CN101277899A - Hydrofluoric acid production apparatus and hydrofluoric acid production method - Google Patents
Hydrofluoric acid production apparatus and hydrofluoric acid production method Download PDFInfo
- Publication number
- CN101277899A CN101277899A CNA2006800203029A CN200680020302A CN101277899A CN 101277899 A CN101277899 A CN 101277899A CN A2006800203029 A CNA2006800203029 A CN A2006800203029A CN 200680020302 A CN200680020302 A CN 200680020302A CN 101277899 A CN101277899 A CN 101277899A
- Authority
- CN
- China
- Prior art keywords
- hydrofluoric acid
- acid
- distillation
- hexafluorosilicic
- water vapour
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
- B01D5/0003—Condensation of vapours; Recovering volatile solvents by condensation by using heat-exchange surfaces for indirect contact between gases or vapours and the cooling medium
- B01D5/0006—Coils or serpentines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
- B01D5/0057—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
- B01D5/006—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes with evaporation or distillation
- B01D5/0063—Reflux condensation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/20—Fluorine
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Water Treatment By Sorption (AREA)
- Silicon Compounds (AREA)
- Removal Of Specific Substances (AREA)
Abstract
In the production of hydrofluoric acid by holding fluorine by adsorption from a drainage water or waste water containing fluorine with an inorganic ceramic adsorbent mainly composed of active alumina and silicon dioxide and producing hydrofluoric acid from the adsorbent provided after the adsorption, the object is to increase the efficiency of production of hydrofluoric acid and prevent the degradation of the adsorbent. A hydrofluoric acid production apparatus for producing hydrofluoric acid by holding a fluorine ion by adsorption from a fluorine compound or fluorine mixture which contains a fluorine ion with a ceramic adsorbent mainly composed of active alumina and silicon dioxide and producing hydrofluoric acid from the adsorbent provided after the adsorption, the apparatus comprising a distillation means for reacting the adsorbent with a strong alkali or strong acid and generating hexafluorosilicic acid gas by addition of crystalline silicon dioxide, and a cooling means for cooling and hydrolyzing the hexafluorosilicic acid gas produced in the distillation means to produce hydrofluoric acid.
Description
Technical field
The present invention relates to a kind of with sorbent material, from draining, waste liquid, waste gas, in the waste medium contained fluorine cpd or fluoride mixture, the objectionable impurities of fluoride is carried out adsorption treatment, and generate the device and method of hydrofluoric acid (fluoridizing hydracid) by this sorbent material.
Background technology
About removing fluorine contained in draining, the waste liquid, and reclaim the method for this fluorine, the method that is called crystallization is widely known by the people, and this method is separated out principle according to recrystallization, and the fluorion in the waste liquid is made Calcium Fluoride (Fluorspan) (CaF
2) the back taking-up.Yet this crystallization is generating highly purified Calcium Fluoride (Fluorspan) (CaF
2) time have a following problem: can't regenerate from the draining, the waste liquid that contain the impurity beyond the fluorine, only limit to semi-conductor make in employed high-purity hydrogen fluoric acid waste liquid, and in order to obtain the operation that hydrofluoric acid need generate hydrofluoric acid from Calcium Fluoride (Fluorspan).
As the method for head it off, disclosing in following patent documentation 1 has the method for using sorbent material to come the regenerated hydrogen fluoric acid.This method utilization is sorbent material with activated alumina and silicon-dioxide as the inorganic ceramic of principal constituent, from the draining that contains fluorine, waste liquid, fluorine is carried out adsorption treatment, sorbent material after the use adsorption treatment makes hydrofluoric acid regeneration, and utilize distillation mechanism that sorbent material and concentrated sulfuric acid solution are reacted and isolate fluorine from sorbent material, will be liquefied by the hydrogen fluoride gas that distillation procedure generated obtains hydrofluoric acid.If according to this method, even from also direct regenerated hydrogen fluoric acid such as the hydrofluoric acid draining that contains various impurity.
Patent documentation 1: the spy opens the 2004-345949 communique
Summary of the invention
Yet if the method for being put down in writing according to above-mentioned patent documentation 1, when containing other metal ingredient as impurity in sorbent material, the fluorion of fluorochemical combines with other metal ingredient easily, thus the problem of generation hydrofluoric acid formation efficiency reduction.And, the problem that can't use because the silicon-dioxide in the sorbent material because of decomposing disappearance with strong sulfuric acid response, therefore the sorbent material deterioration also takes place.
In view of this problem, problem of the present invention is that utilizing with activated alumina and silicon-dioxide is sorbent material as the inorganic ceramic of principal constituent, from the draining that contains fluorine, waste liquid, fluorine is carried out adsorption treatment, and the sorbent material after the use adsorption treatment generates under the situation of hydrofluoric acid, improve the formation efficiency of hydrofluoric acid, and suppress the sorbent material deterioration.
In order to solve above-mentioned problem, the present invention has following formation.
The 1st described invention is a kind of hydrofluoric acid generating apparatus, it utilizes with activated alumina and silicon-dioxide is sorbent material as the pottery of principal constituent, from the fluorine cpd that contain fluorion or fluoride mixture, fluorion is carried out adsorption treatment, and use the sorbent material after the adsorption treatment to generate hydrofluoric acid; Wherein, possess distillation mechanism and cooling body, described distillation mechanism makes above-mentioned sorbent material and highly basic or strong acid reaction, and add crystallinity silicon-dioxide and generate hexafluorosilicic acid gas, the hexafluorosilicic acid gas that the cooling of described cooling body is generated by above-mentioned distillation mechanism, and be hydrolyzed and generate hydrofluoric acid.
The 2nd described invention is in described hydrofluoric acid generating apparatus, and wherein, described distillation mechanism further adds phosphoric acid.
The 3rd described invention is in described hydrofluoric acid generating apparatus, and wherein, described Heating temperature of distilling mechanism's distillation procedure is set at 110 ℃～160 ℃.
The 4th described invention is in described hydrofluoric acid generating apparatus, wherein, further comprise wiper mechanism, it is after described Heating temperature of distilling distillation procedure described in the mechanism reaches more than 130 ℃, utilize water vapour, hexafluorosilicic acid gas is cleaned to described cooling body from described distillation mechanism.
The 5th described invention is in the 4th described hydrofluoric acid generating apparatus, described wiper mechanism is to send the speed with respect to the water vapour of the about amount below 1/10 of reaction-ure mixture in 1 minute with the initial stage speed setting of the cleaning of water vapour, and interim the cleaning speed of accelerating, reach about 1～5 times stage by the hydrofluoric acid amount that cooling body generated with respect to described reaction-ure mixture, stopping the cleaning of water vapour.In addition, amount herein means quality, and reaction-ure mixture also comprises the total reactant amount of phosphoric acid when meaning the highly basic that comprises quantity of sorbent and interpolation or strong acid and crystallinity silicon-dioxide and then adding phosphoric acid.
The 6th described invention is in the 4th or 5 described hydrofluoric acid generating apparatus, and described cooling body liquefies hexafluorosilicic acid gas and water vapour 1 ℃～20 ℃ scope and forms hydrofluoric acid.
The 7th described invention is a kind of hydrofluoric acid generation method, it utilizes with activated alumina and silicon-dioxide is sorbent material as the pottery of principal constituent, it is saturated to adsorbing fluorion to be carried out adsorption treatment from the fluorine cpd that contain fluorion or fluoride mixture etc., and uses the sorbent material after the adsorption treatment to make hydrofluoric acid regeneration; Wherein, have distillation process and refrigerating work procedure, described distillation process stage is added above-mentioned sorbent material and highly basic or strong acid a certain amount ofly and is reacted, and further add the crystallinity silicon-dioxide of trace and phosphoric acid and react and temporarily generate hexafluorosilicic acid, described refrigerating work procedure simultaneously cools off the hexafluorosilicic acid that liquefies and generated, and one side makes its hydrolysis generate hydrofluoric acid.
The 1st described invention added crystallinity silicon-dioxide and generated hexafluorosilicic acid gas (6HF+SiO in distillation mechanism
2→ H
2SiF
6+ 2H
2O).Thus, can suppress metal ion reaction contained in fluorion and the sorbent material, improve the hydrofluoric acid formation efficiency.And, owing to reduce because of strong acid or highly basic, therefore can suppress the sorbent material deterioration by adding silicon-dioxide that crystallinity silicon-dioxide suppresses sorbent material.
The effect of the 2nd described invention is, in distillation mechanism, even the contained aluminium component of sorbent material by adding phosphoric acid, can be prevented still that the aluminium of stripping from combining with fluorine by strong acid or highly basic stripping, and the stripping of promotion fluorochemical (HF).
The 3rd described invention is set at 110 ℃～160 ℃ by the Heating temperature with distillation procedure in the above-mentioned distillation mechanism, can only distillate hexafluorosilicic acid, and suppress to distillate other heavy metal objectionable impurities.That is, because the boiling point of heavy metal is very high, for example lead is 1740 ℃, and cadmium is 766 ℃, chromium is 2200 ℃, white arsenic is 278 ℃, and mercury is 356 ℃, compared to this, the boiling point of hexafluorosilicic acid is about 110 ℃, therefore 110 ℃～160 ℃ scope, only hexafluorosilicic acid gasifies and distillates, and distillates thereby can suppress heavy metal.
The 4th described invention possesses and utilizes water vapour that hexafluorosilicic acid is cleaned wiper mechanism to cooling body, reaching 130 ℃ in the Heating temperature of above-mentioned distillation procedure utilizes water vapour to clean later on again, preventing thus increases owing to the water vapour cohesion causes liquid measure, can prevent that the concentration of regenerated hydrogen fluoric acid from reducing.Furthermore, owing to preventing that hexafluorosilicic acid is hydrolyzed and stagnates in the path halfway, therefore can prevent the deterioration that distillates of hexafluorosilicic acid.
The 5th described invention is to send the speed with respect to the water vapour of the about amount below 1/10 of reaction-ure mixture in 1 minute with the initial stage speed setting of the cleaning of water vapour, and interim the cleaning speed of accelerating, reaching about 1～5 times stage by the hydrofluoric acid amount that cooling body generated with respect to above-mentioned reaction-ure mixture, stop the cleaning of water vapour, thereby can be with minimal steam vapour amount, carry out the cleaning of hexafluorosilicic acid gas effectively, can prevent that the concentration of the hydrofluoric acid that obtained from reducing.That is, the initial reaction stage stage in distillation mechanism, the positive progress that distillates owing to hexafluorosilicic acid gas, therefore water vapour speed is set at 1 minute total amount lessly and is 1/10 amount with respect to reaction volume, and along with the speed that distillates of hexafluorosilicic acid gas reduces to improve water vapour speed interimly, so that stably clean fluorochemical, reach about 1～5 times moment and stop to clean with respect to cleaning used reaction-ure mixture in the hydrofluoric acid amount that is generated, thereby can suppress to clean used total steam vapour amount, and the roughly whole hexafluorosilicic acid gas that is generated can be driven out of to cooling body.
The effect of the 6th described invention is, in the scope of 1 ℃～20 ℃ of above-mentioned cooling bodies hexafluorosilicic acid gas and water vapour are liquefied and to obtain hydrofluoric acid, thus in the process of the water vapour that is used for cleaning liquefaction, hexafluorosilicic acid can be hydrolyzed and become fluorochemical (HF) and silicon tetrafluoride (SiF
4), owing to having the lower boiling silicon tetrafluoride (SiF of boiling point for-86 ℃
4) can gasification after decomposition, and being expelled to the outside via removing device, the fluorochemical (HF) that therefore only has about boiling point more than 20 ℃ does not gasify, water soluble and become hydrofluoric acid and reclaim.
The 7th described invention still added crystallinity silicon-dioxide and generated hexafluorosilicic acid gas in distillation process, can suppress metal ion reaction contained in fluorion and the sorbent material thus, can improve the hydrofluoric acid formation efficiency.And, reduce because of strong acid or highly basic by adding silicon-dioxide that crystallinity silicon-dioxide suppresses sorbent material, therefore can suppress the sorbent material deterioration.
Description of drawings
Fig. 1 is the structure iron of the hydrofluoric acid generating apparatus of model utility ground expression embodiment.
Fig. 2 be expression relatively sodium hydroxide and sulfuric acid from the experimental result picture of the amount of sorbent material stripping fluorochemical.
Nomenclature
1 distillation tower
2 process furnace
4,5 paths
8 raw material input ports
10 water vapour genetic horizons
11 solution tanks
16 cooling layers
41 crystalline silica grooves
43 phosphoric acid grooves
Embodiment
According to the following graphic embodiments of the present invention that describe in detail.
Fig. 1 represents the mode chart of the hydrofluoric acid generating apparatus of present embodiment.This hydrofluoric acid generating apparatus is provided as the distillation tower 1 of distillation mechanism, the raw material that process furnace 2 is set in the inside of this distillation tower 1 and is communicated in this process furnace 2 drops into path 3, and be provided be communicated with process furnace 2 and the water vapour of top one side of distillation tower 1 supply with the spirrillum path 4 of usefulness, and the hexafluorosilicic acid gas that is communicated with the top opposite side of process furnace 2 and distillation tower 1 send the spirrillum path 5 of usefulness.
Drop into path 3 at raw material, be connected with raw material input port 8 via open and close valve 6 and feeding funnel 7, and further drop into path 3, be connected with crystallinity silica trench 41 via open and close valve 42, and be connected with phosphoric acid groove 43 via open and close valve 44 at raw material.And, at process furnace 2, connecting solution tank 11 via open and close valve 12, this solution tank 11 stores for example sodium hydroxide (NaOH) or strong acid solution sulfuric acid (H for example of strong base solution
2SO
4).Then, at path 4, be connected with water vapour generation trough 10 via open and close valve 9.Water vapour generation trough 10 heating pure water generate the water vapour of pure water, and this water vapour is supplied with in process furnace 2 from path 4, clean the hexafluorosilicic acid gas that circulates in path 5.And, in the bottom of process furnace 2, via pipeline 35 and open and close valve 36 and be provided with the waste liquid tank 37 of closed type.This pipeline 35 be arranged at do not allow the aftermentioned sorbent material by, and only allow waste liquid to run underneath to the solid-liquid separation path of waste liquid tank 37.This solid-liquid separation path also can form netted path or on the top of pipeline 35 strainer is set and constitute.
At the end of sending of path 5, be connected with cooling tower 16 via the access 15 that is provided with valve for preventing reverse-flow 14 as cooling body.This cooling tower 16 will and make its hydrolysis form hydrofluoric acid (HF+H by hexafluorosilicic acid liquefaction of gases that distillation procedure generated
2O); Pipe 17 and cooling coil 18 in this cooling tower 16 possesses, described interior pipe 17 flows down hexafluorosilicic acid gas from its upper end and is connected in above-mentioned valve for preventing reverse-flow 14 lower ends, and described cooling coil 18 helicallies are wound in the periphery of pipe 17 in this and at internal circulation water coolant (process water or pure water) are arranged.And, being connected with remover 46 in the upper end of above-mentioned valve for preventing reverse-flow 14, it removes the silicon tetrafluoride gas that hydrolysis produced by hexafluorosilicic acid gas.In addition, the temperature when using valve for preventing reverse-flow 14 to prevent to be stopped by distillation reduces that the pressure difference of being followed is caused fluoridizes the hydracid adverse current from cooling tower 16 distilled, also can use the open and close valve of attached valve for preventing reverse-flow to replace valve for preventing reverse-flow 14.Furthermore, pipe 17 lower end in above-mentioned is provided with the bin of fluoridizing hydracid 21 that storage has liquefied via open and close valve 19 and pipeline 20.
Next section at bin 21 is connected with the upgrading tower 25,26,27 that a plurality of conducts concentrate mechanism via open and close valve 22, pipeline 23 and open and close valve 24.Upgrading tower 25,26,27th, corresponding to the concentrated mechanism of the purposes purpose hydrofluoric acid concentration that the hydrofluoric acid simmer down to that is liquefied by cooling tower 16 is specific, its moisture as solvent in the hydrofluoric acid by the evaporation specified quantitative is adjusted hydrofluoric acid concentration.The hydrofluoric acid concentration of each upgrading tower 25,26,27 is identical or different respectively all can.In addition, because H
2O is 100 ℃ of evaporations, and the boiling point of hydrofluoric acid is 108 ℃, therefore heat below 100 ℃ concentrated.Then, at upgrading tower 25,26,27 top is provided with pipeline 29, and it possesses the dissipation valve 28 that makes when concentrated water vapour dissipate to the valve for preventing reverse-flow structure in the atmosphere.And at upgrading tower 25,26,27 bottom is provided with via pipeline 30 and open and close valve 31 and stores the bin 32,33,34 that is concentrated to the hydrofluoric acid of specific concentrations.
Then, the hydrofluoric acid generation method to the hydrofluoric acid generating apparatus that uses above-mentioned formation describes.
At first, the adsorbent A that 8 input solid are finished using in the raw material input port.Adsorbent A is with activated alumina (this activated alumina is porous matter and the noncrystalline matter aluminum oxide with big specific surface area, has the strong characteristic of adsorptive power) and silicon-dioxide (SiO
2) be sorbent material as the pottery of principal constituent; Can be from the hydrofluoric acid draining that mixes objectionable impuritiess such as various heavy, waste liquid by this sorbent material, utilize the adsorption filtration method come simultaneously or the interim fluorine that comprises in this draining, the waste liquid removed in interior multiple harmful substances.Here, use the adsorbent A that becomes the absorption state of saturation because of use.In the adsorbent A of this absorption state of saturation, HF (fluorochemical) becomes the silicon-dioxide (SiO as the adsorbent A composition
2) and HF (fluorochemical) bonded compound, i.e. hexafluorosilicic acid (H
2SiF
6) state.That is, easy and other melts combine of fluorion in HF (fluorochemical) monomer, but in the adsorbent A of absorption state of saturation, owing to be rendered as the state of hexafluorosilicic acid, so fluorion is difficult for and other melts combine.This adsorbent A is via feeding funnel 7, open and close valve 6, path 3 and drop down onto process furnace 2.
In this process furnace 2, inject and the corresponding highly basic of weight (for example sodium hydroxide) of adsorbent A or the solution B of strong acid (for example sulfuric acid) from solution tank 11 in advance.Thus, dropping down onto the adsorbent A of finishing using of process furnace 2 and the solution B of highly basic or strong acid reacts and the stripping fluorochemical.In addition, when on adsorbent A, being adsorbed with metal ingredient such as fluorochemical and lead or solvability iron simultaneously, in distillation tower 1 if with strong base solution or strong acid solution reaction, then from adsorbent A except the stripping fluorochemical, also can the stripping metal ingredient.
Dropping into the solution B of process furnace 2 can suitably select according to situation.For example solution B then follows distillation procedure also can microdistillation go out sulfate ion (SiO if use sulfuric acid
4 -), though produce the influence that is mixed in distillate, sulfate ion does not belong to the restrictive substance of draining restriction and underground infiltration lambda limiting process etc., in the metal washing procedure, sometimes also mixing such as hydrofluoric acid and nitric acid, sulfuric acid are used as mixing acid and use, so its influence degree is little.And, sulfate ion has also been established to adsorb with commercially available dedicated ion exchange resin and has been removed or make itself and solvability iron chemical combination and make the general treatment process that iron sulphide carries out precipitation process, and according to circumstances the method for removing processing from distillate also is easy.
Furthermore, handle, can avoid sulfate ion to be mixed in distillate if use sodium hydroxide to carry out stripping.Fig. 2 represents comparison sodium hydroxide and the sulfuric acid experimental result from adsorbent A stripping fluorochemical amount.As shown in Figure 2, handle sodium hydroxide (NaOH) or sulfuric acid (H as stripping from the fluorochemical of the containing metal composition of adsorbent A
2SO
4) the either party all demonstrate stripping, but the result of extraction of sodium hydroxide is big slightly.
So,, carry out stripping with sulfuric acid when the mix sulphur acid ion can not constitute problem and handle, require hydrofluoric acid purity (not having other impurity) Shi Zeyi to handle with sodium hydroxide according to the desired hydrofluoric acid specification of user.
And, from crystallinity silica trench 41 the crystallinity silicon-dioxide and the adsorbent A of trace together dropped into process furnace 2, and further drops into the phosphoric acid of trace from phosphoric acid groove 43.When not adding crystallinity silicon-dioxide, the fluorochemical of stripping and metal ingredient can react and generate metal fluoride in process furnace 2.The boiling point of metal fluoride is very high, is difficult to carry out distillation procedure.Yet,, can prevent fluorochemical (HF) and metal reaction, and generate hexafluorosilicic acid (H once again by adding the crystallinity silicon-dioxide of trace
2SiF
6).
And, if use adsorbent A and sulfuric acid to react as strong acid solution, keep former state and stripping as the hexafluorosilicic acid that the silicon-dioxide of adsorbent A composition and fluorochemical reaction are generated, the composition of adsorbent A disappears, the problem that generation can't reuse, but have the advantage that can prevent this problem by adding crystallinity silicon-dioxide.
In addition,,, follow in the regeneration of the hexafluorosilicic acid of distillation procedure and distillate and significantly to reduce, silicon-dioxide that therefore must selective freezing therefore if use amorphous silicon-dioxide because fluorochemical is difficult to and amorphous silicon dioxde reaction.
Furthermore, when not dropping into micro-phosphoric acid, activated alumina as the adsorbent A principal constituent, that is aluminium component can react with the solution B of highly basic or strong acid, being captured the fluorochemical that enters in the adsorbent A can't stripping, and causes melts combine with aluminium component and generate the reaction of metal fluoride.As the Inhibitors of this reaction, can stop aluminium component and fluorochemical reaction by adding micro-phosphoric acid.
As more than, in process furnace 2,, shown in following chemical formula, generate hexafluorosilicic acid (H from the fluorochemical (HF) of adsorbent A stripping and crystallinity silicon dioxde reaction
2SiF
6) and water (2H
2O).
6HF+SiO
2→H
2SiF
6+2H
2O
Here, the Heating temperature of the distillation procedure that will be undertaken by process furnace 2 is set at 120 ℃～160 ℃, more suitablely is set at 130 ℃～150 ℃, You Yi is set at 145 ℃, then because the boiling point of hexafluorosilicic acid is about 110 ℃, water boiling point is about 100 ℃, so both sides all can become vaporized state.The temperature of scope thus, only low-boiling hexafluorosilicic acid gasification, distillating of hexafluorosilicic acid becomes maximum, thereby can stop other high heavy metal objectionable impurities evaporation of boiling point.
Hexafluorosilicic acid (the H that is generated like this
2SiF
6) utilize the water vapour of sending here from water vapour generation trough 10 to be cleaned to cooling tower 16.Be set at Heating temperature in the distillation tower 1 opportunity of utilizing water vapour to begin to clean and reach stage more than 130 ℃.In addition, if generate water vapour under less than 130 ℃ lesser temps in the temperature of distillation tower 1, then water vapour can condense on the pipe arrangement path halfway, hexafluorosilicic acid gas is stagnated halfway, the result is because the moisture that generates on the pipe arrangement face, can cause hydrolysis in the stage midway that is led to cooling tank 16, the hexafluorosilicic acid concentration that enters cooling tank 16 reduces.And, since water vapour halfway stage cohesion be moisture, so steam vapour amount increases and then hexafluorosilicic acid concentration reduces this vicious cycle and repeats, the efficient that distillates of hexafluorosilicic acid reduces, and causes the regenerated hydrofluoric acid concentration to reduce.On the other hand, if the Heating temperature of using distillation tank 1 is at the water vapour that is generated more than 130 ℃, even mix with 100 ℃ water vapour, temperature still can not become below 100 ℃, almost do not have the water vapour cohesion in the path midway, can roughly send into hexafluorosilicic acid gas to cooling tank 16 to greatest extent.
In addition, if the steam vapour amount of above-mentioned cleaning is many, then the concentration of distillate reduces, that is in cooling tank 16 coolings, hydrolysis takes place and the concentration of the hydrofluoric acid that generates reduces.Therefore, the water vapour speed sent into from water vapour generation trough 10 of following control.That is, water vapour generation speed in the early stage the stage since hexafluorosilicic acid gas distillate energetically progress, therefore be purpose to reduce steam vapour amount, 1 minute speed setting is the speed with respect to the amount of the total amount generation 1/10 of reaction volume, and interim ground pick up speed, reach about about 1 times～5 times stage with respect to reaction volume in distilled liquid measure total amount, stop the cleaning of water vapour.Thus, can carry out distillating of hexafluorosilicic acid gas gross effectively, can prevent that hydrofluoric acid concentration from reducing with minimal steam vapour amount.
The pure water water vapour of delivering to the hexafluorosilicic acid gas of cooling tower 16 and cleaning usefulness in flowing down, manage 17 during, the coil 18 that is cooled is cooled to 1 ℃～20 ℃ temperature range, more suitable be cooled to about 10 ℃ and liquefying.In addition, also can use refrigerant to replace circulating in the water coolant of cooling coil 18, and about being set in cooling temperature below 10 ℃.In this process of cooling, hexafluorosilicic acid is hydrolyzed shown in following reaction formula, and is decomposed into fluorochemical, water and silicon tetrafluoride (gas).
H
2SiF
6→2HF+SiF
4↑
Therefore the boiling point of the silicon tetrafluoride that is generated is low to moderate-86 ℃, be vaporized state under this temperature, from being connected in the valve for preventing reverse-flow 14 of managing 17 upper end in above-mentioned via remover 46 discharge that is decomposed.
On the other hand, about 20 ℃ of the boiling point of the fluorochemical that is generated (HF) can not gasify under the cooling temperature of cooling tower 16, and owing to have rapidly water-soluble character, therefore dissolves in the pure water and becomes hydrofluoric acid, and temporarily be stored in bin 21.
The hydrofluoric acid that is stored in bin 21 is via open and close valve 22, pipeline 23, open and close valve 24 and be supplied to upgrading tower 25,26,27, and is adjusted into required hydrofluoric acid concentration.If the adjustment of relevant this hydrofluoric acid concentration of illustration, pure water with respect to 1900 liters, when the hydrofluoric acid (distillate) that hydrolysis generated by the hexafluorosilicic acid liquefaction of gases is 100 liters, generation concentration is 5% hydrofluoric acid, if make the moisture of 1000 liters of its evaporations at upgrading tower, then become the hydrofluoric acid of 100/ (900+100) * 100=10%, can be with 2 times of hydrofluoric acid concentration simmer down tos.That is, only, can concentrate hydrofluoric acid concentration arbitrarily by the vaporize water component.In addition, if for example hydrofluoric acid concentration that the user expected is a kind, then upgrading tower only is 1 and gets final product.
As above detailed description, the hydrofluoric acid generating apparatus of above-mentioned embodiment is to utilize with activated alumina (Al
2O
3) and silicon-dioxide (SiO
2) be adsorbent A as the pottery of principal constituent, the fluorine cpd or the mixture that will contain fluorochemical HF, the fluorochemical that is contained in for example draining, waste liquid, waste and the waste gas carries out adsorption treatment, and uses the adsorbent A after the adsorption treatment to make hydrofluoric acid regenerated device; Wherein, possess distillation tank 1 and cooling tank 16, distillation tank 1 adds solution B, micro-phosphoric acid and the crystallinity silicon-dioxide of adsorbent A, highly basic or strong acid, after fluorochemical is separated from adsorbent A, generate hexafluorosilicic acid once again, and making its gasification, cooling tank 16 will form hydrofluoric acid by the hexafluorosilicic acid liquefaction of gases and the hydrolysis that distillation procedure generated of water vapour.
According to this structure, distillation tank 1 makes adsorbent A and for example sodium hydroxide or the reaction of vitriolic solution B, make the fluorochemical and other impurity stripping that are adsorbed in adsorbent A, utilize fluorochemical to understand rapidly and the character of crystallinity silicon dioxde reaction, generate hexafluorosilicic acid (H once again
2SiF
6), hexafluorosilicic acid can gasify easily under about temperature more than 110 ℃ and distillate.Owing to the boiling point of hexafluorosilicic acid is about about 110 ℃ than water is high slightly, therefore easily and water sepn, and because boiling point is low, so heat energy is also little, so it is also cheap to distill cost.
And, according to the character of the easy hydrolysis of hexafluorosilicic acid, with after water vapour mixes, water vapour becomes the character of water when utilizing cooling through hexafluorosilicic acid gas that water vapour cleaned, hexafluorosilicic acid and water through liquefaction react and hydrolysis, thereby can easily obtain hydrofluoric acid from hexafluorosilicic acid.
Claims (7)
1. hydrofluoric acid generating apparatus, it utilizes with activated alumina and silicon-dioxide is sorbent material as the pottery of principal constituent, from the fluorine cpd that contain fluorion or fluoride mixture, fluorion is carried out adsorption treatment, and use the sorbent material after the adsorption treatment to generate hydrofluoric acid; Wherein, possess distillation mechanism and cooling body:
Described distillation mechanism adds described sorbent material and highly basic or strong acid reacts, and adds crystallinity silicon-dioxide and generate hexafluorosilicic acid gas,
The cooling of described cooling body is by the described distillation hexafluorosilicic acid gas that mechanism generated, and is hydrolyzed and generates hydrofluoric acid.
2. the described hydrofluoric acid generating apparatus of claim 1, wherein, described distillation mechanism further adds phosphoric acid.
3. claim 1 or 2 described hydrofluoric acid generating apparatus, wherein, the Heating temperature of described distillation mechanism distillation procedure is set at 110 ℃～160 ℃.
4. each described hydrofluoric acid generating apparatus in the claim 1～3, wherein, described hydrofluoric acid generating apparatus further comprises wiper mechanism, after the Heating temperature of this mechanism distillation procedure in described distillation mechanism reaches more than 130 ℃, utilize water vapour that hexafluorosilicic acid gas is cleaned extremely described cooling body from described distillation mechanism.
5. the described hydrofluoric acid generating apparatus of claim 4, wherein, the initial stage speed setting that described wiper mechanism cleans water vapour is to send the speed with respect to the water vapour of the about amount below 1/10 of reaction-ure mixture in 1 minute, and interim the cleaning speed of accelerating, reach about 1～5 times stage by the hydrofluoric acid amount that cooling body generated with respect to described reaction-ure mixture, stopping the cleaning of water vapour.
6. claim 4 or 5 described hydrofluoric acid generating apparatus, wherein, described cooling body liquefies hexafluorosilicic acid gas and water vapour 1 ℃～20 ℃ scope and obtains hydrofluoric acid.
7. hydrofluoric acid generation method, it utilizes with activated alumina and silicon-dioxide is sorbent material as the pottery of principal constituent, from the fluorine cpd or fluoride mixture that contain fluorion, it is saturated to adsorbing that fluorion is carried out adsorption treatment, and use the sorbent material after the adsorption treatment to make hydrofluoric acid regeneration; Wherein, have distillation process and refrigerating work procedure, described distillation process stage is added described sorbent material and highly basic or strong acid a certain amount ofly and is reacted, and further add the crystallinity silicon-dioxide of trace and phosphoric acid and react and temporarily generate hexafluorosilicic acid, hexafluorosilicic acid cooling and liquefaction that described refrigerating work procedure one side will generate, one side makes its hydrolysis generate hydrofluoric acid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP191784/2005 | 2005-06-30 | ||
| JP2005191784A JP3785418B1 (en) | 2005-06-30 | 2005-06-30 | Hydrofluoric acid generating apparatus and hydrofluoric acid generating method |
| PCT/JP2006/313008 WO2007004516A1 (en) | 2005-06-30 | 2006-06-29 | Hydrofluoric acid production apparatus and hydrofluoric acid production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101277899A true CN101277899A (en) | 2008-10-01 |
| CN101277899B CN101277899B (en) | 2011-02-02 |
Family
ID=36635812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800203029A Expired - Fee Related CN101277899B (en) | 2005-06-30 | 2006-06-29 | Hydrofluoric acid production apparatus and hydrofluoric acid production method |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP3785418B1 (en) |
| KR (1) | KR100987041B1 (en) |
| CN (1) | CN101277899B (en) |
| WO (1) | WO2007004516A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515107A (en) * | 2011-10-31 | 2012-06-27 | 深圳市新星轻合金材料股份有限公司 | Zero pollution recovery system of safe anhydrous hydrogen fluoride production |
| CN102774813A (en) * | 2011-05-12 | 2012-11-14 | 特力生有限公司 | Method for preparing hydrofluoric acid |
| CN102772911A (en) * | 2012-08-02 | 2012-11-14 | 浙江诺睿特生物科技有限公司 | Cold trap |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5101121B2 (en) * | 2007-02-01 | 2012-12-19 | 森田化学工業株式会社 | Method and apparatus for separating and recovering acid components from waste liquid containing hydrofluoric acid and silicohydrofluoric acid |
| JP5143440B2 (en) * | 2007-02-01 | 2013-02-13 | 森田化学工業株式会社 | Method and apparatus for separating and recovering acid components from waste liquid containing hydrofluoric acid, hydrochloric acid and silicohydrofluoric acid |
| JP2010206962A (en) * | 2009-03-04 | 2010-09-16 | Central Res Inst Of Electric Power Ind | Method of detecting abnormal conditions in gas-insulated power apparatus |
| GB2571584A (en) * | 2018-03-29 | 2019-09-04 | Vexo International Uk Ltd | Fluid treatment |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0615266A (en) * | 1992-07-02 | 1994-01-25 | Japan Organo Co Ltd | Concentration of fluorine-containing waste water |
| CN2644402Y (en) * | 2003-09-02 | 2004-09-29 | 焦作市多氟多化工有限公司 | Coarse hydrofluoric acid refining apparatus |
| JP2004345949A (en) | 2004-05-24 | 2004-12-09 | Matsushita Electric Ind Co Ltd | Method and apparatus for regenerating hydrofluoric acid |
-
2005
- 2005-06-30 JP JP2005191784A patent/JP3785418B1/en active Active
-
2006
- 2006-06-29 WO PCT/JP2006/313008 patent/WO2007004516A1/en active Application Filing
- 2006-06-29 CN CN2006800203029A patent/CN101277899B/en not_active Expired - Fee Related
- 2006-06-29 KR KR1020077027107A patent/KR100987041B1/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102774813A (en) * | 2011-05-12 | 2012-11-14 | 特力生有限公司 | Method for preparing hydrofluoric acid |
| CN102515107A (en) * | 2011-10-31 | 2012-06-27 | 深圳市新星轻合金材料股份有限公司 | Zero pollution recovery system of safe anhydrous hydrogen fluoride production |
| CN102772911A (en) * | 2012-08-02 | 2012-11-14 | 浙江诺睿特生物科技有限公司 | Cold trap |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3785418B1 (en) | 2006-06-14 |
| KR20080018870A (en) | 2008-02-28 |
| KR100987041B1 (en) | 2010-10-11 |
| CN101277899B (en) | 2011-02-02 |
| JP2008094630A (en) | 2008-04-24 |
| WO2007004516A1 (en) | 2007-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101277899B (en) | Hydrofluoric acid production apparatus and hydrofluoric acid production method | |
| KR101030628B1 (en) | Method of recycling fluorine using an adsorption purification process | |
| KR101842303B1 (en) | Method for the purification of fluorine | |
| JP4576312B2 (en) | Manufacturing method of silicon tetrafluoride and manufacturing apparatus used therefor | |
| CN104973573B (en) | A kind of preparation method of the preparation method and high-pure hydrofluoric acid of high-purity hydrogen fluoride | |
| CN106430117A (en) | Method for preparing analytical pure sulfuric acid by using smelting flue gas | |
| JP2023524919A (en) | Separation and purification method for refining industrial-level high-concentration HF to electronic-level FTrPSA | |
| CN108313983A (en) | The hydrofluoric acid purifying prepared for high purity lithium fluoride and preparation method | |
| US7637986B2 (en) | Process for refining nitrogen trifluoride gas using alkali earth metal exchanged and impregnated zeolite | |
| CN102256896A (en) | Process for the preparation of fluorine compound | |
| CN101027248B (en) | Process for producing fluorine gas | |
| EP1938888B1 (en) | Isotope concentration method | |
| JP4314015B2 (en) | Portable ultra-high purity acetylene feeder | |
| JP2001232134A (en) | Method and device for neon recovering | |
| KR102326287B1 (en) | Method for manufacturing polycrystalline silicon | |
| CN1159220C (en) | Process for purifying and recovering ammonia gas | |
| CN210463763U (en) | N2O purification device and production system | |
| IL160854A (en) | Process and apparatus for purifying hydrogen bromide | |
| CN112110589B (en) | Harmless treatment method of high-concentration buffer hydrofluoric acid etching waste liquid | |
| CN103011172A (en) | Purification method of impurity iodine in silicon tetrafluoride gas | |
| JP2004345949A (en) | Method and apparatus for regenerating hydrofluoric acid | |
| TWI717295B (en) | Electronic grade hydrofluoric acid manufacturing system and method for manufacturing electronic grade hydrofluoric acid using the system | |
| JP3481920B2 (en) | Concentration method of fluorine compound | |
| KR102612965B1 (en) | Adsorbent composition for carbon monoxide gas purification and carbon monoxide purification method using the adsorbent composition | |
| CN113620252B (en) | Electronic grade hydrofluoric acid manufacturing system and method for manufacturing electronic grade hydrofluoric acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: JAPAN VERTEX CO., LTD. Free format text: FORMER NAME: J-TOP SERVICE CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: Osaka Japan Co-patentee after: Sakaikouhan Co., Ltd. Patentee after: Apex Japan Ltd Address before: Osaka Japan Co-patentee before: Sakaikouhan Co., Ltd. Patentee before: J-top Service Co., Ltd. |
|
| C56 | Change in the name or address of the patentee |
Owner name: TOP CO., LTD. Free format text: FORMER NAME: JAPAN VERTEX CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: Osaka Japan Patentee after: Apex Japan Inc Patentee after: Sakaikouhan Co., Ltd. Address before: Osaka Japan Patentee before: Apex Japan Ltd Patentee before: Sakaikouhan Co., Ltd. |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110202 Termination date: 20130629 |