CN115676851A - Method and device for preparing ammonium bifluoride from solid ammonium fluoride - Google Patents
Method and device for preparing ammonium bifluoride from solid ammonium fluoride Download PDFInfo
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- CN115676851A CN115676851A CN202211476157.2A CN202211476157A CN115676851A CN 115676851 A CN115676851 A CN 115676851A CN 202211476157 A CN202211476157 A CN 202211476157A CN 115676851 A CN115676851 A CN 115676851A
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- ammonium fluoride
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- mist
- ammonium bifluoride
- bifluoride
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- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 title claims abstract description 122
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000007787 solid Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 91
- 238000000926 separation method Methods 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 33
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 61
- 239000003595 mist Substances 0.000 claims description 40
- 239000002002 slurry Substances 0.000 claims description 37
- 239000000047 product Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000001802 infusion Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 4
- 239000011440 grout Substances 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 abstract description 12
- 239000011737 fluorine Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 53
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 8
- 229910017855 NH 4 F Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
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- 239000003960 organic solvent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- -1 ammonium fluorosilicate Chemical compound 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
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- 239000000706 filtrate Substances 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
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- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- 229910000976 Electrical steel Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
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- 150000002222 fluorine compounds Chemical class 0.000 description 1
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- 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
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- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention relates to the technical field of fluorine chemical industry, in particular to a method and a device for preparing ammonium bifluoride from solid ammonium fluoride, which are characterized in that the solid ammonium fluoride is adopted as a raw material, a saturated ammonium fluoride solution is prepared by adding water to dissolve the solid ammonium fluoride, ammonia gas is formed by heating and concentrating the saturated ammonium fluoride solution to realize partial decomposition of ammonium fluoride, the relative content of fluorine components in a solution system is increased, the relative content of ammonia components is reduced, an ammonium bifluoride product is formed, and the density of ammonium bifluoride in the solution can be 1.5g/cm in a big bag 3 Ammonium fluoride density of 1.11g/cm 3 And is close to 1.0g/cm of water 3 The characteristics of, realize centrifugal separation, obtain ammonium bifluoride product, the very big degree has reduced the degree of difficulty of ammonium bifluoride product production, has ensured the purity of ammonium bifluoride product, has reduced the water resource consumption of ammonium bifluoride product preparation in-process, has ensured fluorine element conversion rate, can realize fluorine element at whole system cycle conversion, reduce cost.
Description
Technical Field
The invention relates to the technical field of fluorine chemical industry, in particular to a method and a device for preparing ammonium bifluoride from solid ammonium fluoride.
Background
The ammonium bifluoride is white or colorless transparent orthorhombic crystal, is easy to deliquesce and agglomerate in air, and is easy to dissolve in water. The aqueous solution is strongly acidic and has the sour taste of hydrogen fluoride; slightly soluble in alcohol, decomposed in hot water, and sublimed at high temperature. The composite material is mainly used as a glass etching agent, a preservative, a beryllium oxide metal beryllium solvent, a chemical reagent, a boiler water supply system and steam generation system cleaning agent, a fermentation industry disinfectant, a silicon steel plate surface treating agent, an oxidant for manufacturing ceramics and aluminum-magnesium alloy, an organic synthetic fluorinating agent, an electroplating solution, a rare element extracting solvent, an oil field sandstone acidification treating agent and the like.
Ammonium acid fluorides are generally prepared by a liquid phase process, which is mainly due to: the gas phase method for producing the ammonium bifluoride is to react ammonia gas and hydrogen fluoride in a specific container, however, the reaction process has high requirements on equipment materials, large investment and high preparation cost, and if no special requirements exist, the gas phase method is not adopted usually, so that the process for preparing the ammonium bifluoride product by the liquid phase method is developed rapidly. At present, liquid phase methods are classified into a hydrogen fluoride-liquid ammonia method, a fluorosilicic acid-liquid ammonia method, a fluorine-containing waste liquid-liquid ammonia method, a hydrogen fluoride-ammonium fluoride solution method, and the like, depending on the raw materials used. For example: the patent No. 201310103008.6 discloses that ammonium fluoride is prepared into a saturated ammonium fluoride solution, then a hydrofluoric acid solution is added to react, after the reaction is completed, the ammonium bifluoride is prepared through vacuum concentration, crystallization and filtration, so that the purposes of shortening the flow and improving the purity of the ammonium bifluoride product are achieved. For another example: patent No. 201210046742.9 discloses that unsaturated ammonium fluoride solution is reacted with hydrofluoric acid to prepare an ammonium bifluoride product, so that the purposes of reducing energy consumption and improving product purity are achieved. For another example: 201810441726.7 discloses that introducing hydrogen fluoride into an ammonium bifluoride-ammonium fluoride solution to completely convert ammonium fluoride into ammonium bifluoride to obtain an ammonium bifluoride solution, concentrating and drying to obtain ammonium bifluoride, and resource recycling and high-value utilization are realized. For another example: the patent No. 201810947727.9 discloses a production process for producing an ammonium bifluoride product by reacting anhydrous hydrogen fluoride and ammonia in an organic solvent, and the preparation of ammonium bifluoride is realized by utilizing the difference of the solubilities of the anhydrous hydrogen fluoride, the ammonia and the ammonium bifluoride in the organic solvent, so that the obtained ammonium bifluoride powder has small granularity and high purity, and the organic solvent in the reaction process can be recycled; for another example: the patent numbers are: 201510943013.7 discloses that ammonium fluoride filtrate is vacuum-concentrated to obtain thick slurry, then the thick slurry is dissolved, hydrogen fluoride is used to adjust pH, cooling and crystallization are carried out to prepare ammonium bifluoride product, and the utilization rate of fluorine and ammonia is improved, so that the content of ammonium bifluoride in the obtained product reaches more than 99.58%.
Therefore, in the prior art, most of the ammonium bifluoride production is obtained by the interaction of the raw material containing an ammonium component or an ammonia component and hydrogen fluoride, so that after the acid with high corrosion performance, such as hydrogen fluoride, is added, the requirement on reaction equipment is high, and the preparation cost is high; the research on the production of ammonium bifluoride by directly using ammonium fluoride and water as raw materials is relatively few, but an ammonium fluoride solution is directly used as a raw material, and is concentrated at 85 ℃ in vacuum until the water content is less than 4%, and then dried to obtain a solid ammonium bifluoride product, such as: the disclosure of patent No. 200310104114.2, however, in the technical literature, the direct concentration-drying process is adopted to prepare the ammonium bifluoride product, which results in a purity of less than 98.5% and higher energy consumption in the concentration process.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a method and a device for preparing ammonium bifluoride from solid ammonium fluoride.
The method is realized by the following technical scheme:
one of the objects of the invention is to provide a method for preparing ammonium bifluoride from solid ammonium fluoride, which comprises the following steps:
s1: adding water to dissolve solid ammonium fluoride to prepare a saturated ammonium fluoride solution;
NH 4 F(s)+H 2 O→NH 4 F(l)
s2: concentrating the saturated ammonium fluoride solution, and performing mist-end separation to generate ammonia-containing gas and slurry;
2NH 4 F(l)→NH 4 HF 2 +NH 3 ↑+H 2 O(l)
s3: centrifugally separating the slurry to obtain ammonium bifluoride and ammonium fluoride solution;
s4: circularly sending the ammonium fluoride solution to the step S1 to dissolve solid ammonium fluoride; washing and drying the ammonium bifluoride to obtain an ammonium bifluoride product, and returning the washing liquid to the step S1 to dissolve solid ammonium fluoride; the ammonia-containing gas is used for preparing ammonium fluoride.
NH 4 F(l)+NH 4 F(s) → saturated NH 4 F(l)
Solid ammonium fluoride is adopted as a raw material, added with water to be dissolved to prepare a saturated ammonium fluoride solution, and then heated and concentrated to realize partial decomposition of ammonium fluoride to form ammonia gas, so that the relative content of fluorine components in a solution system is increased, the relative content of ammonia components is reduced, an ammonium bifluoride product is formed, and the density of the ammonium bifluoride is higher than that of ammonium fluoride (the density of the ammonium bifluoride is 1.5 g/cm) 3 Density of ammonium fluoride: 1.11g/cm 3 ) The characteristics of, ammonium bifluoride crystal forms the thick liquid after sinking, through centrifugal separation, obtains the ammonium bifluoride product, and the very big degree has reduced the degree of difficulty of ammonium bifluoride product production, has ensured the purity of ammonium bifluoride product, has reduced the water resource consumption of ammonium bifluoride product preparation in-process, has ensured fluorine element conversion rate, can realize fluorine element at whole system cycle conversion, reduce cost.
In order to realize the maximum conversion to produce ammonium bifluoride products and improve the conversion rate of ammonium bifluoride in one pass, preferably, in the step S2, the saturated ammonium fluoride solution is subjected to mist-end separation to produce ammonia-containing gas and slurry, the slurry is subjected to cyclic heating concentration, after the mist-end separation, ammonia-containing gas and low-concentration ammonium fluoride solution are produced, and the low-concentration ammonium fluoride solution is circularly sent to the step S1 to dissolve the solid ammonium fluoride.
More preferably, in step S2, after the saturated ammonium fluoride solution is concentrated, ammonia-containing gas and slurry are generated through mist-end separation, the slurry is circularly heated and concentrated, after the mist-end separation, ammonia-containing gas and low-concentration ammonium fluoride solution are generated, and the low-concentration ammonium fluoride solution is circularly sent to step S1 to dissolve the solid ammonium fluoride.
In the invention, the concentration is carried out under the condition that the vacuum degree is 0.04MPa and the temperature is increased to 50-70 ℃. Realize concentrating the ammonium fluoride solution under this condition, realize that the moisture converts steam into in the ammonium fluoride, then realize the formation of ammonium bifluoride to utilize and get into the separation of fog end in the fog end separation process, realize quick release, make gas escape upwards, liquid escapes downwards, and causes the temperature to descend through the pressure release, and the steam that the moisture produced is condensed and forms the water droplet circulation, and ammonia is then direct escape, has reduced water resource consumption rate.
In order to improve the purity of the ammonium bifluoride and ensure the yield of the ammonium bifluoride, preferably, the washing and drying are carried out by dissolving the ammonium bifluoride with normal-temperature water, reducing the temperature and concentrating the ammonium bifluoride to be less than 10 ℃, filtering to obtain an ammonium bifluoride filter cake and a washing liquid, and drying the ammonium bifluoride filter cake at 55 ℃ to obtain the ammonium bifluoride filter cake.
The invention provides a device for preparing ammonium bifluoride from solid ammonium fluoride, which comprises a dissolving tank and a mist-end separating tank, wherein a circulating liquid port and a charging port are formed in the side wall, close to the top end, of the dissolving tank; a liquid circulation port is formed in the side wall, close to the bottom, of the mist-end separation tank, a concentrated liquid port is formed in the side wall, close to the top, of the mist-end separation tank, a concentrator is arranged between the concentrated liquid port and the liquid circulation port, and a liquid pump is arranged between the concentrator and the liquid circulation port; the slurry discharge port is communicated with the slurry port through a pipeline; the centrifugal separator is connected with the bottom end of the liquid discharge port, a centrifugal slag outlet and a centrifugal liquid outlet are formed in the centrifugal separator, and a circulating pipe is arranged between the centrifugal liquid outlet and the circulating liquid port.
Dissolving solid ammonium fluoride by a dissolving tank, sending an ammonium fluoride solution in the dissolving tank into a mist end separating tank, in the ammonium fluoride solution concentrated by a concentrator, decomposing part of ammonium fluoride components into ammonia gas, and enabling a large amount of fluorine to remain in the liquid to form ammonium bifluoride, retaining the ammonium bifluoride in the liquid, and then circulating the ammonium bifluoride back into the mist end separator to release pressure to realize mist end separation, so that the mist end escapes upwards, the liquid falls downwards, and the gas (ammonia gas) remaining in the mist end is gradually exposed and escapes, so that the ammonia gas is separated, and an ammonium bifluoride product and a low-concentration ammonium fluoride solution are obtained along with centrifugal separation.
In order to facilitate recycling of the low-concentration ammonium fluoride solution, the circulating pipe is preferably provided with an infusion pump.
In order to facilitate the full conversion of ammonium fluoride into ammonium bifluoride, improve the yield of ammonium bifluoride and achieve the aim of gap treatment, preferably, a liquid conveying pump is arranged on a pipeline communicated between the slurry discharging port and the slurry port; a valve is arranged between the infusion pump and the grout outlet.
In order to accelerate the dissolution, preferably, a stirring component is arranged in the dissolving tank; in order to facilitate the dismantlement, change and overhaul, preferably, the stirring subassembly includes the (mixing) shaft, is located dissolving tank inner section be equipped with the stirring leaf on the (mixing) shaft, be equipped with the weeping hole on the stirring leaf, the stirring leaf with connect through the connector between the (mixing) shaft, the connector adopts the bolt straining fixed, just the connector with integrated into one piece between the stirring leaf.
In order to increase the probability of blocking the water vapor from entering the ammonia gas pipe when the water vapor formed in the condensation stage enters the mist separation tank to be depressurized and then cooled to form water drops, the top end of the inside of the mist separation tank is preferably provided with a conical baffle. More preferably, the ammonia pipe is vertically upwards installed for at least 1m, a cooler is arranged on the outer wall of the vertically upwards ammonia pipe, and the cooler can reduce the temperature in the ammonia pipe to be less than 5 ℃. The tail end of the ammonia pipe is connected with an ammonia gas absorption device or a device for preparing products such as ammonium fluosilicate and the like by taking ammonia gas as a raw material.
Compared with the prior art, the invention has the technical effects that:
(1) the invention has the advantages of simple process flow, simple required equipment, low treatment difficulty and low energy consumption, and greatly reduces the preparation cost of the ammonium bifluoride product.
(2) The device has the advantages of simple structure, convenient installation and low device cost, can realize the cyclic utilization of water resources, reduces the consumption of the water resources and improves the yield of ammonium bifluoride products.
(3) The invention is easy to be popularized and implemented in industrialization.
(4) Compared with the prior art documents, the method has the greatest difference that after dissolution, concentration under vacuum is adopted, and mist-end separation treatment is carried out, so that pressure relief and temperature reduction are realized to recover water vapor, the water vapor content when ammonia escapes is reduced, the water resource is recycled, the purity of the obtained ammonium bifluoride product is improved, the product qualification rate is improved, the product purity is over 99.3 percent, the quality is greatly improved, the energy consumption is reduced, and the production cost of the ammonium bifluoride is reduced.
Drawings
FIG. 1 is a schematic view of the inventive process.
FIG. 2 is a schematic process flow diagram of an alternative embodiment of FIG. 1.
FIG. 3 is a schematic process flow diagram of an alternative embodiment of FIG. 1.
Fig. 4 is a schematic structural diagram of the overall device of the present invention.
Fig. 5 is a schematic structural view of the stirring assembly of fig. 4.
1-dissolving tank 2-fog-powder separating tank 3-centrifugal separator 4-infusion pump 5-circulating pipe 6-liquid-infusion pump 7-concentrator 8-concentrated liquid port 9-baffle 10-ammonia pipe 11-slurry port 12-valve 13-slurry discharge port 14-charging port 15-stirring component 16-circulating liquid port 15.1-stirring shaft 15.2-connector 15.3-stirring blade 15.4-leakage hole 15.5-bolt.
Detailed Description
The technical solution of the present invention is further defined in the following description with reference to the accompanying drawings and the specific embodiments, but the scope of the claimed invention is not limited to the description.
As shown in fig. 1 and 4, in this example, a method for preparing ammonium bifluoride from solid ammonium fluoride, solid ammonium fluoride is dissolved with water in a dissolving tank 1 to prepare a saturated ammonium fluoride solution; NH (NH) 4 F(s)+H 2 O→NH 4 F(l)；
Saturated ammonium fluoride solution is subjected to a treatment at a vacuum of 0.04MPa and a temperature of 50-70 deg.C, for example: after being concentrated for 0.5h at constant temperature of 50 ℃,60 ℃,70 ℃ and the like, the mixture is sent into a mist end separation tank 2 for mist end separation, the generated ammonia gas and water vapor are subjected to rapid pressure relief and temperature reduction after entering the mist end separation tank 2, the temperature in the absorption solution is reached, the water vapor is rapidly converted into water drops and falls downwards, then the water drops and the undecomposed ammonium fluoride solution and ammonium bifluoride solution form a solution, the ammonia gas escapes upwards, and then ammonia-containing gas and slurry are generated through separation; 2NH 4 F(l)→NH 4 HF 2 +NH 3 ↑+H 2 O(l)；
By utilizing the characteristic of higher density of the ammonium bifluoride, the ammonium bifluoride crystal is settled at the bottom end of the mist end separation tank 2, and an ammonium bifluoride product and an ammonium fluoride solution are obtained through centrifugal separation; the ammonium fluoride solution is sent into dissolving tank 1 through circulating pipe 5, adds solid ammonium fluoride and prepares saturated ammonium fluoride solution, make full use of the water resource, simultaneously, utilizes the effect of fog end knockout drum 2, has reduced vapor and has escaped along with the escape of ammonia, has reduced water resource consumption, has realized water resource cyclic utilization in the technology, has reduced ammonium bifluoride preparation cost. For the ammonia gas that produces, the ammonia pipe 10 discharge at 2 tops of fog end knockout drum is used for ammonia absorption utilization and is prepared ammonium sulfate, connects it in the fluorine chemical industry production ammonium fluorosilicate in more excellent scheme, and reuse ammonium fluorosilicate preparation ammonium fluoride realizes the operation and the utilization of ammonium fluoride circulation supply, increases the utilization ratio to ammonium, reduce cost.
And adding normal-temperature water to dissolve the obtained ammonium bifluoride, cooling the ammonium bifluoride to less than 10 ℃ to recrystallize and separate out the ammonium bifluoride, directly filtering the ammonium bifluoride to wash the ammonium bifluoride, and drying the ammonium bifluoride to constant weight at 55 ℃ to obtain an ammonium bifluoride product, wherein the purity of the ammonium bifluoride product is over 99.35 percent. And the filtrate obtained by filtering is returned to the dissolving tank 1 to dissolve solid ammonium fluoride, so as to prepare saturated ammonium fluoride solution. And when the single process in the embodiment does not circularly enter the dissolving tank 1, the conversion rate of converting the ammonium fluoride into the ammonium bifluoride reaches over 38 percent.
As shown in fig. 2 and 4, in this embodiment, based on the above embodiment, the slurry entering the mist end separation tank 2 is pumped by the liquid pump 6 and sent into the concentrator 7, and then sent into the mist end separation tank 2 to be decompressed, cooled and separated, and after twice concentration and operation according to the operation method of the above embodiment, the purity of the obtained ammonium bifluoride reaches above 99.39%, and when the slurry is not circulated into the dissolution tank 1 in a single pass in this embodiment, the conversion rate of ammonium fluoride into ammonium bifluoride reaches above 65%.
As shown in fig. 3 and 4, in this embodiment, based on the embodiment shown in fig. 1 and 4, the saturated ammonium fluoride solution in the dissolving tank 1 is directly sent into the mist end separation tank 2, and then is pumped into the concentrator 7 by the liquid pump 6, and then is sent into the mist end separation tank 2 to be decompressed, cooled and separated, after two times of concentration, and then is operated according to the operation method of the above embodiment, the purity of the obtained ammonium bifluoride reaches above 99.33%, and when the ammonium bifluoride is not recycled into the dissolving tank 1 in a single pass in this embodiment, the conversion rate of the ammonium bifluoride into the ammonium bifluoride reaches above 65.8%.
As shown in FIG. 4, the invention matches the corresponding device structure to meet the process requirement of preparing ammonium bifluoride by taking solid ammonium fluoride as a raw material, and is embodied in detail.
In some embodiments, the device for preparing ammonium bifluoride from solid ammonium fluoride comprises a dissolving tank 1 and an end-mist separation tank 2, wherein a circulating liquid port 16 and a charging port 14 are arranged on the side wall of the dissolving tank 1 close to the top end, a slurry discharge port 13 is arranged at the bottom end of the dissolving tank 1, an ammonia pipe 10 is arranged at the top of the end-mist separation tank 2, a slurry port 11 is arranged on the side wall of the end-mist separation tank 2 close to the top end, and a liquid discharge port is arranged at the bottom of the end-mist separation tank 2; a liquid circulation port is formed in the side wall, close to the bottom, of the mist-dust separating tank 2, a concentrated liquid port 8 is formed in the side wall, close to the top, of the mist-dust separating tank 2, a concentrator 7 is arranged between the concentrated liquid port 8 and the liquid circulation port, and a liquid pump 6 is arranged between the concentrator 7 and the liquid circulation port; the slurry discharge port 13 is communicated with the slurry port 11 through a pipeline; the bottom end of the liquid outlet is connected with a centrifugal separator 3, a centrifugal slag outlet and a centrifugal liquid outlet are arranged on the centrifugal separator 3, and a circulating pipe 5 is arranged between the centrifugal liquid outlet and the circulating liquid outlet 16.
When in use, solid ammonium fluoride is loaded into the dissolving tank 1 from the charging port 14, water is metered into the dissolving tank from the charging port 14, the solid ammonium fluoride is contacted with the water and dissolved in the dissolving tank 1, after the dissolution is finished and a saturated ammonium fluoride solution is formed, the saturated ammonium fluoride solution in the dissolving tank 1 is discharged into the mist end separating tank 2 through the slurry discharging port 13, the saturated ammonium fluoride solution entering the mist end separating tank 2 is pumped out by the liquid pumping pump 6 and sent into the concentrator 7, the saturated ammonium fluoride solution is heated to 50-70 ℃ and the vacuum degree in the concentrator 7 is controlled to be 0.04MPa, the saturated ammonium fluoride solution is sent into the mist end separating tank 2 through the concentrate port 8 after concentration treatment for 0.5h, the realization is because of the gas-liquid separation of the gas mixture that the concentration produced, make in fog-end knockout drum 2, the gas mixture receives quick pressure release and dispels the heat, then realize that the vapor condensation that produces becomes the drop whereabouts, and the ammonia is then discharged from ammonia pipe 10, make and contain ammonium bifluoride, ammonium fluoride, the liquid composition of water falls into the bottom of fog-end knockout drum 2 again, discharge through the leakage fluid dram again, send into centrifugal separator 3 in, through centrifugal separation, obtain ammonium bifluoride filter cake and the filtrating that contains ammonium bifluoride, the filtrating that will contain ammonium bifluoride returns to dissolving tank 1 in through circulating pipe 5, after 14 supplementary ammonium bifluoride compositions in the department of charging, ammonium bifluoride is produced in a recycling manner. The device simple structure, high durability and convenient use, and the characteristic that make full use of ammonium bifluoride crystal density is big, make it sink in 2 bottoms of fog end knockout drum, ammonium bifluoride solution is located the upper strata in fog end knockout drum 2, can constantly be taken out and the cycle is concentrated by drawing liquid pump 6, and the ammonium bifluoride crystal that is located the lower floor then can be by the discharge fluid dram centrifugation after-production ammonium bifluoride, to a certain extent, can ensure the purity of ammonium bifluoride product, more can improve the conversion rate of ammonium bifluoride to the conversion of ammonium bifluoride one way, reduce ammonium bifluoride product manufacturing cost.
The mist dust separating tank 2 adopted by the invention is of a cone-shaped structure at the bottom, a cylindrical structure is arranged at the upper end of the cone-shaped structure, and the liquid circulating port is arranged at the connecting point of the cone-shaped structure and the cylindrical structure, so that the generated ammonium bifluoride is enabled to be fully recycled from the lower layer to the cone-shaped structure, and the efficiency of producing ammonium bifluoride products is improved. In some embodiments, the top end of the mist end separation tank 2 is in an inverted cone shape, so that when the water vapor entering the mist end separation tank 2 contacts the top of the inverted cone shape, the water vapor is condensed and falls, the ammonia gas is directly discharged from the ammonia gas pipe 10, the water vapor content in the ammonia gas is reduced, and the water resource is recycled to a great extent.
In some embodiments, in order to enable water vapor in the ammonia gas discharged from the ammonia gas pipe 10 to be sufficiently condensed and recycled into the tank of the mist-end separation tank 2, the ammonia gas pipe 10 is vertically installed upwards for at least 1m, and a cooler is arranged on the outer wall of the vertically upward ammonia gas pipe and is capable of reducing the temperature in the ammonia gas pipe to be less than 5 ℃. The condenser employed is a conventional cooling device, for example: the cold and hot water heat exchanger adopts a water tank with the temperature less than 5 ℃ to wrap the outer surface of the ammonia gas pipe 10, so that the heat exchange in the ammonia gas pipe 10 is realized, and the cooling purpose is further achieved. This embodiment is not shown in the drawings and is conventional in the art. And the condensed water vapor forms water drops and falls down to the interior of the mist separator tank 2 along the vertical ammonia gas pipe 10.
In some embodiments, as shown in fig. 4, the circulation tube 5 is provided with an infusion pump 4. The separated liquid obtained by the treatment of the centrifugal separator 3 can be conveniently circulated into the dissolving tank 1, and the circulation efficiency is improved.
In some embodiments, as shown in fig. 4, an infusion pump 4 is arranged on the pipeline communicating between the slurry outlet 13 and the slurry port 11; a valve 12 is arranged between the infusion pump 4 and the grout outlet 13. The saturated ammonium fluoride solution in the dissolving tank 1 is conveniently sent into the mist end separating tank 2.
In some embodiments, as shown in fig. 4, a stirring assembly 15 is provided in the dissolving tank 1 to accelerate the dissolution of the ammonium fluoride solids. As shown in fig. 4 and 5, the stirring assembly 15 includes a stirring shaft 15.1, is located at the inner section of the dissolving tank 1, a stirring blade 15.3 is arranged on the stirring shaft 15.1, a liquid leakage hole 15.4 is arranged on the stirring blade 15.3, the stirring blade 15.3 is connected with the stirring shaft 15.1 through a connector 15.2, the connector 15.2 is fastened and fixed by a bolt 15.5, and the connector 15.2 is integrally formed with the stirring blade 15.3. Easy maintenance, and overall stability of the stirring assembly 15.
In some embodiments, as shown in fig. 4, the top end of the interior of the mist separation tank 2 is provided with a conical baffle 9. The efficiency of condensing the water vapor into water drops due to the removal of the wall surface is improved, the water vapor content in the ammonia gas is reduced, and the water resource consumption is reduced.
In order to better explain the invention, the process research of preparing ammonium bifluoride product from solid ammonium fluoride and water is carried out by using the device shown in fig. 4 and 5.
Example 1
Reacting NH 4 Dissolving F(s) in water to obtain saturated ammonium fluoride solution, concentrating the saturated ammonium fluoride solution at 50 deg.C under 0.04MPa for 0.5 hr, directly feeding into a mist-dust separating tank 2 for mist-dust separation to allow the gas component to escape upward, allowing the undecomposed ammonium fluoride solution and ammonium bifluoride solution to fall down and enter the bottom of the mist-dust separating tank 2 to form NH 4 F-NH 4 HF 2 -H 2 And (4) an O system. When ammonium bifluoride in the system is saturated, ammonium bifluoride crystals are separated out and sink to the bottom of the mist powder separation tank 2, and after centrifugal separation is released through a valve, the filter cake obtained through centrifugal separation is NH 4 HF 2 And centrifugally separating the liquid and returning to prepare a saturated ammonium fluoride solution.
Subjecting the obtainedNH 4 HF 2 Dissolving the filter cake with normal temperature water (20 ℃), cooling and concentrating to a temperature of less than 10 ℃, filtering to obtain a washed filter cake and a washed liquid, returning the washed liquid to prepare a saturated ammonium fluoride solution, and drying the washed filter cake at 55 ℃ to obtain NH 4 HF 2 . Through determination: NH (NH) 4 HF 2 Purity of 99.35%, NH 4 Conversion of F to NH 4 HF 2 Per pass conversion of 38.15%.
Example 2
On the basis of example 1, the NH is prepared by treating the same as example 1 according to the process flow shown in FIG. 2 4 HF 2 The product was subjected to cyclic concentration in the mist end separation step shown in FIG. 2 under the same concentration conditions as in example 1, in such a manner that the liquid introduced into the mist end separation tank 2 was extracted, sent into the concentrator 7, concentrated at a vacuum degree of 0.04MPa and 50 ℃ for 0.5 hour, sent into the mist end separation tank 2 for mist end separation, and subjected to cyclic operation twice to obtain NH according to the operation of example 1 4 HF 2 . Through determination: NH 4 HF 2 Purity of 99.39%, NH 4 Conversion of F to NH 4 HF 2 The per pass conversion of (d) was 65.32%.
Example 3
On the basis of example 1, the NH was prepared by treating the same as example 1 according to the process flow shown in FIG. 3 4 HF 2 The product is prepared by directly feeding saturated ammonium fluoride solution prepared by dissolving in the dissolving tank 1 into the mist-end separation tank 2, circularly concentrating by the concentrator 7 under the conditions of vacuum degree of 0.04MPa and concentration at 50 ℃ for 0.5h, feeding into the mist-end separation tank 2 for mist-end separation, circularly operating twice, and obtaining NH according to the operation mode of the embodiment 1 4 HF 2 . Through determination: NH 4 HF 2 Purity 99.33%, NH 4 Conversion of F to NH 4 HF 2 The per pass conversion of (d) was 65.86%.
The invention can be realized by referring to the prior art or common general knowledge and conventional technical means which are well known by the technical personnel in the field. For example: the valves are arranged between the connecting pipelines of the corresponding equipment so as to control the flow of solution and slurry in the pipelines in time, and the adopted valves can be screw thread valves and the like. The invention realizes the direct conversion of solid ammonium fluoride to ammonium bifluoride products, achieves the purposes of concentration-release and the like, realizes the release of ammonia gas from mist end generated by concentration in the mist end separating tank 2, further realizes the preparation of the ammonium bifluoride products by deamination, shortens the process flow, avoids the adoption of hydrofluoric acid and reduces the cost of raw materials.
The above description is only for the purpose of illustrating the present invention and the appended claims, and the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (10)
1. A method for preparing ammonium bifluoride from solid ammonium fluoride is characterized by comprising the following steps:
s1: dissolving solid ammonium fluoride in water to prepare saturated ammonium fluoride solution;
s2: concentrating the saturated ammonium fluoride solution, and performing mist-end separation to generate ammonia-containing gas and slurry;
s3: centrifugally separating the slurry to obtain ammonium bifluoride and ammonium fluoride solution;
s4: circularly sending the ammonium fluoride solution to the step S1 to dissolve solid ammonium fluoride; washing and drying the ammonium bifluoride to obtain an ammonium bifluoride product, and returning the washing liquid to the step S1 to dissolve the solid ammonium fluoride; the ammonia-containing gas is used for preparing ammonium fluoride.
2. The method for preparing ammonium bifluoride from solid ammonium fluoride according to claim 1, wherein in step S2, the saturated ammonium fluoride solution is subjected to mist-end separation to generate ammonia-containing gas and slurry, the slurry is subjected to cyclic heating concentration, the mist-end separation generates ammonia-containing gas and low-concentration ammonium fluoride solution, and the low-concentration ammonium fluoride solution is recycled to step S1 to dissolve the solid ammonium fluoride.
3. The method for preparing ammonium bifluoride from solid ammonium fluoride according to claim 2, wherein in step S2, the saturated ammonium fluoride solution is concentrated and then subjected to mist-end separation to generate ammonia-containing gas and slurry, the slurry is concentrated by cyclic heating, the mist-end separation is performed to generate ammonia-containing gas and a low-concentration ammonium fluoride solution, and the low-concentration ammonium fluoride solution is recycled to step S1 to dissolve the solid ammonium fluoride.
4. The process for producing ammonium acid fluoride according to claim 1, 2 or 3, wherein the concentration is carried out under a vacuum of 0.04MPa and at an elevated temperature of 50 to 70 ℃.
5. The method for preparing ammonium bifluoride from solid ammonium fluoride according to claim 1, wherein the washing and drying are carried out by dissolving with water at normal temperature, reducing the temperature and concentrating to less than 10 ℃, filtering to obtain ammonium bifluoride filter cake and washing liquid, and drying the ammonium bifluoride filter cake at 55 ℃.
6. The device for preparing ammonium bifluoride from solid ammonium fluoride is characterized by comprising a dissolving tank (1) and a mist end separating tank (2), wherein a circulating liquid port (16) and a charging port (14) are formed in the side wall, close to the top end, of the dissolving tank (1), a slurry discharging port (13) is formed in the bottom end of the dissolving tank (1), an ammonia pipe (10) is formed in the top of the mist end separating tank (2), a slurry port (11) is formed in the side wall, close to the top end, of the mist end separating tank (2), and a liquid discharging port is formed in the bottom of the mist end separating tank (2); a liquid circulation port is formed in the side wall, close to the bottom, of the mist-end separation tank (2), a concentrated liquid port (8) is formed in the side wall, close to the top, of the mist-end separation tank (2), a concentrator (7) is arranged between the concentrated liquid port (8) and the liquid circulation port, and a liquid pump (6) is arranged between the concentrator (7) and the liquid circulation port; the slurry discharge port (13) is communicated with the slurry port (11) through a pipeline; the bottom end of the liquid outlet is connected with a centrifugal separator (3), a centrifugal slag outlet and a centrifugal liquid outlet are arranged on the centrifugal separator (3), and a circulating pipe (5) is arranged between the centrifugal liquid outlet and the circulating liquid outlet (16).
7. The apparatus for preparing ammonium bifluoride from solid ammonium fluoride according to claim 6, wherein the circulation pipe (5) is provided with an infusion pump (4).
8. The apparatus for preparing ammonium bifluoride from solid ammonium fluoride according to claim 6, wherein an infusion pump (4) is arranged on the pipeline communicating the slurry outlet (13) and the slurry port (11); a valve (12) is arranged between the infusion pump (4) and the grout outlet (13).
9. The apparatus for preparing ammonium bifluoride from solid ammonium fluoride according to claim 6, wherein a stirring assembly (15) is arranged in the dissolving tank (1), the stirring assembly (15) comprises a stirring shaft (15.1), a stirring blade (15.3) is arranged on the stirring shaft (15.1) at the inner section of the dissolving tank (1), a liquid leakage hole (15.4) is formed in the stirring blade (15.3), the stirring blade (15.3) is connected with the stirring shaft (15.1) through a connector (15.2), the connector (15.2) is fastened and fixed by a bolt (15.5), and the connector (15.2) and the stirring blade (15.3) are integrally formed.
10. The device for preparing ammonium bifluoride from solid ammonium fluoride according to claim 6, wherein the top end of the interior of the mist separation tank (2) is provided with a conical baffle plate (9).
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| US3106449A (en) * | 1961-07-17 | 1963-10-08 | Grace W R & Co | Production of ammonium hydrogen fluoride |
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