CN103663522B - Crystallization system and the crystallization method thereof of sodium fluoroaluminate crystal is generated from hydrofluoric acid waste liquid - Google Patents
Crystallization system and the crystallization method thereof of sodium fluoroaluminate crystal is generated from hydrofluoric acid waste liquid Download PDFInfo
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Abstract
The invention discloses a kind of from hydrofluoric acid waste liquid generation sodium fluoroaluminate (Na
3alF
6) crystallization system of crystal and crystallization method thereof, it mainly arranges certain flow and dispersed dosing section in this system response groove notch, make medicament be batch fixing quantity and add in hydrofluoric acid waste liquid dispersedly to react, and coordinate the method steps of trend crystallization: a hydrofluoric acid waste liquid influent stream step, one sodium aluminate administering step, one crystallization reaction step, one sodium fluoroaluminate crystal separates out settling step, one filtration step, and a drain step, the operator scheme purification hydrofluoric acid waste liquid of known chemical coagulation is replaced with crystallization operation pattern, promote reaction efficiency and the crystallization purity of hydrofluoric acid waste liquid and medicament, reach efficient recovery fluorine, reduce the volume of chemical sludge and generate the object of tool high economic benefit sodium fluoroaluminate crystal.
Description
Technical field
The present invention relates to a kind of crystallization system generating sodium fluoroaluminate crystal from hydrofluoric acid waste liquid, particularly relate to a kind of crystallization system that effectively the fluorion crystallization in hydrofluoric acid waste liquid can be turned to sodium fluoroaluminate crystal; The invention still further relates to a kind of crystallization method of this crystallization system.
Background technology
High concentration of hydrofluoric acid (HF, 49%) or hydrofluoric acid nitration mixture, for the scientific and technological industrys such as semi-conductor (IC), display panels (TFT-LCD), solar cell are widely used in etching technique, thus output concentration up to 49% or be low to moderate 0.5% various concentration and bulky hydrofluoric acid spent acid, need to carry out liquid waste disposal.
Current hydrofluoric acid waste liquid treatment process, to add as CaO, Ca (OH)
2, CaCl
2react Deng the fluorion in calcium containing compound and waste liquid and generate Calcium Fluoride (Fluorspan) (CaF
2) sludge cake, reach the object of the fluorion removed in waste liquid, but, after this method needs that in treating processes high concentration of hydrofluoric acid thin up is become low concentration hydrofluoric acid waste liquid, add calcium containing compound again, fluorion and the true son of calcium is made to produce calcium fluoride precipitate, especially react completely for making, actual chemical feeding quantity is generally theoretical value more than two times, not only increase operational difficulty degree, running cost is high, more can produce compared to hydrofluoric acid waste liquid volume about 5 to 10 times, but Calcium Fluoride (Fluorspan) purity is wherein low only have 15 to 40% calcium fluoride sludge, secondary pollution is formed to environment and is difficult to the economic benefit with recycling.
Although there is Dutch DHV company at present, fluidized bed crystallization groove (the Fluidized-BedCrystallizer of U.S. PERMUTIT company designs, FBC) technology, and the high thin air trunking crystallizer tank (HighAspectRateDraftTubeAgitatedCrystallizer of E.I.Du Pont Company, HARDTAC) technology can assist the problem improving aforementioned crystalline purity, but it should be noted that, the volume loading rate of such as fluorine, Al/F mol ratio, pH value, the fluoro-containing concentration of influent stream waste liquid ... etc. being all the variable affecting crystallization purity, crystallization purity is caused to want be promoted to the purity rubric that meets industry demand and have the economic benefit being recovered utilization to seem very difficult, the economic benefit that in another recovery mud, crystallization produces to running cost and the crystallization of recoverable will become another consideration emphasis.
No. I233428th, TaiWan, China patent is had to disclose a kind for the treatment of process and treatment agent thereof of fluoride waste, its fluorine-containing waste liquid in middle layer after leaving standstill adds by the confection containing aluminium or compounds containing sodium and combination thereof, to adjust the pH value of fluorine-containing waste liquid and the positively charged ion removed in fluorine-containing waste liquid, add by the treatment agent containing aluminium, form containing sodium and chlorine-containing compound again, make the fluorion in fluorine-containing waste liquid and medicament carry out chemical coagulation effect, reach and form sodium aluminum fluoride sodium fluoroaluminate throw out for doing him;
But the treatment process of this patent does not state clearly its fluorine-containing liquid waste concentration, and it is high with the water ratio of traditional chemical Coagulation with Treatment, still has the bulky problem of chemical sludge, another use chlorine-containing compound PAC (PolyaluminumChloride; Polynary poly aluminium chloride) as coagulant aids, affect the sedimentary purity of sodium aluminum fluoride, especially this patent treatment process obtains sodium aluminum fluoride with noncrystalline program, and its throw out purity is obviously difficult to the value reaching recycling.
No. I353343rd, TaiWan, China patent discloses and a kind ofly in hydrofluoric acid waste liquid, reclaims fluorine and manufacture the method for silicofluoride, it, mainly in hydrofluoric acid containing (HF) waste liquid and the direct contact reacts of silicon-containing compound, makes the hydrofluoric acid in waste liquid and silicon-containing compound react and generates silicofluoric acid (H
2siF
6) after, the concentration of adjustment fluorine silicon acid waste liquid, and the alkali added containing sodium or potassium or an alkali metal salt, thus generate silicofluoride throw out, again through Sodium Silicofluoride or potassium silicofluoride being isolated in waste liquid and after drying, reaching and form callable Sodium Silicofluoride, potassium silicofluoride product;
But, in the silicofluoride manufacture method of this patent, there is the performance constraint that hydrofluoric acid containing waste liquid and fluorine silicon acid waste liquid must be made to maintain 5 to 15wt%, too low or too high cannot output meet economic benefit silicofluoride and increase running cost, especially silicofluoric acid is thermopositive reaction with containing sodium or the alkali of potassium or the neutralization of an alkali metal salt, make the temperature of reaction in operating process form another controling parameters, cause the operational difficulty degree promoting this patent.
Because above-mentioned conventional operation problem, inventor conceives a kind of crystallization system and the crystallization method thereof that generate sodium fluoroaluminate crystal from hydrofluoric acid waste liquid, above-mentionedly carries out to generate fluorine-containing xln the problem that fluorine recovery produces to eliminate.
Summary of the invention
The object of the present invention is to provide a kind of crystallization system generating sodium fluoroaluminate crystal from hydrofluoric acid waste liquid, medicament mainly to react with batch fixing quantity through a dispersion impeller dispersed adding in hydrofluoric acid waste liquid by it, the operator scheme purification hydrofluoric acid waste liquid of known chemical coagulation is replaced with crystallization operation pattern, the volume of effective reduction chemical sludge, and reach the object promoting xln purity.
Another object of the present invention is to provide a kind of crystallization method generating sodium fluoroaluminate crystal from hydrofluoric acid waste liquid, the method is to tend to the reaction conditions of crystallization, medicament is batch fixing quantity and adds in hydrofluoric acid waste liquid dispersedly and react, make the fluorine in waste liquid and medicament react the sodium fluoroaluminate crystal of generating structure closely, in graininess, reach efficient recovery fluorine and the object of generation tool high economic benefit sodium fluoroaluminate crystal.
For reaching above-mentioned purpose, according to a kind of crystallization system generating sodium fluoroaluminate crystal from hydrofluoric acid waste liquid provided by the present invention, it comprises a high concentration of hydrofluoric acid waste liquid tank exports a certain amount of hydrofluoric acid waste liquid to batch crystallization reaction section reactive tank through one batch of fixing quantity section, and a sodium aluminate pharmacy slot exports a homodisperse sodium aluminate liquid through one batch of fixing quantity section and certain flow and dispersed dosing section and to flow in this reactive tank quantitative hydrofluoric acid waste liquid with this and carry out crystallization reaction; Wherein:
This reactive tank, be top formed have a notch and one dispensing space, bottom has an outlet and a reaction compartment; This constant flow and dispersed dosing section, cording has a dispersion impeller to be provided with plural fluid apertures, and this dispersion impeller periphery and this reactive tank inwall level set firmly, and this reactive tank inside is for this dispersion impeller is every being set as this dispensing space of shape and this reaction compartment; By this, this quantitative hydrofluoric acid waste liquid is made to be placed in this reaction compartment, the a certain amount of sodium aluminate solution that batch fixing quantity section of this sodium aluminate solution exports is that this dispersion impeller is every being located in this dispensing space, and distribute through this fluid apertures of this dispersion impeller, form this homodisperse sodium aluminate liquid stream and input this reaction compartment and this quantitative hydrofluoric acid waste liquid uniform contact is carried out reacting and generates sodium fluoroaluminate crystal.
According to a kind of crystallization system generating sodium fluoroaluminate crystal from hydrofluoric acid waste liquid provided by the invention, wherein, this constant flow and dispersed dosing section have a controlling board and stack on this dispersion impeller top, and one propulsion source be located at bottom this dispersion impeller, it is affixed that this propulsion source cording has a transmission shaft to place this dispersion impeller center and this controlling board center, this dispersion impeller system is provided with the fluid apertures of this plural number radiation arrangement, and this controlling board is provided with plural number to should the through hole of dispersion impeller fluid apertures quantity, this propulsion source is made to drive this controlling board to rotate, this controlling board through hole and this dispersion impeller fluid apertures this quantitative sodium aluminate solution of block that misplaces circulates, or, this controlling board through hole and this dispersion impeller fluid apertures involutory, this homodisperse sodium aluminate liquid stream is made to enter reaction compartment and this quantitative hydrofluoric acid waste liquid contact reacts from dispensing spatial flow.
According to a kind of crystallization method generating sodium fluoroaluminate crystal from hydrofluoric acid waste liquid provided by the invention, the method step comprises: a, hydrofluoric acid waste liquid influent stream step: input in a reactive tank by a high concentration of hydrofluoric acid waste liquid through a batch fixing quantity, this reactive tank system is top formed a notch and a dispensing space, bottom has an outlet and a reaction compartment, and this quantitative hydrofluoric acid waste liquid system is placed in this reaction compartment; B, sodium aluminate administering step: the dispersion impeller that offers plural equally distributed fluid apertures is provided, by this dispersion impeller with its periphery with should be that horizontal configuration sets firmly with this reactive tank inwall, this reactive tank inside is configured as this dispensing space and this reaction compartment for this dispersion impeller every establishing, by a sodium aluminate solution after batch fixing quantity, input a certain amount of sodium aluminate solution in this dispensing space with every batch of time of administration of 1 to 1.5 hour; C, crystallization reaction step: make this quantitative sodium aluminate solution flow through this dispersion impeller fluid apertures and form a homodisperse sodium aluminate liquid and flow to into this reaction compartment, and mat controls the flow velocity that this quantitative sodium aluminate solution enters this reactive tank reaction compartment, make this homodisperse sodium aluminate liquid stream in batch time of administration, slow and this quantitative hydrofluoric acid waste liquid carries out crystallization reaction, and stops when this quantitative sodium aluminate solution is used up; D, sodium fluoroaluminate crystal separate out settling step: mixing solutions in reactive tank is left standstill 60 to 90 minutes, makes the aluminum ion of the fluorion in this high concentration of hydrofluoric acid waste liquid and this sodium aluminate solution and sodium ion carry out crystallization reaction to separate out sodium fluoroaluminate crystal and to be settled down to reaction tank bottom; E, filtration step: waste liquid after crystal and crystallization reaction is flowed out from the outlet of this reaction tank bottom and filters, to obtain this sodium fluoroaluminate crystal, and discharges a low concentration hydrofluoric acid waste liquid.
According to a kind of crystallization method generating sodium fluoroaluminate crystal from hydrofluoric acid waste liquid provided by the invention, wherein, the crystal purity of the sodium fluoroaluminate crystal of this filtration step gained is greater than 80%, and the water ratio of this sodium fluoroaluminate crystal is for being less than 15%.
Having about the present invention for reaching above-mentioned purpose, the technology adopted, means and other effects, hereby lifting a better possible embodiments and coordinating graphic being described in detail as follows.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation:
Fig. 1 is the program circuit schematic diagram of the sodium fluoroaluminate crystallization system of hydrofluoric acid waste liquid of the present invention;
Fig. 2 is the crystallization reaction groove structural representation of present system;
Fig. 3 A-3B is the hole count controlling board structural representation of sodium aluminate medicine system of the present invention;
Fig. 4 A is 20 hole dispersion impellers and the hole count controlling board unitized construction schematic diagram of sodium aluminate medicine system of the present invention;
Fig. 4 B is 16 hole dispersion impellers and the hole count controlling board unitized construction schematic diagram of sodium aluminate medicine system of the present invention;
Fig. 4 C is 8 hole dispersion impellers and the hole count controlling board unitized construction schematic diagram of sodium aluminate medicine system of the present invention;
Fig. 5 is the crystallization method step schematic diagram of present system;
Fig. 6 is sodium fluoroaluminate crystal X-ray diffraction analysis figure of the present invention;
Fig. 7 is known a kind of sodium fluoroaluminate crystal X-ray diffraction analysis figure;
Fig. 8 is known another kind of sodium fluoroaluminate crystal X-ray diffraction analysis figure.
Primary clustering nomenclature:
High concentration of hydrofluoric acid waste liquid tank V1
Sodium aluminate pharmacy slot V2
Batch fixing quantity section F1, F2
Dosing side Pu F21 liquidometer F22
Constant flow and dispersed dosing section A
Dispersion impeller A1 fluid apertures A11
Controlling board A2 through hole A20
First sets of vias A21 second sets of vias A22
Third through-hole group A23
Propulsion source A3 transmission shaft A31
Batch crystallization reaction section R
Reactive tank R1 notch R11
Outlet R12 dispensing space R13
Reaction compartment R14
Micro-filtration section S
Low concentration hydrofluoric acid liquid waste disposal section W
High concentration of hydrofluoric acid waste liquid 1 is hydrofluoric acid waste liquid 11 quantitatively
Sodium aluminate solution 2 is sodium aluminate solution 21 quantitatively
Waste liquid 3 after drop-wise sodium aluminate solution 22 crystal and crystallization reaction
Low concentration hydrofluoric acid waste liquid 4 sodium fluoroaluminate crystal 5
Liquid level H angle θ
Center line L
Hydrofluoric acid waste liquid influent stream step S1
Sodium aluminate administering step S2
Crystallization reaction step S3
Sodium fluoroaluminate crystal separates out settling step S4
Filtration step S5
Drain step S6
Embodiment
First, as Figure 1-3, provided by the present invention a kind of from the crystallization system of hydrofluoric acid waste liquid generation sodium fluoroaluminate crystal and the preferred embodiment of crystallization method thereof; Crystallization system as shown in Figure 1, this crystallization system mainly comprises a high concentration of hydrofluoric acid waste liquid tank V1, one batch of fixing quantity section F1, sodium aluminate pharmacy slot V2, one batch of fixing quantity section F2, certain flow and dispersed dosing section A, a batch crystallization reaction section R, a micro-filtration section S, and a low concentration hydrofluoric acid liquid waste disposal section W; Following form illustrates numbering and the title thereof of this system each section of program, and between each section, fluid is numbered and title:
The each segment number of system and title thereof:
Each intersegmental fluid numbering and title thereof:
As shown in Figure 1, the high concentration of hydrofluoric acid waste liquid tank V1 of crystal system of the present invention is for storing high concentration of hydrofluoric acid waste liquid 1, this sodium aluminate pharmacy slot V2 is for storing sodium aluminate solution 2, through these two batches of fixing quantity section F1, F2, respectively by quantitative hydrofluoric acid waste liquid 11 influent stream to this batch crystallization reaction section R, and quantitative sodium aluminate solution 21 is delivered to this constant flow and dispersed dosing section A, quantitative sodium aluminate solution 21 is formed homodisperse sodium aluminate solution 22 by the design of its medicament dispersion impeller of mat, the quantitative hydrofluoric acid waste liquid 11 using and be contained in batch crystallization reaction section R carries out crystallization reaction, separate out through leaving standstill after homodisperse sodium aluminate liquid stream 22 is used up again, precipitation sodium fluoroaluminate crystal, then waste liquid 3 after crystal and crystallization reaction is isolated sodium fluoroaluminate crystal 5 and low concentration hydrofluoric acid waste liquid 4 through this micro-filtration section S, finally this low concentration hydrofluoric acid waste liquid 4 is inputted this low concentration hydrofluoric acid liquid waste disposal section W process,
Wherein, as shown in Figure 2, the batch crystallization reaction section R of present system is provided with a reactive tank R1, and this reactive tank R1 is top formed a notch R11 and dispensing space R13, and bottom has an an outlet R12 and reaction compartment R14; As shown in Figure 3A, this constant flow and dispersed dosing section A have the dispersion impeller A1 made with stainless steel plate and are located at quantitative hydrofluoric acid waste liquid 11 ullage in this reactive tank R1, this dispersion impeller A1 is provided with plural fluid apertures A11 and sets firmly with its periphery and this reactive tank R1 inwall level, with by this reactive tank R1 inside for this dispersion impeller A1 every being set as this dispensing space R13 of shape and this reaction compartment R14;
By this, this quantitative hydrofluoric acid waste liquid 11 is made to be placed in this reaction compartment R14, the a certain amount of sodium aluminate solution 21 of this batch of fixing quantity section F2 output is for this dispersion impeller A1 is every being located in the R13 of this dispensing space, and distribute through this fluid apertures A11 of this dispersion impeller A1, form this homodisperse sodium aluminate liquid stream 22 and input this reaction compartment R14 and this quantitative hydrofluoric acid waste liquid 11 uniform contact is carried out reacting and generates sodium fluoroaluminate crystal 5.
Please coordinate shown in Fig. 3 A, 3B with Fig. 2, when only arranging dispersion impeller A1 in reactive tank R1, be added to the quantitative sodium aluminate solution 21 of reactive tank R1 dispensing space R13, the direct fluid apertures A11 by dispersion impeller A1 is entered reaction compartment R14 dispersedly and quantitative hydrofluoric acid waste liquid 11 carries out crystallization reaction, and when homodisperse sodium aluminate liquid stream 22 flow velocity is less than quantitative sodium aluminate solution 21 flow velocity, this quantitative sodium aluminate solution 21 is accumulated on the upside of dispersion impeller A1 and forms a liquid level H;
It should be noted that, during owing to only arranging dispersion impeller A1 in reactive tank R1, flow velocity and the flow of this homodisperse sodium aluminate liquid stream 22 will be subject to very big limitation, by this, as Fig. 2, shown in 3B, crystallization system of the present invention stacks in this dispersion impeller A1 top the controlling board A2 that is provided with plural through hole A20, and this controlling board of propulsion source A3 drived control A2 that mat one is located at bottom this dispersion impeller A1 rotates, utilize the dislocation or involutory of dispersion impeller A1 fluid apertures A11 and controlling board A2 through hole A20, reach the quantitative sodium aluminate solution 21 liquid level H maintained on the upside of dispersion impeller A1, and adjust the flow velocity that this homodisperse sodium aluminate liquid stream 22 enters reactive tank R1 reaction compartment R14, the object of flow, wherein:
This propulsion source A3 has a transmission shaft A31, and to place this dispersion impeller A1 center and this controlling board A2 center affixed, this dispersion impeller A1 is provided with the fluid apertures A11 of this plural number radiation arrangement, and this controlling board A2 is provided with plural number to should the through hole A20 of dispersion impeller A1 fluid apertures A11 quantity, this propulsion source A3 is made to drive this controlling board A2 to rotate, this controlling board A2 through hole A20 and this dispersion impeller A1 fluid apertures A11 this quantitative sodium aluminate solution 21 of block that misplaces circulates, after being able to be accumulate to certain liquid level on the upside of dispersion impeller A1 to make quantitative sodium aluminate solution 21, revolve control this controlling board A2 through hole A20 and this dispersion impeller A1 fluid apertures A11 more involutory, to guarantee that homodisperse sodium aluminate liquid stream 22 can flow into reactive tank R1 reaction compartment R14 without interruption and contact mixing with this quantitative hydrofluoric acid waste liquid 11 and carry out crystallization reaction,
In addition, as Fig. 3 A, shown in 3B, the present invention for sodium aluminate solution 2 is can be uniformly dispersed with high concentration of hydrofluoric acid waste liquid 1 contact reacts, and reach the object of the flow adjusting homodisperse sodium aluminate liquid stream 22, the plural fluid apertures A11 of this dispersion impeller A1 offers along the arrangement of rice word radiation direction centered by this transmission shaft A31, this controlling board A2 is then provided with at least two and arranges along rice word radiation direction the one first sets of vias A21 and one second sets of vias A22 that offer centered by this transmission shaft A31, respectively this sets of vias A21, A22 is made up of plural through hole A20, each group of through hole A21, sandwiched one angle θ between the rice word arrangement radiation direction of A22, and this first sets of vias A21 has should this plural through hole A20 of dispersion impeller A1 fluid apertures A11 quantity, this two sets of vias A22 has this plural through hole A20 being less than this dispersion impeller A1 fluid apertures A11 quantity,
In the present embodiment, as shown in Fig. 3 A, 3B, this dispersion impeller A1 has that 20 fluid apertures A11 are dispersed to be located in this meter of word radiation direction, this controlling board A2 has three rice word arrangement sets of vias, be respectively this first sets of vias A21, this second sets of vias A22 and a third through-hole group A23, wherein, this first sets of vias A21 has 20 this through hole A20, this second sets of vias A22 has 16 this through hole A20, and this third through-hole group A23 has 8 this through hole A20;
Please coordinate shown in Fig. 4 A-4C with Fig. 3 A, 3B, the operation use-pattern of dispersion impeller A1 of the present invention and controlling board A2 is described; Wherein, as shown in Figure 3 B, define a center line L and extend along the wherein exhausting hole of this first sets of vias A21, a wherein exhausting hole of this second sets of vias A22 and this third through-hole group A23 and this center line L this angle θ of sandwiched and lay respectively at this center line L both sides; In the present embodiment, respectively this sets of vias is rice word radiation arrangement, make this angle θ of sandwiched between each through hole be 15 degree, and this second sets of vias A22 forms in from the negative 15 degree of angles place of this center line L skew, this third through-hole group A23 forms in this center line L and offsets positive 15 degree of angles place;
So, when this controlling board A2 is involutory with its first sets of vias A21 and this dispersion impeller A1 fluid apertures A11, as shown in Figure 4 A, first sets of vias A21 is transmission state in being communicated to this fluid apertures A11, circulate for homodisperse sodium aluminate liquid stream 22, this second, third sets of vias A22, A23 then cover for this dispersion impeller A1, avoid sodium aluminate solution to pass through; As shown in Figure 4 B, after the center line L of display and control dish A2 rotates positive 15 degree of angles, involutory with its second sets of vias A22 and dispersion impeller A1 fluid apertures A11, and cover first, the structure aspect of third through-hole group A21, A23; Again as shown in Figure 4 C, the center line L of display and control dish A2 rotates negative 15 degree of angles, and with the involutory structure aspect of third through-hole group A23 and dispersion impeller A1 fluid apertures A11; Therefore dispersion impeller A1 of the present invention and controlling board A2 through above-mentioned tool different through hole A20 quantity sets of vias A21, the pairing form of A22, A23 and fluid apertures A11, reach and control the object that sodium aluminate solution 2 enters the flow velocity of reaction in reactive tank R1.
Another in the present embodiment, batch fixing quantity section F2 of this sodium aluminate solution 2 has a dosing side Pu F21 enters this constant flow and dispersed dosing section A flow with the sodium aluminate solution 2 controlling this sodium aluminate pharmacy slot V2 output, and this dosing side Pu F21 and liquidometer F22 and this dosing help Pu F21 to be electrically connected, to detect the quantitative sodium aluminate solution 21 liquid level H that this reactive tank R1 offers medicine in the R13 of space, this liquidometer F22 can be a ultrasound liquidometer; Again, this reactive tank R1 exports R12 place and is provided with a micro-filtration section S, it can be the filter bag machine that size of mesh is less than or equal to 10 microns (μm), for filtering waste liquid 3 after a crystal and crystallization reaction that this reactive tank R1 discharges, and export low concentration hydrofluoric acid waste liquid 4 and a sodium fluoroaluminate crystal 5, and a low concentration hydrofluoric acid liquid waste disposal section W is connected with this micro-filtration section S, for the low concentration hydrofluoric acid waste liquid 4 of process fluorinion concentration lower than 3000 milligrams/liter (mg/L).
The above is the present invention generates the crystallization system embodiment of sodium fluoroaluminate crystal primary member and configuration explanation thereof from hydrofluoric acid waste liquid, as crystallization mode and effect thereof of present pre-ferred embodiments, does following explanation.
Please coordinate shown in Fig. 1-Fig. 4 C with Fig. 5, the present invention generates the crystallization method of sodium fluoroaluminate crystal from hydrofluoric acid waste liquid, aforementioned crystalline system is coordinated to use, the method step mainly comprises a hydrofluoric acid waste liquid influent stream step S1, a sodium aluminate administering step S2, a crystallization reaction step S3, an a sodium fluoroaluminate crystal precipitation settling step S4 and filtration step S5, wherein:
This hydrofluoric acid waste liquid influent stream step S1: a high concentration of hydrofluoric acid waste liquid 1 is inputed in a reactive tank R1 through a batch fixing quantity, this reactive tank R1 is top formed a notch R11 and dispensing space R13, bottom has an an outlet R12 and reaction compartment R14, and this quantitative hydrofluoric acid waste liquid 11 is placed in this reaction compartment R14; In the present embodiment, described quantitative hydrofluoric acid waste liquid 11 has 20,000 to 200, the hydrofluoric acid concentration of 000 milligram/liter.
This sodium aluminate administering step S2: the dispersion impeller A1 that offers plural equally distributed fluid apertures A11 is provided, by this dispersion impeller A1 with its periphery with should be that horizontal configuration sets firmly with this reactive tank R1 inwall, this reactive tank R1 inside is configured as this dispensing space R13 and this reaction compartment R14 for this dispersion impeller A1 every establishing, by a sodium aluminate solution 2 after batch fixing quantity, input a certain amount of sodium aluminate solution 21 in the R13 of this dispensing space with every batch of time of administration of 1 to 1.5 hour, the concentration of described quantitative sodium aluminate solution 21 is 30 to 300 grams/liters;
In the present embodiment, the through hole A20 of this controlling board A2 and the fluid apertures A11 of this dispersion impeller A1 is with the aperture size with 0.8mm, when the liquid level H that this quantitative sodium aluminate solution 21 accumulates on this dispersion impeller A1 top is 10 to 2 centimeters, the mean flow rate of single fluid apertures A11 is 1.2 public ls/h;
This crystallization reaction step S3: make this quantitative sodium aluminate solution 21 flow through this dispersion impeller A1 fluid apertures A11 and form a homodisperse sodium aluminate liquid stream 22 and enter this reaction compartment R14, and mat controls the flow velocity that this quantitative sodium aluminate solution 21 enters this reactive tank R1 reaction compartment R14, make this homodisperse sodium aluminate liquid stream 22 in batch time of administration, slow and this quantitative hydrofluoric acid waste liquid 11 carries out crystallization reaction, and stops when this quantitative sodium aluminate solution 21 is used up;
This sodium fluoroaluminate crystal separates out settling step S4: mixing solutions in reactive tank R1 is left standstill 60 to 90 minutes, the aluminum ion of the fluorion in this high concentration of hydrofluoric acid waste liquid 1 and this sodium aluminate solution 2 and sodium ion is made to carry out crystallization reaction to separate out sodium fluoroaluminate crystal 5 and to be settled down to bottom reactive tank R1, the aluminum ion (Al of solution in described reactive tank R1
3+)/fluorion (F
-) mol ratio is 1:4 to 1:8;
This filtration step S5: waste liquid 3 after crystal and crystallization reaction is flowed out from this reactive tank R1 outlet at bottom R12 and filters, to obtain this sodium fluoroaluminate crystal 5, and discharges a low concentration hydrofluoric acid waste liquid 4;
In the present embodiment, this filtration step S5 separately coordinates a drain step S6, whether the hydrofluoric acid concentration that this drain step S6 measures this low concentration hydrofluoric acid waste liquid 4 exceeds an emission concentration, if concentration, lower than this emission concentration, is directly discharged, if higher than this emission concentration, be back to this high concentration of hydrofluoric acid waste liquid tank V1 and store recycling processing.
By this, the present invention arranges this disk body A1 through at reactive tank R1 notch R11, reach and make sodium aluminate solution with homodisperse drop-wise form to the slow titration of hydrofluoric acid waste liquid, and through leave standstill after crystallization, formed and a kind ofly fluorion and sodium aluminate in waste liquid are fully reacted and the operator scheme of convergence crystallization, significantly increase the purity of the sodium fluoroaluminate crystal of precipitation, while output tool high economic benefit sodium fluoroaluminate crystal, more improve waste water treatment efficiency with fluoride ion recovery height in waste liquid, and obviously can reduce the chemical sludge volume that known chemical coagulation process process waste water formed.
Separately detect shown in data sheet one, table two about sodium fluoroaluminate crystallization operation parameter of the present invention, data and obtained sodium fluoroaluminate crystal thereof:
Wherein, the solids water ratio of the sample one to five that table one, table two disclose, crystal purity, with this is to certify that through sodium fluoroaluminate crystal obtained by crystallization system provided by the invention and crystallization method thereof, really reach crystal purity and be greater than 80%, and sodium fluoroaluminate crystal water ratio is less than 15%; In addition, the sodium fluoroaluminate (sodium aluminum fluoride) above-mentioned experiment sampled, measures the X-ray diffraction situation of this sample, and this is the short-cut method of qualification substance crystallization kenel, is also called powder diffraction.Spectrally each diffraction angle, just according to Bragg diffraction method (Braggdiffractionlaw), can calculate the vertical range in all groups of faces in crystallization.Moreover each atomic density difference in crystallization, then intensity during each diffraction is also just different, and therefore by a powder diffraction spectrum, the power of each spectral line and position, just can identify the existence of a certain crystalline material.But owing to not having its standard x RD spectrum in current institute fluorine analysis sodium aluminate (sodium aluminum fluoride) ray diffraction (XRD) database, therefore only can with the characteristic of its XRD spectrum of comparison preliminary in pertinent literature.Wherein, the crystal that Fig. 6 is sampled for the present invention tests carries out X-ray diffraction analysis spectroscopic data, Fig. 7 is document 1 (HelveticaChimicaActa – Vol.91,2008, NanotubesMadefromDeeplyUndercooledCryolite/AluminaMelts; MichalKorenkoetal.) sodium fluoroaluminate carries out X-ray diffraction analysis spectroscopic data, and Fig. 8 is document 2 (Monatsheftefu ¨ rChemie138,1211 – 1215,2007, ThermalAnalysisoftheSystemNa3AlF6 – NaVO3; Maria ' nKuchar1 ' ketal.) sodium fluoroaluminate carries out X-ray diffraction analysis spectroscopic data.Sodium fluoroaluminate crystal X-ray diffraction analysis as shown in Figure 6, the crystal that known the present invention obtains according to table one parameter, data, compared with the X-ray diffraction analysis spectrum of Fig. 7, Fig. 8 annex Literature one, two sodium fluoroaluminate crystal, can prove that crystal of the present invention is sodium fluoroaluminate crystal.
In sum, the present invention generates crystallization system and the crystallization method thereof of sodium fluoroaluminate crystal from hydrofluoric acid waste liquid, the mode that mat coordinates this dispersion impeller A1 to be disperseed with quantitative and even by sodium aluminate solution 2, directly with high concentration of hydrofluoric acid waste liquid 1 instead and crystallization, thus the sodium fluoroaluminate crystal 5 that output water ratio is low, crystallization purity is high, reach the volume effectively reducing chemical sludge, and promote the object of xln purity; In addition, because the present invention's whole process completes crystallization reaction in this reactive tank R1, the flow process of liquid waste disposal is significantly reduced, and reduce the problem such as inconvenience and multitask sequence of system conversion bins or treatment trough, more effectively reduce manpower and the time of processing operation, therefore the present invention reaches really, and improvement is known generates the sedimentary technical problem of sodium fluoroaluminate from hydrofluoric acid waste liquid.
Above by specific embodiment to invention has been detailed description, but these are not construed as limiting the invention.Without departing from the principles of the present invention, those skilled in the art also can make many distortion and improvement, and these also should be considered as protection scope of the present invention.
Claims (18)
1. one kind generates the crystallization system of sodium fluoroaluminate crystal from hydrofluoric acid waste liquid, it comprises a high concentration of hydrofluoric acid waste liquid tank exports a certain amount of hydrofluoric acid waste liquid to batch crystallization reaction section reactive tank through one batch of fixing quantity section, and a sodium aluminate pharmacy slot exports a homodisperse sodium aluminate liquid through one batch of fixing quantity section and certain flow and dispersed dosing section and flow in described reactive tank and carry out crystallization reaction with described quantitative hydrofluoric acid waste liquid; It is characterized in that:
Described reactive tank, top formed have a notch and a dispensing space, and bottom has an outlet and a reaction compartment;
Described constant flow and dispersed dosing section, have a dispersion impeller and be provided with plural fluid apertures, and described dispersion impeller periphery and described reactive tank inwall level set firmly, and described reactive tank is inner for described dispersion impeller is every being set as to offer medicine described in shape space and described reaction compartment; By this, described quantitative hydrofluoric acid waste liquid is made to be placed in described reaction compartment, the a certain amount of sodium aluminate solution of described batch of fixing quantity section output is that described dispersion impeller is every being located in described dispensing space, and through the described fluid apertures distribution of described dispersion impeller, form described homodisperse sodium aluminate liquid stream and input described reaction compartment and described quantitative hydrofluoric acid waste liquid uniform contact is carried out reacting and generates sodium fluoroaluminate crystal.
2. the crystallization system of sodium fluoroaluminate crystal is generated as claimed in claim 1 from hydrofluoric acid waste liquid, it is characterized in that, described constant flow and dispersed dosing section have a controlling board and stack on described dispersion impeller top, and one propulsion source be located at bottom described dispersion impeller, described propulsion source has a transmission shaft, and to place described dispersion impeller center and described controlling board center affixed, described dispersion impeller is provided with the fluid apertures of described plural number radiation arrangement, and described controlling board is provided with the through hole of the corresponding described dispersion impeller fluid apertures quantity of plural number, described propulsion source is made to drive described controlling board to rotate, described controlling board through hole and the described dispersion impeller fluid apertures quantitative hydrofluoric acid waste liquid described in block that misplaces circulates, or, described controlling board through hole and described dispersion impeller fluid apertures involutory, described homodisperse sodium aluminate liquid stream is made to enter reaction compartment and described quantitative hydrofluoric acid waste liquid contact reacts from dispensing spatial flow.
3. the crystallization system of sodium fluoroaluminate crystal is generated as claimed in claim 1 from hydrofluoric acid waste liquid, it is characterized in that, described constant flow and dispersed dosing section have a controlling board and stack on described dispersion impeller top, and one propulsion source be located at bottom described dispersion impeller, described propulsion source has a transmission shaft, and to place described dispersion impeller center and described controlling board center affixed, wherein:
Described dispersion impeller, plural fluid apertures described in it is offered along the arrangement of rice word radiation direction centered by described transmission shaft;
Described controlling board, be provided with at least two and arrange along rice word radiation direction one first sets of vias and one second sets of vias offered centered by described transmission shaft, each described sets of vias is made up of plural through hole, sandwiched one angle between the rice word arrangement radiation direction of each group of through hole, and described first sets of vias has the described plural through hole of corresponding described dispersion impeller fluid apertures quantity, described two sets of vias have the described plural through hole being less than described dispersion impeller fluid apertures quantity;
Described propulsion source is made to drive described controlling board to rotate, described controlling board through hole and the described dispersion impeller fluid apertures quantitative sodium aluminate solution described in block that misplaces circulates, or, described controlling board with its first group of through hole or its second group of through hole and described dispersion impeller fluid apertures involutory, make described homodisperse sodium aluminate liquid stream enter reaction compartment and described quantitative hydrofluoric acid waste liquid contact reacts from dispensing spatial flow.
4. the crystallization system of sodium fluoroaluminate crystal is generated as claimed in claim 3 from hydrofluoric acid waste liquid, it is characterized in that, described dispersion impeller has that 20 fluid apertures are dispersed to be located in described rice word radiation direction, described controlling board has three meters of word arrangement sets of vias, be respectively described first sets of vias, described second sets of vias and a third through-hole group, wherein, described first sets of vias has 20 described through holes, described second sets of vias has 16 described through holes, and described third through-hole group has 8 described through holes.
5. the crystallization system of sodium fluoroaluminate crystal is generated as claimed in claim 1 from hydrofluoric acid waste liquid, it is characterized in that, batch fixing quantity section of described sodium aluminate solution has a dosing side Pu enters described constant flow and dispersed dosing section flow with the sodium aluminate solution controlling the output of described sodium aluminate pharmacy slot, and described dosing helps Pu and a liquidometer and described dosing to help Pu to be electrically connected, to detect the quantitative sodium aluminate solution liquid level in described reactive tank dispensing space.
6. the crystallization system of sodium fluoroaluminate crystal is generated as claimed in claim 1 from hydrofluoric acid waste liquid, it is characterized in that, described reactive tank exit is provided with a micro-filtration section, for filtering waste liquid after a crystal and crystallization reaction that described reactive tank discharges, and export a low concentration hydrofluoric acid waste liquid and a sodium fluoroaluminate crystal, and a low concentration hydrofluoric acid liquid waste disposal section is connected with described micro-filtration section, for the described low concentration hydrofluoric acid waste liquid of process.
7. generate the crystallization system of sodium fluoroaluminate crystal as claimed in claim 6 from hydrofluoric acid waste liquid, it is characterized in that, described micro-filtration section is for having the filter bag machine being less than or equal to 10 μm of size of meshes.
8. the crystallization system of sodium fluoroaluminate crystal is generated as claimed in claim 6 from hydrofluoric acid waste liquid, it is characterized in that, described low concentration hydrofluoric acid liquid waste disposal section is for the low concentration hydrofluoric acid waste liquid of process fluorinion concentration lower than 3000 milligrams/liter (mg/L).
9. generate a crystallization method for sodium fluoroaluminate crystal from hydrofluoric acid waste liquid, it is characterized in that, described method steps comprises:
A, hydrofluoric acid waste liquid influent stream step: a high concentration of hydrofluoric acid waste liquid is inputed in a reactive tank through a batch fixing quantity, described reactive tank is top formed a notch and a dispensing space, bottom has an outlet and a reaction compartment, and described quantitative hydrofluoric acid waste liquid is placed in described reaction compartment;
B, sodium aluminate administering step: the dispersion impeller that offers plural equally distributed fluid apertures is provided, be that horizontal configuration sets firmly by described dispersion impeller with its periphery and described and described reactive tank inwall, described reactive tank inside is configured as described dispensing space and described reaction compartment for described dispersion impeller every establishing, by a sodium aluminate solution after batch fixing quantity, input in a certain amount of sodium aluminate solution to described dispensing space with every batch of time of administration of 1 to 1.5 hour;
C, crystallization reaction step: make described quantitative sodium aluminate solution flow through described dispersion impeller fluid apertures and form a homodisperse sodium aluminate liquid and flow to into described reaction compartment, and mat controls the flow velocity that described quantitative sodium aluminate solution enters described reactive tank reaction compartment, make described homodisperse sodium aluminate liquid stream in batch time of administration, slowly carry out crystallization reaction with described quantitative hydrofluoric acid waste liquid, and stop when described quantitative sodium aluminate solution is used up;
D, sodium fluoroaluminate crystal separate out settling step: mixing solutions in reactive tank is left standstill 60 to 90 minutes, makes the aluminum ion of the fluorion in described high concentration of hydrofluoric acid waste liquid and described sodium aluminate solution and sodium ion carry out crystallization reaction to separate out sodium fluoroaluminate crystal and to be settled down to reaction tank bottom;
E, filtration step: waste liquid after crystal and crystallization reaction is flowed out from described reaction tank bottom outlet and filters, to obtain described sodium fluoroaluminate crystal, and discharges a low concentration hydrofluoric acid waste liquid.
10. the crystallization method of sodium fluoroaluminate crystal is generated as claimed in claim 9 from hydrofluoric acid waste liquid, it is characterized in that, described filtration step separately coordinates a drain step, whether the hydrofluoric acid concentration measuring described low concentration hydrofluoric acid waste liquid exceeds an emission concentration, if concentration, lower than described emission concentration, is directly discharged, if higher than described emission concentration, be back to for storing the high concentration of hydrofluoric acid waste liquid tank exporting described high concentration of hydrofluoric acid waste liquid.
11. as claimed in claim 9 from the crystallization method of hydrofluoric acid waste liquid generation sodium fluoroaluminate crystal, it is characterized in that, dispersion impeller top in described sodium aluminate administering step has stacked a controlling board, bottom is provided with a propulsion source, described propulsion source has a transmission shaft, and to place described dispersion impeller center and described controlling board center affixed, described dispersion impeller is provided with the fluid apertures of described plural number radiation arrangement, and described controlling board is provided with the through hole of the corresponding described dispersion impeller fluid apertures quantity of plural number, described propulsion source is made to drive described controlling board to rotate, described controlling board through hole and the described dispersion impeller fluid apertures quantitative sodium aluminate solution described in block that misplaces circulates, or, described controlling board through hole and described dispersion impeller fluid apertures involutory, described quantitative sodium aluminate solution is made to flow into reaction compartment and described quantitative hydrofluoric acid waste liquid contact reacts from the dispersion of dispensing space uniform.
12. as claimed in claim 9 from the crystallization method of hydrofluoric acid waste liquid generation sodium fluoroaluminate crystal, it is characterized in that, dispersion impeller top in described sodium aluminate administering step has stacked a controlling board, bottom is provided with a propulsion source, described propulsion source has a transmission shaft, and to place described dispersion impeller center and described controlling board center affixed, wherein:
Described dispersion impeller, plural fluid apertures described in it is offered along the arrangement of rice word radiation direction centered by described transmission shaft;
Described controlling board, be provided with at least two and arrange along rice word radiation direction one first sets of vias and one second sets of vias offered centered by described transmission shaft, each described sets of vias is made up of plural through hole, sandwiched one angle between the rice word arrangement radiation direction of each group of through hole, and described first sets of vias has the described plural through hole of corresponding described dispersion impeller fluid apertures quantity, described two sets of vias have the described plural through hole being less than described dispersion impeller fluid apertures quantity;
Described propulsion source is made to drive described controlling board to rotate, described controlling board through hole and the described dispersion impeller fluid apertures quantitative hydrofluoric acid waste liquid described in block that misplaces circulates, or, rotating described controlling board makes its first sets of vias or its second sets of vias and described dispersion impeller fluid apertures involutory, makes described quantitative sodium aluminate solution flow into reaction compartment and described quantitative hydrofluoric acid waste liquid contact reacts from the dispersion of dispensing space uniform.
13. crystallization method generating sodium fluoroaluminate crystal from hydrofluoric acid waste liquid as described in claim 9 or 11 or 12, it is characterized in that, the fluid apertures aperture of the described dispersion impeller in described sodium aluminate administering step is 0.8mm, and the liquid height that described quantitative sodium aluminate solution accumulates on described dispersion impeller top is when being 10 to 2 centimeters, the mean flow rate of single described fluid apertures is 1.2 public ls/h.
14. as claimed in claim 12 from the crystallization method of hydrofluoric acid waste liquid generation sodium fluoroaluminate crystal, it is characterized in that, described dispersion impeller has that 20 fluid apertures are dispersed to be located in described rice word radiation direction, described controlling board has three meters of word arrangement sets of vias, be respectively described first sets of vias, described second sets of vias and a third through-hole group, wherein, described first sets of vias has 20 described through holes, described second sets of vias has 16 described through holes, and described third through-hole group has 8 described through holes.
15. as claimed in claim 9 from the crystallization method of hydrofluoric acid waste liquid generation sodium fluoroaluminate crystal, it is characterized in that, described crystallization reaction step controls the flow of described quantitative sodium aluminate solution with a dosing side Pu, and described dosing side Pu and a liquidometer are electrically connected the quantitative sodium aluminate solution liquid level of offeing medicine in space to detect described reactive tank, and according to the described quantitative sodium aluminate solution flow quantity of described liquid level adjustment.
16. as claimed in claim 9 from the crystallization method of hydrofluoric acid waste liquid generation sodium fluoroaluminate crystal, it is characterized in that, quantitative hydrofluoric acid waste liquid in described hydrofluoric acid waste liquid influent stream step has 20,000 to 200, the hydrofluoric acid concentration of 000 milligram/liter, the concentration of the quantitative sodium aluminate solution in described sodium aluminate administering step is 30 to 300 grams/liters.
17., as claimed in claim 9 from the crystallization method of hydrofluoric acid waste liquid generation sodium fluoroaluminate crystal, is characterized in that, separate out in settling step, the aluminum ion (Al of solution in described reactive tank at described sodium fluoroaluminate crystal
3+)/fluorion (F
-) mol ratio is 1:4 to 1:8.
18. as claimed in claim 9 from the crystallization method of hydrofluoric acid waste liquid generation sodium fluoroaluminate crystal, and it is characterized in that, the crystal purity of the sodium fluoroaluminate crystal of described filtration step gained is greater than 80%, and the water ratio of described sodium fluoroaluminate crystal is less than 15%.
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| TWI588097B (en) * | 2014-11-21 | 2017-06-21 | 大桂環境科技股份有限公司 | Method for treating fluoride containing waste water |
| CN106521186A (en) * | 2016-11-15 | 2017-03-22 | 云南驰宏锌锗股份有限公司 | New method for removing fluorine in zinc solution through sodium aluminate |
| TWI637915B (en) * | 2017-07-15 | 2018-10-11 | 大桂環境科技股份有限公司 | Fluorinated wastewater treatment system |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5291780A (en) * | 1976-01-23 | 1977-08-02 | Union Carbide Corp | Liquiddliquid contact system |
| TW453978B (en) * | 1998-06-23 | 2001-09-11 | Ind Tech Res Inst | Crystallization process for removing fluoride from wastewater |
| TWI233428B (en) * | 2000-03-09 | 2005-06-01 | Ming-Huei Liau | Method for treating fluoro-containing wastewater and treating agent thereof |
| CN101891228A (en) * | 2010-07-21 | 2010-11-24 | 多氟多化工股份有限公司 | Method for producing cryolite |
| CN202113845U (en) * | 2011-06-22 | 2012-01-18 | 南通市康桥油脂有限公司 | Multilayer distributor type fat hydrolysis tower |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5291780A (en) * | 1976-01-23 | 1977-08-02 | Union Carbide Corp | Liquiddliquid contact system |
| TW453978B (en) * | 1998-06-23 | 2001-09-11 | Ind Tech Res Inst | Crystallization process for removing fluoride from wastewater |
| TWI233428B (en) * | 2000-03-09 | 2005-06-01 | Ming-Huei Liau | Method for treating fluoro-containing wastewater and treating agent thereof |
| CN101891228A (en) * | 2010-07-21 | 2010-11-24 | 多氟多化工股份有限公司 | Method for producing cryolite |
| CN202113845U (en) * | 2011-06-22 | 2012-01-18 | 南通市康桥油脂有限公司 | Multilayer distributor type fat hydrolysis tower |
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