CN101913565B - Method for preparing hydrogen fluoride from flousper powder and sulfuric acid - Google Patents
Method for preparing hydrogen fluoride from flousper powder and sulfuric acid Download PDFInfo
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Abstract
The invention discloses a method for preparing hydrogen fluoride from flousper powder and sulfuric acid. The method comprises the following specific steps of: adding solution of sulfuric acid and the flousper powder into a reactor with a stirrer respectively, wherein the molar ratio of calcium fluoride to the sulfuric acid is 1:3-1:30, the granularity of the flousper powder is 280 to 1,220 meshes, and the reaction temperature is controlled to between 90 and 300 DEG C; generating hydrogen fluoride gas and calcium sulfate solid after the reaction; purifying, condensing and rectifying the hydrogen fluoride gas to obtain anhydrous hydrogen fluoride, or purifying and absorbing the hydrogen fluoride gas to obtain hydrofluoric acid; transferring the calcium sulfate solid and the sulfuric acid to a filtering system from the reactor to perform solid-liquid separation; returning the separated solution of sulfuric acid to the reactor; and washing and drying the calcium sulfate solid separated from the sulfuric acid to form a by-product. The method has the advantages of simple equipment, high reaction efficiency, low cost and easy industrialized production.
Description
Technical field
The present invention relates to the hydrofluoric method of a kind of production, more specifically say a kind of take Fluorspar Powder and sulfuric acid as the hydrofluoric method of raw material production.
Background technology
Hydrogen fluoride is the basic material of fluorine chemical, molecular formula HF; Hydrogen fluoride and its aqueous solution can be used for making the organic or inorganic fluorochemical, such as fluorocarbon, various fluorine refrigerant, fluoro-resin, aluminum fluoride, Potassium monofluoride, sodium aluminum fluoride etc., can be used for glass etching, plating, pottery processing, petroleum industry catalyzer, forst bulb manufacturing, metal founding desanding, the removal of graphite ash, metal cleaning (brass, stainless steel) and semi-conductor (germanium, silicon) manufacturing etc.; It also is the main raw material of making element fluorine.
Hydrofluoric conventional production methods is take Fluorspar Powder and sulfuric acid as raw material, after mixing near the proportioning of theoretical value (molar ratio of Fluorspar Powder and sulfuric acid is 1: 1), enters in the very huge rotary type Reaktionsofen, produces chemical reaction; Because reaction is an endothermic process, the high-temperature gas heating must be continuously forced in the outside of converter, and the material in the guarantee converter fully reacts.Generate hydrogen fluoride gas and gypsum (calcium sulfate) slag behind Fluorspar Powder and the sulfuric acid reaction; Hydrogen fluoride gas becomes the hydrogen fluoride product through washing, condensation, rectifying, the operation such as degassed, and gypsum tailings becomes the powdery solid waste residue through operations such as neutralization, tail gas absorption, coolings.There is following shortcoming in this conventional production methods:
1, in order to reach certain production capacity and to guarantee that the chemical reaction of material is abundant, converter must be very huge; For example producing 10000 tons of hydrofluoric converter internal diameters per year is 3.2 meters, and length is 32 meters, and furnace wall thickness is 80 millimeters; The deadweight of such converter is above 200 tons; If need larger production capacity, converter is also just larger.Therefore the manufacturing cost of converter is very high.In process of production, the converter deadweight adds materials inside weight, and gross weight reaches 300～500 tons, and the power consumption that drives its rotation is very large.Because Fluorspar Powder and sulfuric acid are to mix according to the proportioning near theoretical value, the variation of the forms such as reaction process pulp-like has occured, is solidified shape, rare sticking shape, powdery; When rare sticking shape, very large to the corrosion of converter inwall, so that the maintenance cost of converter is very high.
2, because the chemical reaction of Fluorspar Powder and sulfuric acid is thermo-negative reaction, for the carrying out that guarantees to react, must provide continuously heat energy, therefore will be in the heating of the converter outside, heat is passed to the material of converter inside, guarantee the carrying out of reaction.Realize by high-temperature gas during heating, high-temperature gas first thermal energy transfer to the converter furnace wall, the furnace wall is given material thermal energy transfer again, such type of heating thermo-efficiency is very low, its heat utilization rate only has an appointment 25%.Original temperature of reaction just can be carried out more than 90 ℃ as long as keep, but in order to guarantee the process that material is advanced and obtain complete reaction in the time in converter, only have and temperature of reaction is brought up to 200 ℃～500 ℃ (not so reaction not exclusively, do not have the material of reaction to discharge with gypsum tailings, become dangerous solid waste, also wasted simultaneously valuable starting material) so that the temperature of high-temperature gas must reach 550 ℃～650 ℃.The hydrogen fluoride gas temperature that pyroreaction is produced is also higher, and the coolant quantity that consumes when making hydrogen fluoride liquid by condenser is very large, and energy consumption is very high.
3, in theory, Fluorspar Powder is thinner, and is faster with the reaction of sulfuric acid, guarantees that the time of fully reacting is shorter, and required temperature of reaction also needn't be too high.But it is very large that too thin Fluorspar Powder can airborne dust in converter, and the dust that hydrogen fluoride gas is carried secretly out the time from converter will be more, so that the subsequent disposal of hydrogen fluoride gas is difficult to carry out, perhaps the purification refine cost is very high.Therefore, produce hydrogen fluoride with the reactive system that converter is such, Fluorspar Powder can not be too thin; And can not be too thin just because of Fluorspar Powder, but guarantee again to react completely, have to Converter Design is become bulky, have to improve temperature of reaction.
Therefore, the traditional process equipment investment is large, and the production process energy consumption is large, and equipment life is low, and the products production cost is high.
For this reason, number of patent application is 200710166276.7 Chinese patent application " producing hydrofluoric method under a kind of condition of environment protection low temperature liquid condition ", disclose a kind of take liquid ice acetic acid or strong phosphoric acid as medium, sulfuric acid and Fluorspar Powder are added in the medium, by the oligodynamical of Fluorspar Powder in medium, at 90 ℃～100 ℃ and sulfuric acid reaction, reach the hydrofluoric method of producing.But Glacial acetic acid belongs to volatile raw material, and recovery difficult is large, and cost recovery is high, and Glacial acetic acid is very large with the hydrogen fluoride mutual solubility, so that the refining cost height of hydrogen fluoride product; During take phosphoric acid as medium, phosphoric acid and Fluorspar Powder, hydrogen fluoride react, and generate hexafluorophosphoric acid and fluorophosphate, have both consumed phosphoric acid and have also consumed hydrogen fluoride; Also so that the large or refining cost of hydrofluoric refining difficulty is high, and the phosphoric acid price is also expensive, will make hydrofluoric production cost very high; Therefore the formation industrial production line is not arranged at present.
Summary of the invention
The objective of the invention is for the deficiencies in the prior art, provide that a kind of equipment is simple, reaction efficiency is high low-cost and easily form the hydrofluoric production technique of suitability for industrialized production, the method is take Fluorspar Powder and sulfuric acid as raw material.
The technical solution used in the present invention is as follows: a kind of with Fluorspar Powder and the hydrofluoric method of gas washing in SA production, concrete steps are as follows: sulphuric acid soln and Fluorspar Powder are added respectively in the reactor of band stirring, and feed ratio is that the molar ratio of Calcium Fluoride (Fluorspan) and sulfuric acid is 1: 3～1: 30; And the fineness of Fluorspar Powder is 280 orders～1220 orders; Temperature of reaction is controlled at 90 ℃～300 ℃; Produce hydrogen fluoride gas and calcium sulphate solid after the reaction; Hydrogen fluoride gas is purified, condensation, rectifying obtain anhydrous hydrogen fluoride; Or purified, absorb and to obtain hydrofluoric acid; Calcium sulphate solid is transferred to filtering system with sulfuric acid from reactor, carries out solid-liquid separation, and the sulphuric acid soln of separating comes back in the reactor; After calcium sulphate solid is separated, through washing and oven dry, become byproduct from sulfuric acid.
Preferably, the blending ratio of Fluorspar Powder and sulfuric acid is Calcium Fluoride (Fluorspan): the molar ratio of sulfuric acid is 1: 10～1: 17.
Preferably, the fineness of Fluorspar Powder is 500 orders～800 orders.
Preferably, temperature of reaction is controlled at 120 ℃-220 ℃.
Preferably, the control of temperature of reaction is by sulphuric acid soln being heated in interchanger and being circulated in the reactor, perhaps by realizing to jacketed or with the reactor direct heating of coil pipe, and type of heating can be electric energy, steam, thermal oil or other heat-transfer medium.
Preparation method provided by the present invention, the chemical principle that is mainly concerned with is as follows:
A. major ingredient Calcium Fluoride (Fluorspan) and the sulfuric acid reaction in the Fluorspar Powder generates hydrogen fluoride and gypsum:
CaF
2+H
2SO
4→2HF↑+CaSO4↓
B. part silicon-dioxide and the hydrogen fluoride reaction in the Fluorspar Powder generates silicon tetrafluoride and water:
SiO
2+4HF→SiF
4↑+2H
2O
Compared with prior art, the present invention has following beneficial effect:
1, operational path is novel, reasonable, and equipment is simple, and reduced investment is simple to operate, realizes easily suitability for industrialized production.
2, the weight of common response still only has percentum of converter weight, and facility investment greatly reduces, energy-conservation just very obvious during device fabrication.The equipment maintenance cost of production process also reduces greatly.
3, because reaction is carried out always, dust can be do not produced in excessive sulfate liquid, therefore very thin Fluorspar Powder can be adopted; Thereby greatly shortened the reaction times, temperature of reaction also needn't be too high.Reacting required heat energy is to conduct to reaction mass by hot water, steam, thermal oil or other heat-conducting medium, perhaps carrying out " liquid-liquid " heat transfer by interchanger and sulphuric acid soln realizes, therefore better than the heat-transfer effect of conventional high-temperature air mode, heat utilization rate improves greatly.
4, the power consumption of the reactor of band stirring only has converter to rotate 1/tens of power consumption; The hydrogen fluoride gas that low-temp reaction generates required energy consumption when condensation is also lower; Owing to do not have dust, hydrogen fluoride gas not to need washing; Therefore production process is energy-saving and cost-reducing, can greatly reduce the hydrogen fluoride production cost.
5, the dust pollution of decrease gypsum tailings has also reduced the possibility that tail gas leaks.
6, present technique is used for the technological transformation of existing hydrogen fluoride production line, can impel existing enterprise to save energy and reduce the cost, reduce and pollute, increase economic benefit.
Description of drawings
Fig. 1 is the process flow sheet of embodiment one to nine;
Fig. 2 is the process flow sheet of embodiment ten.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiment.
Embodiment one:
1, take the quality percentage composition of Calcium Fluoride (Fluorspan) as 97% Fluorspar Powder and the sulfuric acid of mass percent as 93% as raw material.Fluorspar Powder is crushed to the 280-320 order from about original about 90 orders.
2, the jacketed of a 500L, the reactor that band stirs, the steam of access 0.6MPa in the chuck are set; By the consumption of control steam, can control temperature of reaction.
3, be mass percent that 93% sulfuric acid 132kg passes in the reactor; Open steam valve heating sulfuric acid to 120 ℃, under agitation, slowly add Fluorspar Powder 20kg; At this moment the mol ratio of Calcium Fluoride (Fluorspan) and sulfuric acid is about Calcium Fluoride (Fluorspan): sulfuric acid=1: 5.Stir; The control temperature of reaction is at 90 ℃～120 ℃; Fully reaction.Produce hydrogen fluoride gas and calcium sulphate solid (gypsum) after the reaction, after the hydrogen fluoride gas of generation purified, condensation became hydrogen fluoride liquid.Then separate sulfuric acid and gypsum, and clean gypsum.Finally obtain hydrogen fluoride liquid 9.3kg, gypsum 33.63kg.By analysis, Calcium Fluoride Content is 1.57% in the gypsum, that is: the reaction conversion ratio of Calcium Fluoride (Fluorspan) is 97.23%.
4, the sulfuric acid after the separation mixes with the scavenging solution that cleans gypsum, adds 98% sulfuric acid, makes mixed sulfuric acid concentration reach 93%, waits until next time and uses.
Embodiment two:
1, take the quality percentage composition of Calcium Fluoride (Fluorspan) as 97% Fluorspar Powder and the sulfuric acid of mass percent as 93% as raw material.Fluorspar Powder is crushed to the 480-520 order from about original about 90 orders.
2, the jacketed of a 500L, the reactor that band stirs, the steam of access 0.6MPa in the chuck are set; By the consumption of control steam, can control temperature of reaction.
3, be mass percent that 98% sulfuric acid 264kg passes in the reactor; Open steam valve heating sulfuric acid to 150 ℃, under agitation, slowly add Fluorspar Powder 20kg; At this moment the mol ratio of Calcium Fluoride (Fluorspan) and sulfuric acid is about Calcium Fluoride (Fluorspan): sulfuric acid=1: 10.Stir; The control temperature of reaction is at 120 ℃～150 ℃; Fully reaction.Produce hydrogen fluoride gas and calcium sulphate solid (gypsum) after the reaction, after the hydrogen fluoride gas of generation purified, condensation became hydrogen fluoride liquid.Then separate sulfuric acid and gypsum, and clean gypsum.Finally obtain hydrogen fluoride liquid 9.5kg, gypsum 34.27kg.By analysis, Calcium Fluoride Content is 1.57% in the gypsum, that is: the reaction conversion ratio of Calcium Fluoride (Fluorspan) is 99.16%.
4, the sulfuric acid after the separation mixes with the scavenging solution that cleans gypsum, adds 105% sulfuric acid, makes mixed sulfuric acid concentration reach 98%, waits until next time and uses.
Embodiment three:
1, take the quality percentage composition of Calcium Fluoride (Fluorspan) as 97% Fluorspar Powder and the sulfuric acid of mass percent as 93% as raw material.Fluorspar Powder is crushed to the 780-820 order from about original about 90 orders.
2, the jacketed of a 500L, the reactor that band stirs, admittance deep fat in the chuck are set; Control the temperature of reaction of material in reactor by electric-heating heat-conductive oil.
3, be mass percent that 98% sulfuric acid 395kg passes in the reactor; Start electric heating system, the sulfuric acid temperature is risen to 180 ℃, under agitation, slowly add Fluorspar Powder 20kg; At this moment the mol ratio of Calcium Fluoride (Fluorspan) and sulfuric acid is about Calcium Fluoride (Fluorspan): sulfuric acid=1: 15.Stir; The control temperature of reaction is at 150 ℃～180 ℃; Fully reaction.Produce hydrogen fluoride gas and calcium sulphate solid (gypsum) after the reaction, after the hydrogen fluoride gas of generation purified, condensation became hydrogen fluoride liquid.Then separate sulfuric acid and gypsum, and clean gypsum.Finally obtain hydrogen fluoride liquid 9.4kg, gypsum 34.17kg.By analysis, Calcium Fluoride Content is 0.38% in the gypsum, that is: the reaction conversion ratio of Calcium Fluoride (Fluorspan) is 99.33%.
4, the sulfuric acid after the separation mixes with the scavenging solution that cleans gypsum, adds 105% sulfuric acid, makes mixed sulfuric acid concentration reach 98%, waits until next time and uses.
Embodiment four:
1, take the quality percentage composition of Calcium Fluoride (Fluorspan) as 97% Fluorspar Powder and the sulfuric acid of mass percent as 98% as raw material.Fluorspar Powder is crushed to the 1180-1220 order from 90 original orders.
2, the jacketed of a 500L, the reactor that band stirs, admittance deep fat in the chuck are set; Control the temperature of reaction of material in reactor by electric-heating heat-conductive oil.
3, be mass percent that 98% sulfuric acid 264kg passes in the reactor; Start electric heating system, the sulfuric acid temperature is risen to 210 ℃, slowly add Fluorspar Powder 20kg, at this moment the mol ratio of Calcium Fluoride (Fluorspan) and sulfuric acid is about Calcium Fluoride (Fluorspan): sulfuric acid=1: 10.Stir; The control temperature of reaction is at 180 ℃～210 ℃; Fully reaction.Produce hydrogen fluoride gas and calcium sulphate solid (gypsum) after the reaction, after the hydrogen fluoride gas of generation purified, water was absorbed as 40% hydrofluoric acid.Then separate sulfuric acid and gypsum, and clean gypsum.Finally obtain hydrofluoric acid solution 23.7kg, gypsum 34.18kg.By analysis, Calcium Fluoride Content is 0.62% in the gypsum, that is: the reaction conversion ratio of Calcium Fluoride (Fluorspan) is 98.90%.
4, the sulfuric acid after the separation mixes with the scavenging solution that cleans gypsum, adds 105% sulfuric acid, makes mixed sulfuric acid concentration reach 97%, waits until next time and uses.
Embodiment five:
1, take the quality percentage composition of Calcium Fluoride (Fluorspan) as 97% Fluorspar Powder and the sulfuric acid of mass percent as 93% as raw material.Fluorspar Powder is crushed to the 480-520 order from about original about 90 orders.
2, the jacketed of a 500L, the reactor that band stirs, the steam of access 0.6MPa in the chuck are set; By the consumption of control steam, can control temperature of reaction.
3, be mass percent that 93% sulfuric acid 79kg passes in the reactor; Open steam valve heating sulfuric acid to 150 ℃, under agitation, slowly add Fluorspar Powder 20kg; At this moment the mol ratio of Calcium Fluoride (Fluorspan) and sulfuric acid is about Calcium Fluoride (Fluorspan): sulfuric acid=1: 3.Under agitation control temperature of reaction at 120 ℃～150 ℃; Fully reaction.Produce hydrogen fluoride gas and calcium sulphate solid (gypsum) after the reaction, after the hydrogen fluoride gas of generation purified, condensation became hydrogen fluoride liquid.Then separate sulfuric acid and gypsum, and clean gypsum.Finally obtain hydrogen fluoride liquid 9.1kg, gypsum 34.3kg.By analysis, Calcium Fluoride Content is 2.68% in the gypsum, that is: the reaction conversion ratio of Calcium Fluoride (Fluorspan) is 95.27%.
4, the sulfuric acid after the separation mixes with the scavenging solution that cleans gypsum, and the adding mass percent is 98% sulfuric acid, makes mixed sulfuric acid concentration reach 93%, waits until next time and uses.
Embodiment six:
1, take Calcium Fluoride (Fluorspan) quality percentage composition as 97% Fluorspar Powder and the sulfuric acid of mass percent as 98% as raw material.Fluorspar Powder is crushed to the 280-320 order from about original about 90 orders.
2, the reactor that the jacketed of a 500L is set, stirs with strength; The inlet pipe that strength stirs links to each other with compressed air reservoir through an interchanger again.Adopt coal gas direct heating interchanger, can make pressurized air heating and intensification, top temperature can reach 600 ℃.
3, Fluorspar Powder 20kg is added in the reactor.Starting the electric-heating heat-conductive oil system, is mass percent that 98% sulfuric acid 746kg passes in the reactor when being warming up to 300 ℃, closes electric heating system; At this moment the mol ratio of Calcium Fluoride (Fluorspan) and sulfuric acid is about Calcium Fluoride (Fluorspan): sulfuric acid=1: 30.Open the gas heating system heated compressed air, and pressurized air is heated to 270 ℃～300 ℃, high temperature compressed air enters reactor, as stirring replenishing of power and reaction heat.The control temperature of reaction is fully reacted at 270 ℃～300 ℃.Produce hydrogen fluoride gas and calcium sulphate solid (gypsum) after the reaction, after the hydrogen fluoride gas of generation purified, water was absorbed as 20% hydrofluoric acid.Then separate sulfuric acid and gypsum, and clean gypsum.Finally obtain hydrofluoric acid solution 47.2kg, gypsum 34.0kg.By analysis, Calcium Fluoride Content is 1.12% in the gypsum, that is: the reaction conversion ratio of Calcium Fluoride (Fluorspan) is 98.04%.
4, the sulfuric acid after the separation mixes with the scavenging solution that cleans gypsum, and the adding mass percent is 105% sulfuric acid, makes mixed sulfuric acid concentration reach 98%, waits until next time and uses.
Embodiment seven:
1, take Calcium Fluoride (Fluorspan) quality percentage composition as 97% Fluorspar Powder and the sulfuric acid of mass percent as 98% as raw material.Fluorspar Powder is crushed to the 780-820 order from about original about 90 orders.
2, the jacketed of a 500L, the reactor that band stirs, admittance deep fat in the chuck are set; Control the temperature of reaction of material in reactor by electric-heating heat-conductive oil.
3, be mass percent that 98% sulfuric acid 262kg passes in the reactor; Start the electric-heating heat-conductive oil system, the sulfuric acid temperature is risen to 270 ℃, under agitation, slowly add Fluorspar Powder 20kg; At this moment the mol ratio of Calcium Fluoride (Fluorspan) and sulfuric acid is about Calcium Fluoride (Fluorspan): sulfuric acid=1: 10.Under agitation control temperature of reaction at 240 ℃～270 ℃; Fully reaction.Produce hydrogen fluoride gas and calcium sulphate solid (gypsum) after the reaction, after the hydrogen fluoride gas of generation purified, water was absorbed as 40% hydrofluoric acid.Then separate sulfuric acid and gypsum, and clean gypsum.Finally obtain hydrofluoric acid solution 23.9kg, gypsum 34.2kg.By analysis, Calcium Fluoride Content is 0.62% in the gypsum, that is: the reaction conversion ratio of Calcium Fluoride (Fluorspan) is 98.91%.
4, the sulfuric acid after the separation mixes with the scavenging solution that cleans gypsum, and the adding mass percent is 105% sulfuric acid, makes mixed sulfuric acid concentration reach 95%, waits until next time and uses.
Embodiment eight:
1, take Calcium Fluoride (Fluorspan) quality percentage composition as 97% Fluorspar Powder and the sulfuric acid of mass percent as 98% as raw material.Fluorspar Powder is crushed to the 1180-1220 order from about original about 90 orders.
2, the jacketed of a 500L, the reactor that band stirs, admittance deep fat in the chuck are set; Control the temperature of reaction of material in reactor by electric-heating heat-conductive oil.
3,98% sulfuric acid 522kg is passed in the reactor; Start the electric-heating heat-conductive oil system, the sulfuric acid temperature is risen to 180 ℃, under agitation, slowly add Fluorspar Powder 20kg; At this moment the mol ratio of Calcium Fluoride (Fluorspan) and sulfuric acid is about Calcium Fluoride (Fluorspan): sulfuric acid=1: 21.Under agitation control temperature of reaction at 210 ℃～240 ℃; Fully reaction.Produce hydrogen fluoride gas and calcium sulphate solid (gypsum) after the reaction, after the hydrogen fluoride gas of generation purified, water was absorbed as 40% hydrofluoric acid.Separate sulfuric acid and gypsum, and clean gypsum.Finally obtain hydrofluoric acid solution 23.9kg, gypsum 34.2kg.By analysis, Calcium Fluoride Content is 0.57% in the gypsum, that is: the reaction conversion ratio of Calcium Fluoride (Fluorspan) is 98.99%.
4, the sulfuric acid after the separation mixes with the scavenging solution that cleans gypsum, and the adding mass percent is 105% sulfuric acid, makes mixed sulfuric acid concentration reach 96%, waits until next time and uses.
Embodiment nine:
1, take the quality percentage composition of Calcium Fluoride (Fluorspan) as 97% Fluorspar Powder and the sulfuric acid of mass percent as 98% as raw material.Fluorspar Powder is crushed to the 680-720 order from about original about 90 orders.
2, the jacketed of a 500L, the reactor that band stirs, admittance deep fat in the chuck are set; Control the temperature of reaction of material in reactor by electric-heating heat-conductive oil.
3, Fluorspar Powder 20kg is added in the reactor.Starting the electric-heating heat-conductive oil system, is mass percent that 98% sulfuric acid 423kg passes in the reactor when being warming up to 240 ℃; At this moment the mol ratio of Calcium Fluoride (Fluorspan) and sulfuric acid is about Calcium Fluoride (Fluorspan): sulfuric acid=1: 17.Under agitation control temperature of reaction at 210 ℃～240 ℃; Fully reaction.Produce hydrogen fluoride gas and calcium sulphate solid (gypsum) after the reaction, after the hydrogen fluoride gas of generation purified, condensation became hydrogen fluoride liquid.Then separate sulfuric acid and gypsum, and clean gypsum.Finally obtain hydrogen fluoride liquid 9.36kg, gypsum 34.2kg.By analysis, Calcium Fluoride Content is 0.32% in the gypsum, that is: the reaction conversion ratio of Calcium Fluoride (Fluorspan) is 99.35%.
4, the sulfuric acid after the separation mixes with the scavenging solution that cleans gypsum, and the adding mass percent is 98% sulfuric acid, makes mixed sulfuric acid concentration reach 93%, waits until next time and uses.
Embodiment ten:
1, take the quality percentage composition of Calcium Fluoride (Fluorspan) as 97% Fluorspar Powder and the sulfuric acid of mass percent as 93% as raw material.Fluorspar Powder is crushed to the 980-1020 order from about original about 90 orders.
2, the reactor of the band stirring of a 500L is set, links to each other admittance deep fat in the shell of tubular heat exchange with a tubular heat exchange; Control the temperature of sulfuric acid by electric-heating heat-conductive oil.
3, starting the electric-heating heat-conductive oil system, interchanger is heated to 200 ℃～220 ℃, is mass percent that 93% sulfuric acid 746kg is slowly by in the heat transfer tube of interchanger; Enter in the reactor after the sulfuric acid temperature risen to 180 ℃, under agitation, slowly add Fluorspar Powder 20kg; At this moment the mol ratio of Calcium Fluoride (Fluorspan) and sulfuric acid is about Calcium Fluoride (Fluorspan): sulfuric acid=1: 30.Under agitation control temperature of reaction at 150 ℃～180 ℃; Fully reaction.Produce hydrogen fluoride gas and calcium sulphate solid (gypsum) after the reaction, after the hydrogen fluoride gas of generation purified, condensation became hydrogen fluoride liquid.Separate sulfuric acid and gypsum, and clean gypsum.Finally obtain hydrogen fluoride liquid 9.3kg, gypsum 34.1kg.By analysis, Calcium Fluoride Content is 0.76% in the gypsum, that is: the reaction conversion ratio of Calcium Fluoride (Fluorspan) is 98.67%.
4, the sulfuric acid after the separation mixes with the scavenging solution that cleans gypsum, adds 98% sulfuric acid, makes mixed sulfuric acid concentration reach 93%, is circulated in the interchanger and reuses.
Claims (1)
1. one kind with Fluorspar Powder and the hydrofluoric method of gas washing in SA production, it is characterized in that concrete steps are as follows:
Sulphuric acid soln and Fluorspar Powder are added respectively in the reactor of band stirring, and feed ratio is that the molar ratio of Calcium Fluoride (Fluorspan) and sulfuric acid is 1: 21; And the fineness of Fluorspar Powder is 1180 orders～1220 orders; Temperature of reaction is controlled at 210 ℃～240 ℃; Produce hydrogen fluoride gas and calcium sulphate solid after the reaction; Hydrogen fluoride gas is purified, condensation, rectifying obtain anhydrous hydrogen fluoride; Or purified, absorb and to obtain hydrofluoric acid; Calcium sulphate solid is transferred to filtering system with sulfuric acid from reactor, carries out solid-liquid separation, and the sulphuric acid soln of separating comes back in the reactor; After calcium sulphate solid is separated, through washing and oven dry, become byproduct from sulfuric acid.
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| CN109260784B (en) * | 2018-10-17 | 2020-12-01 | 嘉兴久珥科技有限公司 | Moving bed filter for preparing hydrogen fluoride particle layer |
| CN113213427A (en) * | 2021-06-18 | 2021-08-06 | 国药集团化学试剂有限公司 | Preparation method of high-purity hydrofluoric acid |
| CN113244873A (en) * | 2021-07-15 | 2021-08-13 | 联仕(昆山)化学材料有限公司 | Electronic-grade hydrofluoric acid preparation device |
| CN113800471B (en) * | 2021-10-19 | 2023-05-02 | 浙江容跃环保科技有限公司 | Method for preparing hydrogen fluoride from single cryolite and reaction device thereof |
| CN113772630A (en) * | 2021-10-19 | 2021-12-10 | 浙江容跃环保科技有限公司 | Method for preparing hydrogen fluoride from cryolite |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3825655A (en) * | 1971-07-29 | 1974-07-23 | Bayer Ag | Production of hydrogen fluoride and metal sulfates |
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2010
- 2010-08-12 CN CN 201010252433 patent/CN101913565B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3825655A (en) * | 1971-07-29 | 1974-07-23 | Bayer Ag | Production of hydrogen fluoride and metal sulfates |
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| CN101913565A (en) | 2010-12-15 |
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