CN107311109B - A kind of circulating fluidized bed system and method with Fluorspar Powder production hydrogen fluoride - Google Patents
A kind of circulating fluidized bed system and method with Fluorspar Powder production hydrogen fluoride Download PDFInfo
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- 239000010436 fluorite Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000000843 powder Substances 0.000 title claims abstract description 31
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910000040 hydrogen fluoride Inorganic materials 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 118
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000007789 gas Substances 0.000 claims abstract description 38
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 21
- 238000005204 segregation Methods 0.000 claims abstract description 20
- 238000009833 condensation Methods 0.000 claims abstract description 16
- 230000005494 condensation Effects 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000012265 solid product Substances 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 39
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 19
- 239000007795 chemical reaction product Substances 0.000 claims description 17
- 239000012071 phase Substances 0.000 claims description 11
- 239000013589 supplement Substances 0.000 claims description 11
- 239000012495 reaction gas Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 238000010574 gas phase reaction Methods 0.000 claims description 7
- 238000003746 solid phase reaction Methods 0.000 claims description 6
- 239000008246 gaseous mixture Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims 1
- 230000008676 import Effects 0.000 claims 1
- 230000002159 abnormal effect Effects 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 239000003292 glue Substances 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 239000000498 cooling water Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019000 fluorine Nutrition 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- B01J8/1872—Details of the fluidised bed reactor
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention discloses a kind of circulating fluidized bed systems and method with Fluorspar Powder production hydrogen fluoride.System includes reactor, cyclic part, solid segregation section, solid segregation section.Reactor part is the place that reaction occurs, and cyclic part isolates the incomplete solid of reaction, back to the reaction was continued in reactor after being settled；Solid separate section separates gas-particle two-phase product, and collects the solid of fully reacting, as solid product；Gas condensation portion will separate remaining gas-phase product out and liquefy and collect in solid segregation section.The invention avoids the appearance that agglomerate glues the abnormal phenomenon such as wall, improve mass transfer, heat transfer efficiency, by the cycling rate of control valve aperture control loop fluidized bed on control tolerance size and inclined tube, the solid product ratio isolated is controlled to control solid reaction degree.Liquid condensation is controlled by condensate temperature and dosage, can control product quality by installing multi-stage condensing device additional when containing other impurities in gaseous product.
Description
Technical field
The present invention relates to a kind of Circulating Fluidized Bed Process for Fluorspar Powder production hydrogen fluoride.
Technical background
Hydrofluoric acid (HF) is the basic product of entire fluorine chemical industry, is mainly used in fluorohydrocarbon industry, accounts for hydrogen fluoride and always disappear
50% or so of consumption；The inorganic fluorines salt dissolvings such as aluminum fluoride and the ice crystal of electrolytic aluminium and aluminium product industry are followed by produced,
Account for 30% or more；Be again pickling of metal, be used as in oil plant iso-butane and butane alkylated reaction catalyst and other
The production industry of fluorinated organic compound.China is continuously increased the demand of anhydrous hydrogen fluoride in recent years.
Hydrogen fluoride production mainly passes through fluorite and obtains with sulfuric acid reaction.Calcirm-fluoride and sulfuric acid reaction are an endothermic reactions,
It industrially needs to react at high temperature, external heating is needed in production process.Current existing production technology mainly has rotary kiln
Technique, gas-solid multicompartment fluidized bed technique, gas-liquid-solid fluidized-bed process, intermittent reaction technique etc..United States Patent (USP) US3102787 is announced
The method of two kinds of Fluorspar Powders and sulfuric acid reaction production hydrogen fluoride.One of which is rotary kiln technology, and one is multilayer gas-solid flows
Change bed process.Rotary kiln technology is most common production technology in current industry.In the technique, Fluorspar Powder and sulfuric acid pass through premix
The modes such as conjunction, stirring, shell revolution react in the rotary kiln with heating rotary shell in mixing.According to internal mix
Agitating member is different, is broadly divided into simple rotary kiln, the rotary kiln with premixer, the rotary kiln with pre-reactor, interior returns
Return slag rotary kiln and several simultaneous with pre-reactor, interior return slag, the rotary kiln of destroyer in slag rotary kiln, pre-reactor.
Rotary kiln technology has obtained sufficient development at present, from production maintenance, operating cost, equipment manufacturing cost, consumption of raw materials be difficult into
One step reduces.Gas-solid multicompartment fluidized bed technique uses vapor and SO3As air inlet, gas phase reaction generates sulfuric acid and releases gas
Big calorimetric provides reaction raw materials sulfuric acid for device, while providing fluorite and heat needed for sulfuric acid reaction.Gas-solid multicompartment fluidized bed work
Skill can be improved the reaction efficiency of reactor and eliminate the problem that fluid sulphuric acid reacts easily tacky with fluorite, has and is swift in response,
Fluorite utilization rate is high, the simple feature of facility compact.Chinese patent CN201210276366.2 is further perfect gas-solid fluidized
Bed process expands available Fluorspar Powder purity range.But (average grain diameter exists since fluorite grain diameter used in industry is smaller
Between 20~40 μm), particle agglomeration caused by strong Van der Waals force makes fluidisation and interlayer transmitting become extremely difficult between particle, more
Laminarization bed reaction technique is not yet really applied in industry in practice.
In addition to such a technique, a kind of gas-liquid-solid fluidized-bed process is also disclosed in Chinese patent CN201210489798.1, makes
It uses phenyl-hexafluoride as inertia dispersing agent, Fluorspar Powder is dispersed, sulfuric acid is dissolved in phenyl-hexafluoride, is reacted with Fluorspar Powder, releases
Hydrogen fluoride gas.The technique is able to solve the problem of Fluorspar Powder bonding, improves the efficiency that powder is contacted with acid.But after reacting
The separation of the calcium sulfate and dispersing agent of discharge there is a problem of very big, and dispersing agent entrainment is excessive and is difficult to separate so that the technique is difficult
Further to develop.
In view of the above-mentioned problems, the invention proposes a kind of Circulating Fluidized Bed Process for Fluorspar Powder production hydrogen fluoride.
In recirculating fluidized bed, on the one hand high fluidizing gas velocity is able to suppress particle agglomeration and viscous wall, effectively eliminates reunion
And influence of the viscous wall to mass-and heat-transfer；It is quickly anti-that another aspect Fluorspar Powder carries out short-time contact progress with sulfuric acid in a fluidized bed
Settler should be entered afterwards to settle, be recirculated back in fluidized bed that the reaction was continued.Fast reaction is able to maintain higher sulfuric acid concentration, keeps away
The problem of reaction rate caused by reaction later period sulfuric acid deficiency substantially slows down is exempted from, production efficiency can be effectively improved.
Summary of the invention
The present invention provides a kind of Circulating Fluidized Bed Process for Fluorspar Powder production hydrogen fluoride, passes through Fluorspar Powder Rapid Circulation
By fluidized-bed reaction, particle agglomeration and viscous wall are effectively inhibited, mass-and heat-transfer efficiency is enhanced, improves production efficiency.
It is an object of the present invention to provide a kind of circulating fluidized bed system for Fluorspar Powder production hydrogen fluoride, packets
Include: reactor is made of more than direct tube section, direct tube section expanding reach, direct tube section undergauge section below and closing heating shell；
Cyclic part, primary cyclone, solid settling section after being exported by gas reactor are connected to reactor air inlet pipe
Control valve and lagging casing in inclined tube section, inclined tube are constituted；Solid segregation section is received by secondary cyclone and solid
Tank is constituted；Gas condensation portion, by condenser, Liquid acquisition tank is constituted.Reaction mass by enter below reactor reactor into
Row reaction enters cyclic part later and isolates solid reactant.The solid retention time of high conversion rate is long, wears tighter
Weight, partial size is smaller, leaves cyclic part above primary cyclone with gas phase reaction material and enters solid segregation section, and
Both ends are descended to respectively obtain gas-particle two-phase product on it after secondary cyclone separates.Gas-phase product is after condenser condenses
It is received by Liquid acquisition tank, solid product enters solid receiving tank.The isolated reaction mass of cyclic part passes through from lower part
Control valve enters the air inlet pipe of reactor lower end and make-up gas is mixed into reactor cycles and reacts.Solid is supplemented from circulation
Supplement is added in part.Above-mentioned reaction mass includes inert filler and reaction raw materials etc.；Make-up gas and supplement solid, including need
Inert filler and reaction raw materials of supplement etc..Wherein reaction raw materials refer to that Fluorspar Powder, sulfuric acid vapor or sulfur trioxide and vapor are mixed
Close gas.
In solid segregation section of the invention, counterbalance valve can be installed additional above solid receiving tank, made in secondary cyclone
Deposition solid passes through by phased manner, reduces solid and receives pressure inside the tank.
System according to the present invention, a second object of the present invention is to provide a kind of sides of Fluorspar Powder production hydrogen fluoride
Method comprising following steps:
1) make the reaction gas with solid circle enter reactor part to be reacted, output is with reaction is not solid completely
The reaction product of body.
2) reaction product with unreacted solid of output enters cyclic part above above-mentioned reactor, isolates partial size
Biggish incomplete reaction solid particle enters solid settling section, and gas and the smaller solid particle of high conversion rate enter solid
Segregation section.Solid control valve by lower diagonal and thereon into solid settling section enters air inlet pipe and reaction gas is mixed
Conjunction is recycled back to reactor.
3) the smaller solid particle of above-mentioned cyclic part is isolated gas and high conversion rate enters the two of solid segregation section
Grade cyclone separator, upper and lower ends distinguish isolated gas-solid phase reaction product, and gas-phase product enters condensation portion.
4) above-mentioned isolated gas phase reaction product enters Liquid acquisition tank after entering condenser condensation.
The method of Fluorspar Powder production hydrogen fluoride of the present invention, the reaction condition of reactor, used reaction raw materials
Type and its dosage, specific as follows:
The present invention uses reaction raw materials, and sulfuric acid vapor or sulfur trioxide and vapor mixed gas are selected in reactor air inlet
At least one of two kinds.The sulfur trioxide and vapor gaseous mixture or 95% or more mass fraction of preferred molar ratio 4:1-1:4
Sulfuric acid vapor.Inert gas can be added into air inlet with reduce sulfuric acid vapor or sulfur trioxide and vapor gaseous mixture divide with
Reaction temperature needed for reducing.Nitrogen, hydrogen fluoride gas etc., preferred fluorinated hydrogen, and mole fraction may be selected in inert gas
30% or less.Inert gas content is excessively high to reduce reaction rate.
30-200 μm of Fluorspar Powder average grain diameter, preferably 50-100 μm used in the present invention.Calcium Fluoride Content is greater than in Fluorspar Powder
80%, preferably 90% or more high-purity calcirm-fluoride.
Above-mentioned steps 1) in, 170-400 degrees Celsius of reactor operation temperature, 250-350 degrees Celsius of preferable temperature；Operation pressure
Power is 0.5-2bar, preferably 0.8-1.2bar；The preferred 0.9-0.12m/s of operating gas velocity 0.07-0.15m/s.
Above-mentioned steps 2) in, cyclic part primary cyclone operating pressure 0.5-2bar, preferably 0.7-1.1bar；Gu
Body settling section operating pressure 0.5-2bar, preferably 0.7-1.1bar.Inclined tube and 30-70 ° of horizontal interfacial angle, preferably 50-60 °,
Upper and lower ends difference in height is greater than 10cm.Control valve aperture 0.1-0.7, preferably 0.3-0.5 on inclined tube press predetermined amount of flow with solid
Solid deposition section, which will not be entered, by gas is advisable.
Above-mentioned predetermined amount of flow is reaction solid enters solid deposition section flow plus benefit from primary cyclone completely
Fill Fluorspar Powder amount of solid.Above-mentioned supplement Fluorspar Powder amount of solid, which is equal in step 3), isolates 0.9-1.2 times of amount of solid, preferably 1-
1.1 again.
Above-mentioned steps 3) in, cyclic part primary cyclone operating pressure；Solid receiving tank operating pressure 0.5-
2bar, preferably 0.7-1.05bar.
Above-mentioned steps 4) in, condenser is divided into two sections, cooling using cooling water and chilled brine respectively.Or cooling is used only
Water, wherein second segment cooling water temperature is lower than 15 degrees Celsius.
There are two types of schemes according to unstrpped gas type difference is used for above-mentioned shell of reactor.One preferred embodiment is to select sulphur
Acid vapor is as unstripped gas, installs closing heating shell needed for needing additional amount of heat to provide reaction, outside reactor additional, uses electricity
Heating.Another preferred embodiment is to select sulfur trioxide and vapor gaseous mixture as unstripped gas, and heat needed for reacting is by sulfur trioxide
It being reacted with water and sulfuric acid heat release offer is provided, additional closing heating shell can be changed to lagging casing or still use closing heating shell,
Use electrical heat tracing.
Using method of the invention, high-purity anhydrous hydrogen fluoride can be produced.
The present invention has the characteristics that prominent and effect as follows compared with prior art:
1, solid-phase reactant quickly flows in reactor, avoids the appearance that agglomerate glues the abnormal phenomenon such as wall, improves
Mass transfer, heat transfer efficiency, being capable of the effectively save energy.
2, the Fluorspar Powder of different-grain diameter being separated using cyclone separator, the large-sized residence time is short, and conversion ratio is low, into
Enter cyclic part to be recycled；The degree of wear of small particle is high, and the residence time is long, and conversion ratio is also high, close to reaction completely, enters
Solid segregation section isolates system as solid reaction product.It is tired to solve the existing reaction late phase reaction of other techniques in this way
Difficulty, the problem of reaction time length.It can be fluidized simultaneously by control valve aperture control loop on control tolerance size and inclined tube
The cycling rate of bed controls the solid product ratio isolated to control solid reaction degree.
3, liquid condensation is controlled by condensate temperature and dosage, causes to contain in gaseous product when charging proportion is led to the problem of
Product quality can be controlled by installing multi-stage condensing device additional when other impurities by having.
Detailed description of the invention
Fig. 1 is the circulating fluidized bed device schematic diagram that Fluorspar Powder of the present invention produces hydrogen fluoride；
Description of symbols:
1 reactor, 2 primary cyclones, 3 solids deposition section, 4 inclined tubes, 5 control valves, 6 secondary cyclones, 7
Counterbalance valve, 8 solid receiving tanks, 9 condensers, 10 Liquid acquisition tanks.
Specific embodiment
Following embodiment is the range being not intended to limit the present invention in order to further illustrate the present invention.
Reaction gas with solid circle enters 1 reactor and is reacted, and output is anti-with incomplete reaction solid
Product is answered to enter cyclic part, 2 primary cyclones isolate the biggish incomplete reaction solid particle of partial size into 3 solids
Settling section, and gas and the smaller solid particle of high conversion rate enter solid segregation section.Solid into solid settling section passes through
4 inclined tube of lower section and 5 control valves thereon enter air inlet pipe and reaction gas mixing circulation returns reactor.Cyclic part is isolated
Gas and the smaller solid particle of high conversion rate enter 6 secondary cyclones of solid segregation section, upper and lower ends are divided respectively
From gas-solid phase reaction product is obtained, gas-phase product enters condensation portion, and solid product enters 8 solid receiving tanks by 7 counterbalance valves.
Gas phase reaction product enters 10 Liquid acquisition tanks after entering the condensation of 9 condensers.
Embodiment 1
It is Celsius to be previously heated to 300 as unstripped gas for sulfur trioxide, vapor and the HF gaseous mixture of molar ratio 1:1:1.5
Degree, with 10.0m3/ h gas velocity enters reactor air inlet pipe, is mixed into reactor with solid circle and is reacted.Reactor operation
350 degrees Celsius of temperature, pressure 1.2bar.Output enters cyclic part with the reaction product of not reaction solid completely, into level-one
Cyclone separator isolates the biggish incomplete reaction solid particle of partial size.Primary cyclone pressure drop 0.05bar.Sink solid
Body enters solid settling section, and gas and the smaller solid particle of high conversion rate enter solid segregation section.Into solid settling section
Solid control valve by lower diagonal and thereon enter air inlet pipe and reaction gas mixing circulation returns reactor.Inclined tube is long
25cm, upper and lower ends difference in height 20cm.The smaller solid particle of gas and high conversion rate that cyclic part is isolated enters solid
The secondary cyclone of segregation section, secondary cyclone pressure drop 0.05bar.Its upper and lower ends distinguishes isolated gas-solid phase
Reaction product, gas-phase product enter condensation portion, and solid product enters solid receiving tank by counterbalance valve.Gas phase reaction product into
Enter Liquid acquisition tank after entering condenser condensation.Condenser is condensed to obtain hydrogen fluoride liquid using 5 degrees Celsius of chilled brines.
Using 35 μm of average grain diameter, the Fluorspar Powder of Calcium Fluoride Content 94% adds below solid settling section as supplement solid
Enter.It is 5.42kg/min that it, which supplements flow,.
It obtains containing calcirm-fluoride 0.8% in solid product, contains 90% or more hydrogen fluoride in the condensate liquid of gaseous product.
Embodiment 2
The sulfuric acid vapor and HF gas of mass fraction 98% are mixed using molar ratio 1:1.5 as unstripped gas, are previously heated to
350 degrees Celsius, with 8.0m3/ h gas velocity enters reactor air inlet pipe, is mixed into reactor with solid circle and is reacted.Reaction
350 degrees Celsius of device operation temperature, pressure 0.95bar.Tiny structure can reduce the leakage probability of hazardous reaction object and product.Reactor
Output with not completely reaction solid reaction product enter cyclic part, by primary cyclone isolate partial size compared with
Big does not react solid particle completely.Primary cyclone pressure drop 0.05bar.Sinking solids enter solid settling section, and gas
Body and the smaller solid particle of high conversion rate enter solid segregation section.Solid into solid settling section passes through lower diagonal and its
On control valve enter air inlet pipe and reaction gas mixing circulation and return reactor.The long 25cm of inclined tube, upper and lower ends difference in height
15cm.The smaller solid particle of gas and high conversion rate that cyclic part is isolated enters the second level cyclonic separation of solid segregation section
Device, secondary cyclone pressure drop 0.05bar.Its upper and lower ends distinguishes isolated gas-solid phase reaction product, gas-phase product into
Enter condensation portion, solid product enters solid receiving tank by counterbalance valve.Gas phase reaction product enters after entering condenser condensation
Liquid acquisition tank.One section of condenser uses 20 degrees Celsius of cooling waters, and two sections are successively condensed using 10 degrees Celsius of cooling waters, are obtained
To hydrogen fluoride liquid.
Using 30 μm of average grain diameter, the Fluorspar Powder of Calcium Fluoride Content 97% adds below solid settling section as supplement solid
Enter.It is 5.21kg/min that it, which supplements flow,.
It obtains containing calcirm-fluoride 0.8% in solid product, contains 90% or more hydrogen fluoride in the condensate liquid of gaseous product.
Claims (9)
1. a kind of circulating fluidized bed system with Fluorspar Powder production hydrogen fluoride, comprising:
1) reactor, by expanding reach, direct tube section undergauge section below and closing heating shell structure more than direct tube section, direct tube section
At undergauge section has the internal diameter being gradually reduced downwards, and is equipped with air inlet pipe in its bottom, and entire reactor is outer by closing heating
Shell is isolated from the outside, and expanding reach side has outlet for connecting cyclic part；
2) cyclic part, by primary cyclone, solid settling section, the inclined tube section for being connected to reactor air inlet pipe, inclined tube
Control valve and lagging casing constitute, primary cyclone import is connected with reactor expanding reach side exit, solid
Settling section is the straight tube that one side is equipped with solid supplement adapter tube, solid settling section upper end and primary cyclone outlet at bottom phase
Even, lower end is connected with inclined tube section, and inclined tube section is connected with the air inlet pipe side wall of reactor undergauge section bottom；Entire cyclic part by
Lagging casing cladding；
3) solid segregation section is made of secondary cyclone and solid receiving tank, and secondary cyclone entrance and level-one are revolved
Wind separator top exit is connected, and solid receiving tank is connected with secondary cyclone outlet at bottom, and solid segregation section separates gas
Gu two-phase product, and the solid of fully reacting is collected, as solid product；
4) gas condensation portion, by condenser, Liquid acquisition tank is constituted, and gas condensation portion will separate remaining in solid segregation section
Gas-phase product out liquefies and collects.
2. a kind of method of the Fluorspar Powder production hydrogen fluoride using system described in claim 1, it is characterised in that including following step
It is rapid:
1) make the reaction gas with solid circle enter reactor to be reacted, output is with the not reaction of reaction solid completely
Product；
2) reaction product with not reaction solid completely of output enters cyclic part, one cyclonic point above above-mentioned reactor
The biggish incomplete reaction solid particle of partial size is isolated from device, into solid settling section, and gas and high conversion rate is smaller
Solid particle enters solid segregation section, into solid settling section solid by lower diagonal and control valve thereon into
Tracheae and reaction gas mixing circulation return reactor；
3) the smaller solid particle of cyclic part is isolated gas and high conversion rate enters the second level whirlwind point of solid segregation section
From device, upper and lower ends respectively obtain gas-solid phase reaction product, and gas-phase product enters condensation portion, and solid phase reaction product enters solid
Receiving tank；
4) the isolated gas phase reaction product of above-mentioned secondary cyclone enters Liquid acquisition tank after entering condenser condensation.
3. method according to claim 2, it is characterised in that: in step 1), 170-400 degrees Celsius of reactor operation temperature,
Operating pressure 0.5-2 bar, operating gas velocity 0.07-0.15 m/s.
4. method according to claim 2, it is characterised in that: in step 1), 250-350 degrees Celsius of reactor operation temperature,
Operating pressure 0.8-1.2 bar, operating gas velocity 0.9-0.12 m/s.
5. method according to claim 2, it is characterised in that: in step 2, cyclic part primary cyclone operation pressure
30-70 ° of power 0.5-2 bar, solid settling section operating pressure 0.5-2 bar, inclined tube and horizontal interfacial angle, upper and lower ends height
Difference is greater than 10 cm, control valve aperture 0.1-0.7 on inclined tube.
6. method according to claim 2, it is characterised in that: in step 2, cyclic part primary cyclone operation pressure
Power 0.7-1.1 bar；50-60 ° of solid settling section operating pressure 0.7-1.1 bar, inclined tube and horizontal interfacial angle, upper and lower ends
Difference in height is greater than 10 cm, control valve aperture 0.3-0.5 on inclined tube.
7. method according to claim 2, it is characterised in that:
Reactor predetermined amount of flow is not react solid completely to enter solid settling section flow plus supplement from primary cyclone
Fluorspar Powder amount of solid, above-mentioned supplement Fluorspar Powder amount of solid are equal to secondary cyclone lower part in step 3) and obtain solid reaction production
0.9-1.2 times of object amount.
8. method according to claim 2, it is characterised in that: select sulfuric acid vapor as unstripped gas.
9. method according to claim 2, it is characterised in that: select sulfur trioxide and vapor gaseous mixture as unstripped gas,
Heat needed for reaction, which is reacted by sulfur trioxide with water, generates sulfuric acid heat release offer.
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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 |
| CN108910826B (en) * | 2018-10-17 | 2019-12-24 | 杨松 | Circulating fluidized bed reaction furnace for preparing hydrogen fluoride |
| CN109019517A (en) * | 2018-10-17 | 2018-12-18 | 杨松 | A kind of application method preparing hydrogen fluoride recirculating fluidized bed reacting furnace |
| CN109260742B (en) * | 2018-10-17 | 2021-06-04 | 杨松 | Use method of circulating fluidized bed rectification device for preparing hydrogen fluoride |
| CN108975275B (en) * | 2018-10-17 | 2020-01-31 | 杨松 | reaction device for preparing hydrogen fluoride |
| CN108910827B (en) * | 2018-10-17 | 2020-01-03 | 杨松 | Process device for preparing hydrogen fluoride |
| CN109250688B (en) * | 2018-10-17 | 2020-03-24 | 杨松 | Degassing device of circulating fluidized bed for preparing hydrogen fluoride |
| CN112142009A (en) * | 2020-09-22 | 2020-12-29 | 宜章弘源化工有限责任公司 | Method and equipment for producing anhydrous hydrogen fluoride |
| CN113262750B (en) * | 2021-07-19 | 2021-11-02 | 联仕(昆山)化学材料有限公司 | Electronic-grade hydrofluoric acid production device |
| CN115722158B (en) * | 2022-11-28 | 2024-07-16 | 兰州理工大学 | Multilayer expansion fluidized bed reactor system and process for producing hydrogen fluoride |
| CN115990439B (en) * | 2022-11-28 | 2024-07-23 | 兰州理工大学 | Anhydrous hydrogen fluoride production equipment and process based on expansion fluidized bed |
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