CN115722158A - Multilayer expanded fluidized bed reactor system and process for producing hydrogen fluoride - Google Patents
Multilayer expanded fluidized bed reactor system and process for producing hydrogen fluoride Download PDFInfo
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- CN115722158A CN115722158A CN202211502940.1A CN202211502940A CN115722158A CN 115722158 A CN115722158 A CN 115722158A CN 202211502940 A CN202211502940 A CN 202211502940A CN 115722158 A CN115722158 A CN 115722158A
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910000040 hydrogen fluoride Inorganic materials 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000008569 process Effects 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 97
- 239000007789 gas Substances 0.000 claims abstract description 72
- 239000002245 particle Substances 0.000 claims abstract description 57
- 239000002253 acid Substances 0.000 claims abstract description 33
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 28
- 239000007853 buffer solution Substances 0.000 claims abstract description 25
- 239000010436 fluorite Substances 0.000 claims abstract description 25
- 239000000872 buffer Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000007664 blowing Methods 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 19
- 239000003599 detergent Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 2
- 238000005054 agglomeration Methods 0.000 abstract description 9
- 230000002776 aggregation Effects 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 24
- 229910001634 calcium fluoride Inorganic materials 0.000 description 6
- 229910004261 CaF 2 Inorganic materials 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000005243 fluidization Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 MgO Chemical class 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
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Abstract
The invention provides a multilayer expanded fluidized bed reactor system for producing hydrogen fluoride, which comprises a multilayer expanded fluidized bed, a cyclone separator, a washing tower and a mixed acid buffer tank, wherein the multilayer expanded fluidized bed is connected with the washing tower through a pipeline; the multilayer expanded fluidized bed comprises a top buffer zone, an upper layer reaction section and a lower layer reaction section, wherein the top buffer zone is connected with a cyclone separator, and the bottom end of the cyclone separator is connected with the lower layer reaction section; the top end of the cyclone separator is connected with a washing tower, the bottom end of the washing tower is connected with a mixed acid buffer tank, and the mixed acid buffer tank is connected with a mixed acid return inlet through a pipeline; also included is a multilayer expanded fluidized bed reactor process for producing hydrogen fluoride using the above system, the process comprising: reacting fluorite with high-temperature feed gas, blowing and drying the high-temperature feed gas to generate product particles, and washing the generated gas by a washing tower to obtain a crude HF product and mixed acid. The invention reduces the water content in the fluidized bed to the utmost extent, thereby avoiding the agglomeration and wall sticking of product particles and improving the mass transfer and heat transfer efficiency.
Description
Technical Field
The invention relates to the technical field of fluorine chemical industry, in particular to a multilayer expansion fluidized bed reactor system and a process for producing hydrogen fluoride.
Background
The hydrogen fluoride is an important fluorine chemical basic product and raw material, and is widely applied to the industries of electronics, chemical industry, petroleum, metallurgy and the like. Fluorite is the main raw material for producing hydrogen fluoride, and the reaction device is one of key devices for producing hydrogen fluoride products.
For a long time, the reaction device for producing hydrogen fluoride is mainly a rotary kiln process, and is mainly obtained by reacting fluorite and sulfuric acid, and the main reaction is as follows: caF 2 +H 2 SO 4 →CaSO 4 +2HF. The reaction is a liquid-solid endothermic reaction process that requires external heat supply. Therefore, the rotary kiln apparatus requires a long barrel, a corrosion-proof housing, a heating device, a drum driving device, and the like to ensure sufficient mixing reaction of the liquid-solid reactants and required reaction heat.
US patent 3282644 proposes increasing SO 3 Gas-phase fed stirred gas-liquid-solid reaction apparatus, passing SO 3 The reaction with water provides heat and excess H to the reactor 2 SO 4 And (4) atmosphere. The exothermic reaction was as follows: SO 3 +H 2 O→H 2 SO 4 . US patent 4120939 further proposes a free fall gas-liquid-solid reactor, in which fluorite raw material freely falls from the upper part of the reactor and liquid H 2 SO 4 Spraying SO from the middle of the reactor 3 And HF gas enters the reactor from the bottom, and the reaction is promoted by controlling the particle size and the descending speed of the particles. The requirement on the sphericity and the fluidity of fluorite particles and calcium sulfate/fluorite composite particles is extremely high, otherwise agglomeration and short circuit are easily caused, and the conversion rate is reduced and even the system is crashed.
In order to improve the particle fluidization and interlayer transfer effect in the gas-solid fluidized bed reactor, the layered fluidization characteristic of fluorite particles is combined, namely the upper layer can be well fluidized, and the fluorite particles on the lower layer can not be fluidized due to bonding agglomeration to form a fixed bed; chinese patent CN107159066 proposes a spouted fluidized bed-fluidized bed composite reaction device so as to improve the problem of agglomeration of lower-layer particles in layered fluidization of fluorite particles. Chinese patent CN107311109 proposes a circulating fluidized bed process, on one hand, the fluidization air velocity is improved to inhibit the agglomeration and wall sticking of particles; on the other hand, the gas-solid contact time is shortened, the fluorite enters a settler for sedimentation after rapid reaction, and then is circulated and refluxed into the fluidized bed for continuous reaction. The rapid reaction can keep higher sulfuric acid concentration, avoids the problem that the reaction rate is greatly slowed down due to insufficient sulfuric acid in the later reaction period, and can effectively improve the production efficiency. Chinese patent CN108910826 also proposes a similar circulating fluidized bed reactor, using H 2 SO 4 Feeding, wherein fluorite is required to be crushed into 3-5 mm particles. In fact, as the reaction gradually proceeds, solid particles are gradually converted from calcium fluoride into calcium sulfate with a larger molecular weight, and in addition, water and sulfuric acid wrap the particles due to the addition of water vapor, so that the adhesive force between the particles is remarkably increased, the phenomena of adhesion and agglomeration occur, the agglomeration affects the heat transfer and reaction effects of the raw materials, and finally the utilization rate of the raw materials is affected.
Accordingly, a multilayer expanded fluidized bed reactor system and process for producing hydrogen fluoride is provided to address the above-mentioned problems.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a multilayer expanded fluidized bed reactor system and a process for producing hydrogen fluoride, aiming at the defects of the prior art, wherein in the multilayer expanded fluidized bed, on one hand, the particle retention time is adjusted by the multilayer expanded fluidized bed structure, and the raw material reaction efficiency is improved; on the other hand, the feeding mode is controlled to reduce the local moisture content in the fluidized bed to the maximum extent, thereby avoiding the agglomeration and wall sticking of product particles and improving the mass transfer and heat transfer efficiency; the circulation of the mixed acid also takes H into consideration 2 SO 4 In the flowThe excessive raw material in the fluidized bed and the recycling rate of the raw materials can effectively improve the production efficiency.
In order to solve the technical problems, the invention adopts the technical scheme that: a multilayer expanded fluidized bed reactor system for producing hydrogen fluoride comprises a multilayer expanded fluidized bed, a cyclone separator, a washing tower and a mixed acid buffer tank; the multilayer expanded fluidized bed comprises a top buffer zone, an upper layer reaction section and a lower layer reaction section, wherein the top buffer zone is connected with the upper end of the side wall of the cyclone separator, the bottom end of the cyclone separator is connected with the lower layer reaction section, and the side wall of the lower layer reaction section is provided with a mixed acid return inlet; the top end of the cyclone separator is connected with the washing tower, the bottom end of the washing tower is connected with the mixed acid buffer tank, and the mixed acid buffer tank is connected with the mixed acid return inlet through a pipeline.
Preferably, the lower end of the top buffer zone is connected with the upper layer reaction section, and the lower end of the upper layer reaction section is connected with the lower layer reaction section through a necking section; and a steam feeding pipe is arranged on the side wall of the neck section.
Preferably, a solid particle feeding pipe is arranged on the side wall of the upper reaction section; the lower extreme of lower floor's reaction section is provided with the export of product residue, the bottom of lower floor's reaction section is provided with gas feed inlet.
Preferably, the bottom end of the cyclone separator is connected with a settling section, the bottom end of the settling section is connected with an inclined tube, and the inclined tube is connected with the lower-layer reaction section; the angle of the included angle between the inclined tube and the horizontal plane is 30-75 degrees.
Preferably, a cold acid feeding and spraying device is arranged at the upper end in the washing tower; and a reboiler and an adjusting valve are arranged on a pipeline between the mixed acid buffer tank and the mixed acid return inlet.
There is also provided a multilayer expanded fluidized bed reactor process for producing hydrogen fluoride using the above system, characterized in that the process comprises the steps of:
s1, reacting fluorite and high-temperature raw material gas in the upper-layer reaction section to generate product particles and mixed gas I, enabling the product particles to enter the lower-layer reaction section to continuously react with excessive high-temperature raw material gas, and blowing and drying the product particles by the high-temperature raw material gas;
s2, the mixed gas obtained in the S1 enters a cyclone separator through a top buffer zone, a second mixed gas and incompletely reacted small particle solids are separated, and the incompletely reacted small particle solids are sent back to the lower layer reaction section for continuous reaction;
and (3) introducing the mixed gas II separated in the S3 and the S2 into the washing tower to be washed by a detergent to obtain crude hydrogen fluoride gas and mixed acid, introducing the mixed acid into the mixed acid buffer tank, and then sending the mixed acid back to the lower layer reaction section to react with the dried product particles.
Preferably, the temperature of the high-temperature feed gas in the S1 is more than or equal to 280 ℃; the reaction temperature is 200-400 ℃, and the pressure is 50-200 kPa.
Preferably, the high-temperature raw material gas in S1 is high-temperature concentrated sulfuric acid gas flow or, SO 3 Gas and water vapor; the flow rate of the fluorite is 6275-6325 kg/h, and the average grain diameter is 50-100 mu m; the high temperature concentrated sulfuric acid gas stream contains 20% by weight of SO 3 (ii) a The SO 3 Feeding of steam with SO in gas and steam 3 The molar ratio of the gas feeds was 1.
Preferably, the pressure drop of the cyclone in S2 is between 0.08 and 0.1bar.
Preferably, the detergent in S3 is 98% wt sulfuric acid; the operation pressure of the washing tower and the mixed acid buffer tank is 50-200 kPa.
Compared with the prior art, the invention has the following advantages:
1. the process of the invention ensures that the solid phase raw material (fluorite) has enough residence time in the multilayer expanded fluidized bed, but avoids the phenomenon that the solid phase raw material is bonded and agglomerated in the lower reaction section to ensure that the fixed bed cannot be fluidized.
2. The process of the invention adopts high-temperature raw material gas to promote the drying of the produced solid product particles, avoids the phenomena of viscosity and agglomeration, is easy to expand and break, improves the mass transfer, heat transfer and reaction efficiency in the multilayer expanded fluidized bed, and promotes the complete conversion of fluorine resources in fluorite.
3. According to the invention, the cyclone separator, the washing tower, the mixed acid buffer tank and other devices promote the circulation reaction of incompletely reacted particles, the product particles do not become dust, and the environmental protection and the safety of downstream devices of the device are ensured; on the other hand, the excessive SO is recycled 3 And H 2 SO 4 And the overall raw material utilization rate is improved.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
FIG. 1 is a schematic diagram of the system of the present invention.
Description of reference numerals:
1-multilayer expanded fluidized bed; 2-lower reaction section; 3-steam feed pipe; 4-a necking section; 5-upper reaction section; 6-solid particle feeding pipe; 7 — top buffer; 8, a cyclone separator; 9-a settling section; 10-inclined tube; 11-cold acid feed spray system; 12-a washing column; 13-mixed acid buffer tank; 14-a reboiler; 15-adjusting valve; 16-mixed acid return inlet; 17-gas feed inlet; and 18, a product residue outlet.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
The multilayer expanded fluidized bed reactor system for producing hydrogen fluoride in the embodiment comprises a multilayer expanded fluidized bed 1, a cyclone separator 8, a washing tower 12 and a mixed acid buffer tank 13; the multilayer expanded fluidized bed 1 comprises a top buffer zone 7, an upper layer reaction section 5 and a lower layer reaction section 2, wherein the lower end of the top buffer zone 7 is connected with the upper layer reaction section 5, and the upper layer reaction section 5 is connected with the lower layer reaction section 2 through a necking section 4; the top end of the top buffer zone 7 is connected with the upper end of the side wall of the cyclone separator 8, the bottom end of the cyclone separator 8 is connected with a settling section 9, the bottom end of the settling section 9 is connected with an inclined tube 10, and the inclined tube 10 is connected with the lower layer reaction section 2; a mixed acid return inlet 16 is formed in the side wall of the lower reaction section 2; the top end of the cyclone separator 8 is connected with the lower end of the side wall of the washing tower 12, the bottom end of the washing tower 12 is connected with the mixed acid buffer tank 13, and the mixed acid buffer tank 13 is connected with the mixed acid return inlet 16 through a pipeline; a reboiler 14 and an adjusting valve 15 are arranged on a pipeline between the mixed acid buffer tank 13 and the mixed acid return inlet 16;
a solid particle feeding pipe 6 is arranged on the side wall of the upper layer reaction section 5; a product residue outlet 18 is formed in the lower end of the side wall of the lower reaction section 2, and a gas feed inlet 17 is formed in the bottom end of the lower reaction section 2; the included angle between the inclined tube 10 and the horizontal plane is 30-75 degrees; a cold acid feeding and spraying device 11 is arranged at the upper end in the washing tower 12; a steam feeding pipe 3 is arranged on the side wall of the neck section 4;
in this embodiment, the diameters of the upper reaction section 5 and the lower reaction section 2 are the same, and the diameter ratio of the upper reaction section 5 to the neck section 4 is (1-4): 1; the heights of the upper reaction section 5, the lower reaction section 2 and the top buffer zone 7 account for 30-90% of the total height of the multilayer expanded fluidized bed 1. The height of the mixed acid return inlet 16 is 10-95% of the height of the lower reaction section 2.
Example 2
This example uses the system of example 1 to produce a multilayer expanded fluidized bed reactor process for hydrogen fluoride comprising the steps of:
s1, introducing fluorite into an upper reaction section 5 of the multilayer expanded fluidized bed 1 from a solid particle feeding pipe 6; introducing a high-temperature concentrated sulfuric acid gas flow with the temperature of 300 ℃ into the multilayer expanded fluidized bed 1 from the gas feed inlet 17 at the gas speed of 36.5 kmol/h; in the upper reaction section 5, the fluorite and the high-temperature concentrated sulfuric acid gas flow react under the conditions that the pressure is 140kPa and the temperature is 300 ℃ to generate product particles and mixed gas I, and the product particles enter the lower reaction section 2 through a neck section 4 to continue to react with the excessive high-temperature concentrated sulfuric acid gas flow; simultaneous SO in high temperature concentrated sulfuric acid gas stream 3 Blowing the product particles with a gas stream, drying the product particles, and the SO 3 Reaction of gas stream with moisture to produce H 2 SO 4 To obtain completely reacted product particles;
the fluorite comprises CaF 2 、CaCO 3 Metal oxides such as MgO, fe 2 O 3 The content of calcium fluoride in the fluorite is 97%, the average particle size is 100 mu m, and the flow rate is 6275kg/h; the high temperature concentrated sulfuric acid gas stream, which contains 20% by weight of SO, is produced from 105 acid 3 ；
The main reaction in S1 is as follows: caF 2 +H 2 SO 4 ＝CaSO 4 +2HF
SO 3 +H 2 O＝H 2 SO 4
The product particles are reaction residues, mainly comprising CaSO 4 、SiO 2 Incompletely reacted CaF 2 And is entrained with H 2 O、H 2 SO 4 Said CaSO 4 The content of calcium fluoride is less than 0.8 percent, and H 2 SO 4 The content of (A) is less than 1.5%; the first mixed gas comprises HF and SiF 4 、CO 2 、H 2 O and unreacted H 2 SO 4 And carrying small particulate solids;
the mixed gas obtained in the S2 and the S1 enters a cyclone separator 8 with the pressure drop of 0.1bar through a top buffer zone 7, secondary mixed gas and incompletely reacted small particle solid are separated, and the incompletely reacted small particle solid is sent back to the lower layer reaction section 2 for continuous reaction;
introducing the mixed gas II separated in the S3 and the S2 into the washing tower 12 at the pressure of 140kPa, washing by using sulfuric acid with the weight percent of 98% to obtain crude hydrogen fluoride gas and mixed acid, introducing the mixed acid into the mixed acid buffer tank 13 at the pressure of 140kPa, returning the mixed acid into the lower reaction section 2 through the reboiler 14 and the regulating valve 15, and reacting with the product particles blown and dried in the S1; the opening degree of the regulating valve 15 is 0.2-0.7;
the scrubber 12 is used for reducing the temperature of the second mixed gas and removing H in the second mixed gas 2 SO 4 、SO 3 、H 2 O and trace amounts of dust; the mixed acid mainly comprises H 2 SO 4 。
Through detection, the content of HF in the crude hydrogen fluoride gas is 91%, and the crude hydrogen fluoride gas contains HF and SiF 4 、CO 2 And SO 2 。
In this embodiment, the reaction temperature may be 200 ℃, 360 ℃ or 400 ℃, and the pressure may be 50kPa, 100kPa or 200kPa; the operating pressure of the scrubber 12 and the mixed acid buffer tank 13 may also be 50kPa, 100kPa, or 200kPa.
Example 3
This example uses the system of example 1 to produce a multi-layered expanded fluidized bed reactor process for hydrogen fluoride comprising the steps of:
s1, introducing fluorite into an upper reaction section 5 of the multilayer expanded fluidized bed 1 from a solid particle feeding pipe 6, and introducing water vapor into the multilayer expanded fluidized bed 1 through a water vapor feeding pipe 3; SO with the temperature of 280 DEG C 3 Gas enters the multilayer expanded fluidized bed 1 from a gas inlet 17 at a gas velocity of 0.2 m/s;
in the upper reaction section 5, the fluorite and SO 3 Gas and steam react under the conditions of 120kPa and 320 ℃ to generate product particles and mixed gas I, the product particles enter the lower reaction section 2 through a neck section 3 and react with high-temperature SO 3 Gas reaction, high temperature SO 3 Gas purging to dry the product particles;
the fluorite comprises CaF 2 、CaCO 3 Metal oxides such as MgO, fe 2 O 3 The content of calcium fluoride in the fluorite is 97%, the average particle size is 50 mu m, and the flow rate is 6325kg/h; the steam feed and SO 3 The molar ratio of the gas feeds was 1;
the principle in S1 is as follows: caF 2 +H 2 SO 4 ＝CaSO 4 +2HF
SO 3 +H 2 O＝H 2 SO 4
The product particles are reaction residues, mainlyTo include CaSO 4 、SiO 2 Incompletely reacted CaF 2 And is entrained with H 2 O、H 2 SO 4 Said CaSO 4 The content of calcium fluoride in the calcium fluoride is less than 0.8 percent, H 2 SO 4 The content of (A) is less than 1.5 percent; the first mixed gas comprises HF and SiF 4 、CO 2 、H 2 O and unreacted H 2 SO 4 ；
S2, the mixed gas obtained in the S1 enters a cyclone separator 8 with the pressure of 0.08bar through a top buffer zone 7, secondary mixed gas and incompletely reacted small particle solids are separated, and the incompletely reacted small particle solids are sent back to the lower layer reaction section 2 for continuous reaction;
s3, introducing the mixed gas obtained in the S2 into the washing tower 12 with the pressure of 120kPa and washing by using sulfuric acid with the weight of 98 percent to obtain crude hydrogen fluoride gas and mixed acid, introducing the mixed acid into the mixed acid buffer tank 13 with the pressure of 120kPa, and feeding the mixed acid back to the lower-layer reaction section 2 through a reboiler 14 and an adjusting valve 15 to react with the product particles obtained in the S1 to obtain completely reacted product particles; the temperature of the top of the washing tower 12 is 80 ℃, the temperature of the mixed acid is 160 ℃, and the opening degree of the regulating valve 15 is 0.2-0.7;
through detection, the content of HF in the crude hydrogen fluoride gas is 91%, and the crude hydrogen fluoride gas contains HF and SiF 4 、CO 2 And SO 2 。
In this embodiment, the reaction temperature may be 200 ℃, 300 ℃ or 400 ℃, and the pressure may be 50kPa, 100kPa or 200kPa; the operating pressure of the scrubber 12 and the mixed acid buffer tank 13 may also be 50kPa, 100kPa, or 200kPa.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (10)
1. A multilayer expanded fluidized bed reactor system for producing hydrogen fluoride is characterized by comprising a multilayer expanded fluidized bed (1), a cyclone separator (8), a washing tower (12) and a mixed acid buffer tank (13); the multilayer expanded fluidized bed (1) comprises a top buffer zone (7), an upper layer reaction section (5) and a lower layer reaction section (2), wherein the top buffer zone (7) is connected with the upper end of the side wall of the cyclone separator (8), the bottom end of the cyclone separator (8) is connected with the lower layer reaction section (2), and the side wall of the lower layer reaction section (2) is provided with a mixed acid return inlet (16); the top end of the cyclone separator (8) is connected with the washing tower (12), the bottom end of the washing tower (12) is connected with the mixed acid buffer tank (13), and the mixed acid buffer tank (13) is connected with the mixed acid return inlet (16) through a pipeline.
2. A multilayer expanded fluidized bed reactor system for producing hydrogen fluoride according to claim 1, characterized in that the lower end of the top buffer zone (7) is connected to the upper reaction section (5), and the lower end of the upper reaction section (5) is connected to the lower reaction section (2) through a neck section (4); and a steam feeding pipe (3) is arranged on the side wall of the necking section (4).
3. A multilayer expanded fluidized bed reactor system for producing hydrogen fluoride according to claim 2, characterized in that the upper reaction section (5) is provided with a solid particle feeding pipe (6) on its side wall; the lower end of the side wall of the lower layer reaction section (2) is provided with a product residue outlet (18), and the bottom end of the lower layer reaction section (2) is provided with a gas feed inlet (17).
4. A multilayer expanded fluidized bed reactor system for producing hydrogen fluoride according to claim 1, wherein a settling section (9) is connected to the bottom end of the cyclone (8), and an inclined tube (10) is connected to the bottom end of the settling section (9), and the inclined tube (10) is connected to the lower reaction section (2); the included angle between the inclined tube (10) and the horizontal plane is 30-75 degrees.
5. A multilayer expanded fluidized bed reactor system for producing hydrogen fluoride according to claim 1, characterized in that the upper end inside the scrubber tower (12) is provided with a cold acid feed spray device (11); a reboiler (14) and an adjusting valve (15) are arranged on a pipeline between the mixed acid buffer tank (13) and the mixed acid return inlet (16).
6. A multilayer expanded fluidized bed reactor process for producing hydrogen fluoride using the system of any one of claims 1 to 5, comprising the steps of:
s1, reacting fluorite and high-temperature raw material gas in the upper-layer reaction section (5) to generate product particles and mixed gas I, enabling the product particles to enter the lower-layer reaction section (2) to continuously react with excessive high-temperature raw material gas, and blowing and drying the product particles by the high-temperature raw material gas;
the mixed gas obtained in the S2 and the S1 enters a cyclone separator (8) through a top buffer zone (7) to separate out a mixed gas II and small particle solids which are not completely reacted, and the small particle solids which are not completely reacted are sent back to the lower layer reaction section (2) to continue to react;
and (3) introducing the mixed gas II separated in the S3 and the S2 into the washing tower (12) to be washed by a detergent to obtain crude hydrogen fluoride gas and mixed acid, introducing the mixed acid into the mixed acid buffer tank (13), and then sending the mixed acid back to the lower layer reaction section (2) to react with the product particles.
7. The process of claim 6, wherein the temperature of the high temperature feed gas in S1 is not less than 280 ℃; the reaction temperature is 200-400 ℃, and the pressure is 50-200 kPa.
8. The process of claim 6, wherein the high temperature feed gas in S1 is a high temperature concentrated sulfuric acid stream or, SO 3 Gas and water vapor; the flow rate of the fluorite is 6275-6325 kg/h, and the average grain diameter is 50-100 mu m; the high temperature concentrated sulfuric acid gas stream contains 20% by weight of SO 3 (ii) a The SO 3 Feeding of steam with SO in gas and steam 3 The molar ratio of the gas feeds was 1.
9. The multilayer expanded fluidized bed reactor process for the production of hydrogen fluoride according to claim 6, characterized in that the pressure drop of the cyclone (8) in S2 is 0.08-0.1 bar.
10. The process of claim 6, wherein the detergent in S3 is 98% wt sulfuric acid; the operation pressure of the washing tower (12) and the mixed acid buffer tank (13) is 50-200 kPa.
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| US3469939A (en) * | 1966-07-08 | 1969-09-30 | Daikin Ind Ltd | Process for manufacturing hydrogen fluoride |
| US4120939A (en) * | 1977-05-26 | 1978-10-17 | E. I. Du Pont De Nemours And Company | Hydrogen fluoride process |
| US4460551A (en) * | 1981-04-28 | 1984-07-17 | Buss Ag | Process and device for manufacturing synthetic anhydrous calcium sulphate and pure hydrofluoric acid |
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