzle set by spouted fluidized bed region, is preferably sprayed in the way of atomization
Inject into spouted fluidized bed conversion zone, balance heat in this region reactor, fluid sulphuric acid evaporates here is transformed into sulfuric acid
Steam, participates in reacting in conversion zone.Fluorite can be crushed in the powerful shearing force of the described spouted area's stream stock of compound reactor
Granuloplastic agglomerate, makes solid particle contact more abundant with admixture of gas, shortens the reaction time, and then improves conversion ratio.
According to the present invention, described fluorite is sour level fluorite, wherein CaF2Content >=60%, grain diameter≤150 μm,
CaF2Charging is 1.2-0.8 with the mol ratio that sulfur trioxide is fed:1, preferably 1.05-0.9:1.
According to the present invention, undergauge section air inlet in the compound reactor bottom is passed through overheated gas mixture, the overheat
Admixture of gas includes vapor, sulfur trioxide, sulfuric acid vapor and hydrogen fluoride gas, and mol ratio is：1:1:1.7, temperature is 360
DEG C -400 DEG C, preferably 370 DEG C -390 DEG C；Vapour pressure is 0.1MPa-0.3MPa, preferably 0.1-0.15MPa.Described gas mixing
The effect of thing is：Condensation of sulfuric acid liberated heat is set to supply fluorite particle and sulfuric acid reaction；The heat loss of equipment in compensation process,
And maintain solid temperature under 100 DEG C-operating pressure between the boiling point of sulfuric acid.
According to the present invention, described gaseous product hydrogen fluoride is first by cyclone separator, by the solid firefly separated
Stone particle and metal sulfate dust send back to conversion zone.Gas from the cyclone separator out is cold within the condenser
But, removed in this stage, high boiling component such as fluosulfonic acid from system.Enter gas-liquid separator, isolated gas afterwards
Phase product hydrogen fluoride and the repeatable fluid sulphuric acid utilized, the fluid sulphuric acid reclaim and send into different zones in bed.From described
The gas obtained in gas-liquid separator is shunted by current divider, and a part sends conversion zone, part feeding subsequent purification list back to
Member obtains product hydrogen fluoride.The gas for sending the conversion zone back to is entered by the spouted stomata and fluidisation stomata of reactor bottom
Bed.The gas entered by reactor bottom, can be entered instead according to certain ratio by spouted stomata and fluidisation stomata
Device is answered, flow rate ratio is 1:12-12:It is adjustable between 1, preferably 1:8-8:1, specific preferred proportion fluidizes situation Lai really by bed
It is fixed.Furthermore, it is possible to hydrogen fluoride gas be added into spouted air-flow stock and fluidisation air-flow stock, to maintain enough spouted stream stock and stream
Change the concentration of gas component in the tolerance or regulation circulating air of stream stock.
FAQs in vapor phase method production hydrogen fluoride reaction device is exactly that reactor clustering phenomena is serious.Due to spouted fluidized
In bed conversion zone, the spouted throughput in center is sufficiently large, and the percussion to agglomerate is strong enough, and particle motion herein is acute
It is strong, it is not likely to produce agglomerate.In addition, the region that agglomerate is also easy to produce is bed bottom, especially proximate to region at wall, particle is active
Property it is not high, when especially with the presence of vapor, between particle viscous force increase so that reunite trend increase, when serious
Bottom stomata or discharging opening can be caused to block, trouble of shutdown is even resulted in.It is therefore desirable to strengthen the particle fortune in this annular space region
It is dynamic, so as to realize the regulation and control to agglomerate herein and elimination.Mainly regulated and controled by increasing annular space area fluidisation stream stock：One side
Face, flows the ratio of stock by increasing annular space area fluidisation stream stock and spouted area, that is, controls general gas flow to turn to annular space area fluidisation stream stock
Move.On the other hand, by increasing circulating air total flow, maintain fluidisation stream stock to have higher flow rate ratio, strengthen the particle in annular space area
Motion is so as to regulate and control and eliminate agglomerate.
According to the present invention, described solid product calcium sulfate is exported from the compound reactor bottoms draw mouthful.
Brief description of the drawings
Come the present invention is described in detail in conjunction with the following drawings.It should be appreciated, however, that accompanying drawing is provided only in more
Understand the present invention well, shall not be construed as limitation of the present invention.
Fig. 1 shows the structural representation that hydrogen fluoride reaction device device is produced according to the spouted fluidized bed of the present invention.
Embodiment
In the present invention, Fig. 1 shows and is combined instead according to a kind of spouted fluidized bed-fluid bed for producing hydrogen fluoride of the present invention
Device device is answered, device is mainly made up of the spouted fluidized bed 20 and superposed fluid bed 19 positioned at reactor bottom.Institute
Stating spouted fluidized bed includes the undergauge section 23 below straight tube cylindrical section 17 and cylinder, and undergauge section is interior with what is be gradually reduced downwards
Footpath, and there is air admission hole 22 in its bottom and multiple open-works 21 of undergauge section are passed through from outside to inside.In addition, spouted fluidized bed
Set in conversion zone at least one conical baffled 5, and described conical baffled there is downward gradually increased external diameter and in Qi Ding
End seal is closed, and its bottom and the inwall of the cylinder are separated, and baffle plate is primarily to the particle of the spouted stream stock entrainment of stop, keeps away
Exempt to block the gas distribution grid between two conversion zones.The fluid bed includes the expansion on fluid bed direct tube section 16 and direct tube section top
Big section 6, direct tube section 16 is main conversion zone, and expanding reach 6 can mainly reduce apparent fluidizing gas velocity, reduces particle and raises
Analysis, so as to prevent the blocking of following cycle pipeline.There is heating furnace 1 outside whole combined-flow fluidized bed reactor.
Fluorite particulate charge position 4 is arranged at the top of fluidized bed region, and reactor is continuously introduced into by feeding screw 3,
Product discharge position 2 is located at spouted fluidized bed region undergauge section.Gas is set between the two reaction zones domain of the compound reactor
Body distribution grid 18 and solid tremie pipe 22, gas distribution grid 18 cause gas to carry out sub-distribution again in fluid bed, it is ensured that gas phase
It is continuous in two regions.It is spouted fluidized that solid tremie pipe 22 moves down into the fluorite particle in fluidized-bed reaction region
In bed conversion zone, further reaction and mixing, are finally gone out in bottom spouted fluidized bed by discharging opening 2 and valve 24
Material.
Spouted fluidized bed and fluidized bed region are provided with least one liquid ejector 15, the position highest injection
The bottom vertical range of device and spouted fluidized bed undergauge section accounts for the 20-90% of the region total length of spouted fluidized bed 16, preferably
30%-80%, more preferably 60-70%.
In the present invention, gas circulation unit includes the cyclone separator 8 after reactor top gas vent, condenser
9th, gas-liquid separator 10, current divider 11 etc..The outlet of reactor top recyclegas enters cyclone separator by Teflon pipeline 7
8 entrances, outlet connection condenser 9.In order to prevent the fine powder of elutriation from blocking subsequent condensation device 9, rotation is set behind expanding reach outlet
Wind separator 8 sends reactor back to after particle is separated.Condenser 9 can be at the top of future autoreactor tower body circulating air pressure
On the one hand power and temperature adjustment remove high boiling component such as fluosulfonic acid in appropriate scope from system, on the other hand will
The temperature of output logistics is maintained in appropriate scope.Medium used in condenser 9 can be water or chemical coolant, it is excellent
Elect water as.Follow-up gas-liquid separator 10 separates gas-liquid mixture, liquid flow stock by pipeline 14 and injector 15, preferably with
The mode of atomization, is sprayed into above spouted fluidized bed region and fluidized bed region charge level respectively.And be free of or containing a small amount of liquid
Gas streams enter current divider 11 shunt after, a part by pipeline 12 and pipeline 13 respectively by aiding in fluidized gas entrance 21
Enter with spouted fluidized gas entrance 22 in spouted fluidized bed, a part enters follow-up purification process as product.
Below by specific embodiment, the invention will be further described.
Embodiment 1
Hydrogen fluoride is produced using spouted fluidized bed as shown in Figure 1-fluid bed compound reactor, compound reactor master
To be made up of the spouted fluidized bed 20 and superposed fluid bed 19 and gas circulation unit positioned at reactor bottom.It is spouted
The undergauge section 23 and air admission hole 22 that fluid bed 20 includes below straight tube cylindrical section 17 and cylinder are constituted, and fluid bed 19 is by straight tube
The expanding reach 6 on section 16 and direct tube section top is constituted.There is heating furnace 1 outside compound reactor.
Cycling element includes the delivery pipe of cyclone separator 8, condenser 9, gas-liquid separator 10, current divider 11 and liquid
Line 14, air shooter line 12,13 etc..Recyclegas flows out from reactor head gas vent, is isolated through cyclone separator 8
The fine particle of entrainment, will circulate air cooling by condenser 9, and separate high-boiling-point impurity, the gas from cooler out
Isolated liquid phase stream stock and gas phase stream stock two parts in gas-liquid separator 10 are sent into, liquid phase stream stock is sprayed by pipeline 14 and liquid
Emitter 15 enters in reactor bed, for the heat in balanced reaction device.And gas phase stream stock is divided into spray by current divider 11
Dynamic gas streams 12 and fluidizing gas stream stock 13, stream stock 12 enters inlet zone by the spouted gas entrance of reactor bottom, flows stock
13 enter annular space area by reactor bottom fluidized gas entrance.Fluidizing gas is main to be steamed by vapor, sulfur trioxide vapor, sulfuric acid
Vapour and hydrogen fluoride gas composition, the temperature into the compound reactor is 386 DEG C, and pressure is 0.1MPa.Fluorite particle is averaged
Particle diameter is 50.6 μm, CaF2Content 93%, is successively sent into reactor by feeding screw.In fluorite particle and charging
The mol ratio of sulphur is 0.95:1, it is 200-400 DEG C to control the temperature range in reactor.At the same time, bottom inlet zone is adjusted
It is respectively the 40% and 20% of the gas gross that gas-liquid separator 10 is exported with annular space area, can so keeps reactor inlet zone
Superficial gas velocity be 2m/s, and the superficial gas velocity in annular space area be 0.08m/s.
After above-mentioned course of reaction carries out 2h, by current divider pipeline 25, hydrogen fluoride content is analyzed, as a result such as table 1.
Embodiment 2
Hydrogen fluoride is produced using spouted fluidized bed compound reactor same as Example 1.Inlet zone and annular space area table
See fluidizing velocity and other conditions keep consistent with embodiment 1.Mainly change following condition：Fluorite particle and sulphur in charging
Mol ratio is 1.0:1, the temperature range in reactor remains as 200-400 DEG C.
After above-mentioned course of reaction carries out 2h, by current divider pipeline 25, hydrogen fluoride content is analyzed, as a result such as table 1.
Embodiment 3
Keep with embodiment identical reaction condition, such as reaction temperature, reaction pressure, fluorite particle with feed in sulphur rub
Your ratio etc..Realized by changing the flow proportional of spouted stream stock, fluidisation stream stock and product hydrogen fluoride stream stock to spouted fluidized
The agglomerate occurred in bed region is effectively controlled.The tolerance in Liu Guji annular spaces area is fluidized, the hundred of the total tolerance of bottom inlet are accounted for
Fraction changes from 30%-50%, and inlet zone tolerance ensures that 40% is constant.
Under conditions of different annular space tolerance, after reaction carries out 2h, calcium sulfate is carried out by pipeline 2 and samples 0.5h,
It it is 50.6 μm by equivalent diameter by the method for screening<d<100 μm of particle is considered as small agglomerate, and d>100 μm of particle is considered as
Big agglomerate.The mass fraction wt% of various agglomerates is counted, regulating and controlling effect of the annular space area tolerance to agglomerate is characterized with this.
On the one hand, agglomerate mass fraction is smaller, illustrates that regulation and control are more effective；On the other hand, large scale agglomerate is fewer, illustrates that regulation and control more have
Effect.Specifically it the results are shown in Table 2.
Table 1
| Embodiment | Hydrogen fluoride content |
| Embodiment 1 | 97% |
| Embodiment 2 | 99% |
Table 2
| Different annular space areas flow | (50.6 μm of wt%<d<100μm) | Wt% (d>100μm) |
| The total tolerance of 30%* | 25% | 20% |
| The total tolerance of 40%* | 23% | 17% |
| The total tolerance of 50%* | 19% | 14% |
As known from Table 1, hydrogen fluoride can be produced using spouted fluidized bed-fluid bed compound reactor of the present invention.
As known from Table 2, using the present invention compound reactor spouted fluidized bed region fluidization gas flow regulation side
Method can efficiently reduce and prevent the agglomerate in region here.
The invention is not limited in specific embodiment disclosed herein, but including falling within the scope of the appended claims
All technical schemes.
Claims (8)
1. a kind of spouted fluidized bed-fluid bed compound reactor for being used to continuously produce hydrogen fluoride, including：Spouted fluidized bed and stream
Change and gas distribution grid and solid tremie pipe are set between bed two reaction zones domain, two conversion zones；Reactor lower part is spouted stream
Change the undergauge section part below bed, including direct tube section and the direct tube section, the direct tube section upper area is provided with least one
It is conical baffled；Undergauge section has the internal diameter being gradually reduced downwards, and has air admission hole in its bottom, passes through the contracting from outside to inside
The multiple open-works and product discharge mouthful of footpath section, and spouted fluidized bed bottom separates by closure closing with the external world；
Reactor top is fluid bed, including fluid bed direct tube section and the expanding reach on direct tube section top, is set at the top of the direct tube section
There is fluorite particulate charge mouthful, there is heating furnace heat preservation and heat supply outside, and the described compound reactor internal temperature of maintenance is at 200-500 DEG C
Between；
Spouted fluidized bed and fluid bed two reaction zones domain are equipped with least one sulfuric acid injector to inject fluid sulphuric acid.
2. spouted fluidized bed-fluid bed compound reactor according to claim 1, it is characterised in that described is spouted
The height ratio in fluidized-bed reaction region and fluidized-bed reaction region is 1:5-5:1.
3. spouted fluidized bed-fluid bed compound reactor according to any one of claim 1-2, it is characterised in that spray
The fluidized bed solid blanking pipeline set between fluidized-bed reaction region is from a distance from wall and from ratio with a distance from bed center
Example is 1:50-50:1, blanking pipeline sets at least one.
4. spouted fluidized bed-fluid bed compound reactor according to any one of claim 1-2, it is characterised in that institute
Rheme puts the undergauge section bottom vertical range of highest sulfuric acid injector and the reactor, and to account for the spouted fluidized bed region total
The 20-90% of length.
5. spouted fluidized bed-fluid bed compound reactor according to claim 1-2, it is characterised in that described stream
Change fluorite particulate charge position and the undergauge section bottom vertical range of the compound reactor at the top of bed and account for the compound reactor
The 80-95% of region total length.
6. a kind of method for producing hydrogen fluoride, its usage right requires that spouted fluidized bed-fluid bed any one of 1-2 is multiple
Close reactor, it is characterised in that comprise the following steps：
A) during fluorite particle is added to reactor by the way that feeding screw is continuous at the top of the compound reactor；
B) overheated gas mixture is passed through from compound reactor bottom undergauge section air inlet, the superheated feedstock gas bag includes water
Steam, sulfur trioxide, sulfuric acid vapor and hydrogen fluoride gas；Pass through liquid ejection outlet above from the spouted fluidized bed conversion zone
Spray into fluid sulphuric acid；
C) gaseous product hydrogen fluoride is exported at the top of the compound reactor, then by cyclone separator dedusting, enters back into condensation
Cooled down in device, then by gas-liquid separator separates gas-phase product hydrogen fluoride and recyclable fluid sulphuric acid, last gas phase is by shunting
A device part sends the reactor back to, and a part carries out subsequent purification as product；Liquid phase is sent to institute according to technological requirement respectively
State compound reactor fluidized bed region and spouted fluidized bed region；
D) solid product calcium sulfate is exported from the reactor bottom.
7. a kind of method for producing hydrogen fluoride according to claim 6, it is characterised in that described fluorite is sour level firefly
Stone, wherein CaF2Content >=60%, granular size≤150 μm, Fluorspar Powder CaF2In with the mol ratio of sulfur trioxide be 1.2-0.8:
1。
8. a kind of method for producing hydrogen fluoride according to claim 6, it is characterised in that the compound reactor bottom
Undergauge section air inlet is passed through overheated gas mixture, and the overheated gas mixture includes vapor, sulfur trioxide and hydrogen fluoride
Gas, mol ratio is 1:1：1.7, temperature is between 360 DEG C -400 DEG C；Vapour pressure is 0.1MPa-0.3MPa.
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| CN108862201A (en) * | 2018-09-12 | 2018-11-23 | 浙江大学 | A method of hydrogen fluoride is prepared using prodan |
| CN108975275A (en) * | 2018-10-17 | 2018-12-11 | 杨松 | It is a kind of to prepare hydrogen fluoride reaction device |
| CN109019517A (en) * | 2018-10-17 | 2018-12-18 | 杨松 | A kind of application method preparing hydrogen fluoride recirculating fluidized bed reacting furnace |
| CN109052325A (en) * | 2018-10-17 | 2018-12-21 | 杨松 | A kind of electron level hydrogen fluoride preparation section |
| CN115875980A (en) * | 2023-01-05 | 2023-03-31 | 唐山精研实业有限责任公司 | Gas inlet and discharge structure for hydrogen-rich reduction large-speed-difference fluidized bed |
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| CN108862201A (en) * | 2018-09-12 | 2018-11-23 | 浙江大学 | A method of hydrogen fluoride is prepared using prodan |
| CN108975275A (en) * | 2018-10-17 | 2018-12-11 | 杨松 | It is a kind of to prepare hydrogen fluoride reaction device |
| CN109019517A (en) * | 2018-10-17 | 2018-12-18 | 杨松 | A kind of application method preparing hydrogen fluoride recirculating fluidized bed reacting furnace |
| CN109052325A (en) * | 2018-10-17 | 2018-12-21 | 杨松 | A kind of electron level hydrogen fluoride preparation section |
| CN115875980A (en) * | 2023-01-05 | 2023-03-31 | 唐山精研实业有限责任公司 | Gas inlet and discharge structure for hydrogen-rich reduction large-speed-difference fluidized bed |
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