CN103721667B - A kind of dephosphorization adsorbent and preparation method efficiently - Google Patents
A kind of dephosphorization adsorbent and preparation method efficiently Download PDFInfo
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Abstract
The invention discloses a kind of dephosphorization adsorbent and preparation method efficiently, the steps include: 1) lanthanide rare slag drying is removed impurity; 2) be then placed in Muffle furnace, calcine between 550-750 DEG C, calcining heating rate 10-20 DEG C/min, Muffle furnace power output percentage is 80%, keep 1-3 hour after reaching maximum temperature, calcining terminates rear cooling naturally, sieves and makes its particle diameter between 0.1-0.25 mm; 3) the rare earth slag after calcining is mixed with phosphorus-containing wastewater according to a certain percentage, 5-10 minute is shaken under 150-250rpm condition, adsorption equilibrium can be reached, and good absorption purifying effect is played to the solution containing phosphate of high concentration, the maximal absorptive capacity calculated according to isotherm adsorption model is 152mg/g, be significantly higher than other mineral sorbing materials of commercial activated charcoal material and report to the absorption property of phosphorus, can obtain the good absorption purifying effect of high-concentration phosphorus-containing wastewater, also achieve the recycling for rare earth slag simultaneously.
Description
Technical field
The present invention relates to the method for comprehensive utilization of slag discarded object, specifically, be use the lanthanide rare slag phosphorus after treatment in adsorbed water body, realize the efficient dephosphorization adsorbent of one and the preparation method of the recycling of slag discarded object and the high-efficient purification of phosphorus-containing wastewater (particularly high-concentration phosphorus-containing wastewater) simultaneously.
Background technology
It is reported, the annual solid waste produced in the whole nation has 85% from mine, and accumulative have the forest of more than 130 ten thousand hectares and meadow to be damaged because digging up mine.The bulk deposition of slag, has has not only occupied a large amount of arable land, there is serious potential safety hazard, and wherein contained harmful substance and slag are stacked the sand dust that storehouse produces and all can be polluted the ecological environment of surrounding area, mine and water resource.Therefore, how rationally to dispose slag, how by its comprehensive reutilization, obtain the concern of relevant enterprise and government organs.
Owing to containing abundant active material in slag, and itself good distribution of pores, larger specific area, it can be used as adsorbent, be applied to wastewater treatment, be i.e. " waste recycling ", meet the theory of sustainable development, should more be paid close attention to and study.It is pointed out that China is as rare-earth mineral producing country maximum in the world, also creates the slag discarded object of flood tide in the production process of rare earth, how rationally to dispose these resources be misplaced, need related scientific research personnel to carry out deeply and the probing into of system.
On the other hand, because the nutrients such as nitrogen phosphorus enter natural water in a large number, cause eutrophication, the productive life of people and ecological safety are caused and has a strong impact on.According to statistics, in China's Main Lakes, what cause eutrophication because of nitrogen and phosphorus pollution accounts for 56% more than of statistics lake.Eutrophication causes the change of aquatic ecosystem 26S Proteasome Structure and Function, shows as water quality deterioration, landscape destruction, water transparency decline, degradation under bio-diversity.Research about body eutrophication shows, although nitrogen and phosphorus are all biological necessary important nutrients, the aquatile such as algae is more responsive to phosphorus under many circumstances.Famous limnologist Vollenweider thinks, in water, total phosphorus concentration is eutrophication more than 0.02mg/L.EPA (USEPA) proposes after investigating to United States 812 lakes and reserviors, and the total phosphorus concentration standard of body eutrophication is higher than 0.02-0.25mg/L.The research of Chinese scholar is pointed out, when total phosphorus concentration is more than 0.02mg/L, water body starts eutrophication process; When in water, phosphorus concentration reaches 0.5mg/L, blue-green algae starts raised growth.
In water body, the minimizing technology of phosphorus has multiple, comprises chemical precipitation method, biological phosphate-eliminating technology, adsorption technology etc.Wherein absorption method dephosphorization is phosphorus in the attachment absorption of adsorbent surface, the process such as ion-exchange or surface precipitation, transfers on adsorbing medium, realize the technology that phosphorus is separated from sewage by the phosphorus of homogeneous phase in water body.
Therefore, can find, slag is made into efficient dephosphorization adsorbent, reduce the content of Phosphorus From Wastewater, thus alleviate the body eutrophication risk that waste water may cause, realize the treatment of wastes with processes of wastes against one another, have a good application prospect and realistic meaning.
Summary of the invention
In the face of being a large amount of entered environment of phosphorus-containing wastewater on the one hand, cause body eutrophication; Another aspect is that the bulk deposition of slag causes the waste of land resource and this present situation of pollution of environment, the invention provides a kind of dephosphorization adsorbent and preparation method efficiently, the efficient dephosphorization adsorbent that preparation is precursor with rare earth slag discarded object, slag after necessarily processing is applied to the adsorption cleaning of phosphorus-containing wastewater, while recycling slag discarded object, reach the object reducing phosphorus in waste water content.
A kind of dephosphorization adsorbent and preparation method are efficiently as two innovation and creation, owing to possessing identical specified features: all adopt lanthanide rare slag to obtain the calcining lanthanide rare slag to the strong adsorption capacity of phosphorus (especially high-concentration phosphorus-containing wastewater) tool in sewage through pretreatment and calcination processing, belong to a total inventive concept, can propose as an application.
To achieve these goals, technical scheme of the present invention is: a kind of preparation method of efficient dephosphorization adsorbent, is characterized in that, comprise the steps:
(1) lanthanide rare slag drying is removed impurity;
(2) the lanthanide rare slag processed through step (1) is placed in Muffle furnace, at 550-750 DEG C, calcines 1-3 hour, calcining terminates rear cooling naturally, sieves and makes its particle diameter between 0.1-0.25mm;
(3) the lanthanide rare slag of calcining is placed in phosphorus-containing wastewater according to 0.5-8.0g/L additive capacity, regulates pH between 3-10, concussion absorption 4-6 minute, make phosphorus be adsorbed in calcining lanthanide rare slag.
Further, step (1) detailed process is as follows, the lanthanide rare slag taking from Gan Nan is dried 6-12 hour in 80-100 degree in electric furnace, and removes impurity.
Further, in step (2), calcining adopts progressively heating mode, and calcining heating rate is set as 10-20 DEG C/min, and Muffle furnace power output percentage is 80%, keeps 1-3 hour after reaching default maximum temperature.
In step (3), concussion speed 100-250rpm, adsorption reaction temperature is 5-40 DEG C.
Further, in step (3), it is that the phosphorus-containing wastewater of 100-200mg/L fully mixes that the lanthanide rare slag of calcining is placed in phosphate concentration according to 0.5-8.0g/L additive capacity.
Preferably, in step (3), regulate PH between 3.7 to 6.2.
Wherein, step (1) be rare earth slag collection and pre-treatment step.The present invention adopts lanthanide rare slag to make dephosphorization adsorbent, and mainly because lanthanide series rare-earth elements oxide may have good absorption property to phosphorus, relevant experiment and bibliographical information all demonstrate this point.And lanthanide rare is after ore dressing, what still may there is certain content does not extract rare earth oxide completely, and often association has other metallic elements multiple and metalloid element simultaneously, and this provides the foundation for next step makes efficient dephosphorization adsorbent.In addition, this step is dried slag, and its object mainly removes the moisture that slag contains, the infringement that when preventing from calcining, the moisture of high level may cause Muffle furnace.Meanwhile, the foreign material such as the stone that may exist in slag are also rejected at this, avoid producing significantly interference to follow-up experiment and test.
The calcination stage that step (2) is slag.The main purpose of high-temperature calcination removes the Bound moisture on mineral surface, and other volatile impurity, reduces moisture film to the absorption resistance of adsorbate (phosphorus), improve porosity and the specific area of slag simultaneously, and then improve adsorption capacity.Calcining heat, at 550-750 DEG C, is because some volatile materials not easily removes under lower temperature conditions, affects the raising of specific surface area and porosity; Also can find that rare earth slag is weightless very fast below 400 degree according to thermogravimetric curve, illustrate that lower calcining heat possibly cannot remove volatile substances and other impurity of rare earth slag surface more fully.On the other hand, higher temperature causes mineral material to produce crystallization, even occurs vitreum, makes a large amount of micropores be burnt mistake, while affecting absorption property lifting, but significantly increases energy consumption.And temperature controls when 550-750 DEG C, there will not be the situation that these two kinds extreme, reach good adsorption and dephosphorization effect.Simultaneously, control heating rate at 10-20 DEG C, and keep 1-3 hour under maximum temperature (being namely warmed up to the temperature to a certain degree keeping calcining at constant temperature, value between the 550-750 DEG C) condition preset, correlated response can be made fully to carry out, to obtain good pore structure.Calcining terminates and after cooling, rare earth slag after calcining is sieved, makes its particle diameter between 0.1-0.25mm, the corresponding higher specific area of particle diameter less on the one hand and higher adsorption capacity, and be beneficial to and fully infiltrate in solution containing phosphate, fully contact with phosphate radical and suction-operated occurs; But on the other hand, correlation test proves, after particle diameter acquires a certain degree, continue to reduce the absorption property that particle diameter obviously can increase material, but in order to maintain too small material particle size, significantly can increase energy consumption; Also can have adverse effect to engineer applied, the particle diameter as too small causes as water penetration during packing material poor simultaneously, easily causes blocking.Therefore, rational particle size range is kept to be the key factor considered by needs during sorbing material practice.And this particle size range disclosed by the invention can take into account above-mentioned two aspects preferably.
Step (3) is the application conditions of calcining lanthanide rare slag, joins in phosphorus-containing wastewater according to a certain percentage by calcining rare earth slag, and regulate pH between 3-10, adsorption reaction temperature is between 5-40 DEG C; In order to reach adsorption equilibrium sooner, advising shaking absorption system, under the concussion speed of 150-250rpm, only needing within 4-6 minute, can adsorption equilibrium be reached.In addition, for given solution phosphorus concentration, the addition of calcining Rare Earth Mine slag adsorbent is higher, also higher to the clearance of phosphorus.
Another technical solution used in the present invention is: a kind of dephosphorization adsorbent efficiently, it is characterized in that: described dephosphorization adsorbent with lanthanide rare slag for precursor, drying, removal impurity, and 1-3 hour is calcined at 550-750 DEG C, get the calcining lanthanide rare slag of particle diameter between 0.1-0.25mm after screening and obtain.
The efficient dephosphorization adsorbent of aforesaid one, according to isotherm adsorption model, dephosphorization adsorbent is that 152mg/g(is with PO to the maximal absorptive capacity of phosphorus
4 3-meter).
The efficient dephosphorization adsorbent of aforesaid one, described calcining lanthanide rare slag comprises lanthanide series rare-earth elements oxide and other element oxide; Other element comprises Ba, V, Si, Y, Ca, Fe, and wherein Ba proportion is maximum.
The efficient dephosphorization adsorbent of aforesaid one, is characterized in that: the BET specific surface area of described calcining lanthanide rare slag is 12.13m
2/ g, pore volume is 0.062mL/g, and aperture is 12.15nm.
The principle of calcining lanthanide rare slag dephosphorization adsorbent prepared by the present invention is: high-temperature calcination adds specific area and the porosity of mineral material; Lanthanide rare slag may due to ore dressing not thoroughly and the appearance of associated minerals, can a certain amount of lanthanide series rare-earth elements oxide and other metal oxides be contained, and the electric charge that lanthanide rare earth oxide surface band is certain, to phosphate radical, there is electrostatic adsorption; The oxide of slag also containing other elements, as the oxide of the elements such as Ba, V, Si, Ca, Fe, also has certain absorption property to phosphate radical simultaneously.
Beneficial effect of the present invention
The invention discloses a kind of dephosphorization adsorbent and preparation method efficiently, accordingly, lanthanide rare slag is after simple pretreatment, 1-3 hour is calcined under 550-750 DEG C of condition, namely can be made into dephosphorization adsorbent phosphate radical to excellent absorption property, its to the nearly 152mg/g(of maximum adsorption performance of phosphate radical namely in theory every 1g calcine the most multipotency absorption 152mg phosphate radical of lanthanide rare slag), apparently higher than the active carbon of bibliographical information and other mineral materials to the absorption property of phosphorus; The time that absorption simultaneously reaches balance is fast, only needs within 4-6 minute, can reach adsorption equilibrium, and this shows that this material is very efficient and quick in the process of Phosphate Sorption, for applying to lay a good foundation in the dephosphorizing process of actual waste water in the future.In addition, experiment shows that the calcining Rare Earth Mine slag adsorbent that the present invention relates to all has excellent performance within the scope of more wide in range pH, and the impact by pH is less, thus range of application is wider.The present invention has also inquired into the conditions such as adsorbent dosage, haptoreaction time, initial phosphate concentration to the impact of adsorption process.By a series of experimental study, calcining lanthanide rare slag disclosed by the invention solves following two problems: one is for lanthanide rare slag provides the mode of recycling, two is for the phosphorus removed in high-concentration phosphorus-containing wastewater provides effective means, really achieve and turn waste into wealth, recycle, meet the theory of sustainable development.
Accompanying drawing explanation
Fig. 1 is that calcining lanthanide rare slag is to the isothermal adsorption regression curve of solution containing phosphate;
Fig. 2 adds the tp removal rate that 2g/L calcines lanthanide rare slag under illustrating different phosphate acid group initial concentration condition;
Fig. 3 is that calcining lanthanide rare slag is to the curve of adsorption kinetics of solution containing phosphate;
Fig. 4 illustrates the impact of the initial pH of solution on calcining lanthanide rare slag adsorption capacity;
Fig. 5 illustrates the desorption experimental result of adsorbent in different solutions being adsorbed with load phosphate radical;
Fig. 6 is that the calcining lanthanide rare slag of different additive amount is to the removal effect schematic diagram of phosphorus in cesspool sewage;
Fig. 7 is the scanning electron microscopic observation collection of illustrative plates of calcining lanthanide rare slag;
Fig. 8 is infrared spectrum (FTIR) scanning spectra of calcining lanthanide rare slag;
Fig. 9 is the x-ray fluorescence analysis collection of illustrative plates of calcining lanthanide rare slag;
Figure 10 is the thermogravimetric analysis collection of illustrative plates of lanthanide rare slag.
Detailed description of the invention
Below in conjunction with Fig. 1-Figure 10 in detail technical scheme of the present invention is described in detail.
A preparation method for efficient dephosphorization adsorbent, its step comprises:
1) the lanthanide rare slag taking from Gan Nan is dried 6-12 hour in 80-100 degree in electric furnace, and remove impurity;
2) be then placed in Muffle furnace, calcine between 550-750 DEG C, calcining heating rate is set as 10-20 DEG C/min, Muffle furnace power output percentage is 80%, reach maximum temperature (peak value) and keep 1-3 hour afterwards, calcining terminates rear cooling naturally, sieves and makes its particle diameter between 0.1-0.25mm;
3) the rare earth slag after calcining is mixed with phosphorus-containing wastewater according to a certain percentage, regulate pH between 3-10,4-6 minute is shaken under 150-250rpm condition, adsorption equilibrium can be reached, and play good absorption purifying effect to the solution containing phosphate of high concentration, the maximal absorptive capacity calculated according to isotherm adsorption model is about 152mg/g.2g/L adsorbent addition corresponding containing the tp removal rate of 200mg/L phosphate radical waste water higher than 60%, and along with the raising of additive capacity, the eliminating rate of absorption of phosphate radical increases.
The original material (precursor) that this method uses is the final waste products after the exploitation ore dressing of lanthanide rare ore deposit, i.e. lanthanide rare slag.
Preferably, the lanthanide rare slag of calcining is placed in high-concentration phosphorus-containing wastewater (phosphate concentration is higher than 100-200mg/L) according to 0.5-8.0g/L additive capacity fully to mix.
Preferably, at pH3-10, adsorption reaction temperature 5-40 DEG C, the hybrid reaction time, higher than 5 minutes, under concussion speed 100-250rpm condition, adsorbs solution containing phosphate.
Embodiment one
In order to obtain the parameter of the absorption property, particularly adsorption capacity of dephosphorization sorbing material prepared by the present invention, the present embodiment has carried out isothermal adsorption experimental study.
The preparation method of high-temperature calcination lanthanide rare slag is as follows:
1) by take from Gan Nan lanthanide rare slag in electric furnace in 80 degree of oven dry 12 hours, and remove impurity;
2) be then placed in Muffle furnace, calcine under 550 DEG C of conditions, calcining heating rate is set as 15 DEG C/min, Muffle furnace power output percentage is 80%, reach maximum temperature (peak value) to keep 1 hour afterwards, calcining terminates rear cooling naturally, sieves and makes its particle diameter between 0.1-0.25mm; Bottle for subsequent use.
The simulated wastewater (between 30 – 180mg/L) containing variable concentrations phosphate radical is configured to potassium dihydrogen phosphate, then mix with calcining lanthanide rare slag adsorbent under 25 DEG C of conditions, the dosage keeping adsorbent is 2g/L, shake under 250rpm condition and spend the night, test phosphate content in supernatant after reaching adsorption equilibrium, method of testing is molybdenum blue colorimetric method.Amount (the q of the phosphate radical of phosphate concentration (Ce) and unit mass sorbent-loaded is balanced by supernatant
e), pass through linear regression, obtain Langmuir model parameter (Fig. 1), and Fig. 2 adds the tp removal rate that 2g/L calcines lanthanide rare slag under illustrating different phosphate acid group initial concentration condition, along with phosphate radical initial concentration significantly increases, tp removal rate slightly declines, but clearance remains on 60% substantially.And then to calculate calcining lanthanide rare slag adsorbent of the present invention to the maximal absorptive capacity of phosphate radical by Langmuir model be 152mg/g.This value to the adsorption capacity of phosphate radical, shows that calcining lanthanide rare slag disclosed by the invention has excellent adsorption cleaning ability to solution containing phosphate apparently higher than the active carbon of bibliographical information and other mineral materials.
Embodiment two
In order to investigate hybrid reaction time and initial phosphate concentration to the impact of calcining lanthanide rare slag adsorb phosphate, the present embodiment has carried out kinetics experiment under 2 kinds of initial phosphate concentration of difference.
The preparation method of high-temperature calcination lanthanide rare slag is with embodiment one.
Adsorption dynamics adsorption kinetics process of the test is as follows: 2g/L is calcined lanthanide rare slag and be placed in beaker containing variable concentrations phosphate radical simulated wastewater, shake under 200rpm condition and start timing, within starting stage 2-3 minute, gather water sample (about 2mL) once, later stage proper extension acquisition time, gather 20 times altogether, dilute and measure phosphate concentration.Initial phosphate concentration is set to 50mg/L and 150mg/L.Use the graph of a relation (Fig. 3) between the amount (qt) of Software on Drawing unit mass sorbent-loaded phosphate radical and incorporation time t.Can find, under this experiment condition, adsorption reaction only needs 4-6 minute can reach adsorption equilibrium state, illustrates that adsorption process is carried out very quick, thus provides convenience to practical application (as filling adsorption column) in the future.Found by models fitting, this course of reaction meets pseudo-second order kinetic Adsorption Model.Can find simultaneously, the time that higher initial concentration reaches balance is slightly long, this may due under higher initial concentration condition, the phosphate anion of more ratios is had to reach granule interior by the mass transport process in particle, and this process is the rate-limiting step of reaction, therefore needing to consume the more time reaches adsorption equilibrium.Totally see, because this adsorption process itself is carried out very fast, initial phosphate concentration is not fairly obvious on the impact of adsorption equilibrium required time.
In addition, can accelerate to adsorb the speed of carrying out by concussion, within the specific limits, concussion speed is higher, and the time reaching adsorption equilibrium is shorter.Experiment shows, within the scope of 150-250rpm, absorption system can be made to take into account carrying out fast of absorption and stablizing, for the practice in future tentatively provides operating parameter of absorption system simultaneously.
Embodiment three
In order to investigate the impact of some critical environmental condition and operating parameter, the present embodiment has investigated pH value of solution and adsorbent dosage to the impact (Fig. 4) of adsorption process.
The preparation method of high-temperature calcination lanthanide rare slag is with embodiment one.
It is as follows that pH affects adsorption test: the phosphate radical solution of configuration 200mg/L, use hydrochloric acid and sodium hydroxide solution adjustment pH between 2-10, then mix with calcining lanthanide rare slag adsorbent under 25 DEG C of conditions, the dosage keeping adsorbent is 2g/L, shake under 250rpm condition and spend the night, after reaching adsorption equilibrium, test phosphate content in supernatant.Can find, (pH is between 3.7 to 6.2) eliminating rate of absorption to solution containing phosphate is the highest under mildly acidic conditions, and clearance is slightly low under comparatively highly acid and alkali condition.Although pH has a certain impact to the absorption property of calcining lanthanide rare slag to phosphorus, but total difference is also little, within the scope of the pH of this embodiment, the peak of the clearance of phosphate radical and minimum are only differed less than 4%, this illustrates that calcining lanthanide rare slag of the present invention has good absorption property within the scope of wider pH, and the impact by pH is limited.
Adsorbent addition on absorption to affect process of the test as follows: the phosphate radical solution of configuration 200mg/L, mix with calcining lanthanide rare slag adsorbent under 25 DEG C of conditions, the dosage of adjustment adsorbent is between 0.5-8.0g/L, shake under 250rpm condition and spend the night, after reaching adsorption equilibrium, test phosphate content in supernatant.Can find, along with the raising of adsorbent dosage, clearance corresponds to adsorbent dosage 0.5g/L by 45.7%() bring up to 57.5%(corresponding to adsorbent dosage 8.0g/L).
Embodiment four
In order to investigate the calcining lanthanide rare slag of load phosphorus under certain condition to the releasability of phosphorus, the present embodiment is intended carrying out desorption experiment (Fig. 5) under different solutions and variable concentrations condition.
The preparation method of high-temperature calcination lanthanide rare slag is with embodiment one.
The preparation of the adsorbent of load phosphorus: initial phosphate concentration is 200mg/L, and the adsorbent dosage added is 2g/L, volume is 0.5L, stirs centrifugal segregation supernatant after 30min, by solid matter filtering drying, just obtains the sorbing material of load phosphorus.
The enforcement of desorption experiment: use four kinds of solution, i.e. hydrochloric acid solution, sodium chloride solution, sodium hydroxide solution and deionized water solution, respectively except 0.01M and 0.05M(deionized water) add the sorbing material of the load phosphorus of above-mentioned acquisition under concentration conditions, control dose is 2g/L, and the content of phosphate radical in supernatant is tested in concussion after spending the night.The computational methods of desorption are as follows:
R(%)=(C
e-C
0)/C
0
Wherein, C
0the phosphate concentration that during sorbing material for preparation load phosphorus, absorption system is initial; C
efor the supernatant phosphate concentration recorded at the end of desorption experiment, R is desorption rate.
Can find, the desorption rate using hydrochloric acid solution process to obtain containing phosphorus adsorbent is the highest, uses the desorption rate lower (about 1.9%) that other three kinds of solution obtain.Meanwhile, desorption rate is relevant with solution concentration, and for hydrochloric acid solution, the desorption rate that 0.01M hydrochloric acid solution obtains is 5.0%, and the desorption rate that 0.05M hydrochloric acid solution obtains is 7.9%.All in all, the calcining lanthanide rare slag that the present invention uses is comparatively strong to the absorption carriage ability of phosphate radical, not easily desorption occurs.This is had certain advantage when applying to purified treatment high-concentration phosphorus-containing wastewater under extreme condition, not easily violent desorption occurs under compared with strong acid-base condition and cannot realize removing of phosphorus.
Embodiment five
For investigating calcining lanthanide rare slag of the present invention to the detergent power of actual phosphorus-containing wastewater, the present embodiment has carried out adsorption test (Fig. 6) to collection from the sewage of septic tank.
Wherein, the preparation method of high-temperature calcination lanthanide rare slag is with embodiment one.
Actual phosphorus-containing wastewater collection, from academy of agricultural sciences of Jiangsu Province dependents' district septic tank, carries out adsorption test after using filter paper to carry out suction filtration to sewage.Experimental condition is that 25 degrees Celsius of 250rpm concussion is spent the night, adsorbent additive capacity is 1,2,4g/L, test phosphorus concentration (in phosphate radical) after gathering water sample dilution.After tested, in this septic tank wastewater, phosphorus content is 3.52mg/L.
Can find, along with the raising of additive capacity, the tp removal rate of calcining lanthanide rare slag of the present invention to actual waste water increases, and when additive capacity is 4g/L, the phosphorus in waste water cannot detect.Although complicated component in septic tank, containing a large amount of organic matters and inorganic salts, COD is higher, and the effect such as the competitive Adsorption caused thus generally can have an impact to the adsorption effect of adsorbent; But the phosphorus-containing wastewater (cesspool sewage as herein) of calcining lanthanide rare slag centering low concentration of the present invention still has good dephosphorization effect, illustrates good application prospect.
Embodiment six
In order to calcining lanthanide rare slag more disclosed by the invention and the most widely used active carbon are to the adsorption capacity of phosphorus, the present embodiment tests merchandise active carbon and calcines the clearance that lanthanide rare slag is 200mg/L solution to phosphate concentration under similarity condition.Wherein, the preparation method of lanthanide rare slag is calcined with embodiment one.Main experimental conditions is: shake under dosage 2g/L, 250rpm condition and spend the night, and the active carbon used is commodity water purification active carbon (the sincere chemical reagents corporation in Shanghai, analyzes pure).Data show, active carbon is 53.76% to the clearance of phosphate radical; And the clearance of calcining rare earth slag of the present invention under similarity condition is 55.53%, a little more than merchandise active carbon.
In addition, according to the sorbing material of bibliographical information to the adsorption capacity of phosphorus, goethite is 0.3mg/g(Water Research to the adsorption capacity of phosphorus, 2006); Modification biological charcoal is 15.3mg/g(Chemical Engineering Journal to the adsorption capacity of phosphorus, 2013); Activated alumina is 10mg/g(non-ferrous metal to the adsorption capacity of phosphorus, 2002); Active carbon is 78.9mg/g(novel charcoal material to the adsorption capacity of phosphate radical, 2011), etc.The dephosphorization adsorbent of above-mentioned report is all starkly lower than the adsorption capacity (152mg/g) of calcining lanthanide rare slag disclosed by the invention to phosphate radical to the adsorption capacity of phosphorus.The experimental data of the present embodiment and the data of bibliographical information show, the adsorption capacity of calcining lanthanide rare slag disclosed by the invention to phosphate radical has very strong competitive advantage, and material source is from slag in addition, and cost is lower, preparation method is simple, has broad application prospects in future.
Embodiment seven
In order to investigate the impact of calcining heat on rare earth slag Phosphate Sorption ability, the present embodiment is calcined slag under condition of different temperatures, and is applied in the adsorption test of phosphorus-containing wastewater.
The preparation of calcining rare earth slag is all consistent with embodiment one except calcining heat.
Calcining heat is set as 550 DEG C, 750 DEG C, 950 DEG C and contrast (without calcining).Adsorption test essential condition is: dosage 2g/L, and initial phosphate concentration is 200mg/L, and concussion speed is 250rpm.Can find, the eliminating rate of absorption of rare earth slag to phosphate radical without calcining, 550 DEG C, 750 DEG C and 950 DEG C calcinings is respectively: 46.30%, 54.21%, 52.84% and 50.29%.Through calcining rare earth slag to the adsorption capacity of phosphate radical higher than without calcining rare earth slag, but be unfavorable for the raising of materials adsorption ability of the present invention when temperature is too high, this may cause surface portion components fuse or decomposition with high temperature, decreases effective adsorption site relevant.Maintain the temperature within the scope of 550-750 DEG C and can obtain good adsorption effect.
Embodiment eight
In order to more understand the performance characteristics of calcining lanthanide rare slag adsorbent in depth, the calcining lanthanide rare slag that the present embodiment is prepared with embodiment one, for analytic target, has carried out the phenetic analysis of material.Mainly comprise scanning electron microscopic observation, IR spectrum scanning, x-ray fluorescence analysis, thermogravimetric analysis, BET specific surface area analysis etc.
The preparation method of high-temperature calcination lanthanide rare slag is with embodiment one.
ESEM (SEM) is analyzed: the present embodiment has carried out SEM observation to high-temperature calcination lanthanide rare slag under amplification 2500 and 25000 condition.Can find, material presents coarse surface, and particulate form, appears in loose structure, grows and has more hole; This adsorption site more for adsorb phosphate provides.Can find by amplifying (25000 times) further, there is the form (Fig. 7) of similar crystallization on surface.
Infrared spectrum analysis: can find that high-temperature calcination lanthanide rare slag surface contains the characteristic peak (1236cm of barium sulfate
-1), show that barium sulfate exists (Fig. 8) in a large number at this lanthanide rare slag surface.
X-ray fluorescence analysis: can find that high-temperature calcination lanthanide rare slag surface contains all multiple metallic elements and metalloid element, primarily of Ba(87.05%), S(8.73%), V(2.10%), Si(1.04%), Y(0.51%), Ca(0.42%), Fe(0.25%), Yb(0.23%) etc. element composition.Wherein material surface Ba element proportion is comparatively large, and namely content is the highest, coincide with the data of infrared spectrum, and this may be relevant with the technique that slag produces and mineral nature.The existence comprising the Determination of multiple metal elements compound of barium sulfate may be that calcining rare earth slag of the present invention has the major reason (Fig. 9) of better absorption property to phosphate radical.
Thermogravimetric analysis: by finding the thermogravimetric analysis of original slag, material quick weight loss before 400 DEG C, the loss of the volatile substances (comprising moisture) that may contain with slag surface is relevant; Between 400-900 DEG C, weightlessness is comparatively slow, illustrates that volatile substances has lost totally; Between 900-1230 DEG C, weightlessness is accelerated again, and may decompose with some mineral of mineral material itself, melting etc. reacts relevant (Figure 10).
BET specific surface area is analyzed: table 1 shows the specific surface area analysis result of calcining lanthanide rare slag, can find, the calcining lanthanide rare slag that the present embodiment makes is grown has good pore structure, the higher (12.13m of specific area
2/ g), pore volume is 0.062mL/g, and aperture is 12.15nm, is beneficial to this material and carries out enrichment to this small-molecule substance of phosphate radical.
The specific surface area analysis of lanthanide rare slag calcined by table 1
Above-described embodiment does not limit the present invention in any form, the technical scheme that the mode that all employings are equal to replacement or equivalent transformation obtains, and all drops on protection scope of the present invention.
Claims (10)
1. a preparation method for efficient dephosphorization adsorbent, is characterized in that, comprises the steps:
(1) lanthanide rare slag drying is removed impurity;
(2) the lanthanide rare slag processed through step (1) is placed in Muffle furnace, at 550-750 DEG C, calcines 1-3 hour, calcining terminates rear cooling naturally, sieves and makes its particle diameter between 0.1-0.25mm;
(3) the lanthanide rare slag of calcining is placed in phosphorus-containing wastewater according to 0.5-8.0 g/L additive capacity, regulates pH between 3-10, concussion absorption 4-6 minute, make phosphorus be adsorbed in calcining lanthanide rare slag.
2. the preparation method of a kind of efficient dephosphorization adsorbent according to claim 1, is characterized in that: step (1) detailed process is as follows, the lanthanide rare slag taking from Gan Nan is dried 6-12 hour in 80-100 degree in electric furnace, and removes impurity.
3. the preparation method of a kind of efficient dephosphorization adsorbent according to claim 2, it is characterized in that, in step (2), calcining adopts progressively heating mode, calcining heating rate is set as 10-20 DEG C/min, Muffle furnace power output percentage is 80%, keeps 1-3 hour after reaching default maximum temperature.
4. the preparation method of a kind of efficient dephosphorization adsorbent according to claim 1 or 2 or 3, is characterized in that, in step (3), concussion speed 100-250 rpm, adsorption reaction temperature is 5-40 DEG C.
5. the preparation method of a kind of efficient dephosphorization adsorbent according to claim 1, it is characterized in that, in step (3), it is that the phosphorus-containing wastewater of 100-200mg/L fully mixes that the lanthanide rare slag of calcining is placed in phosphate concentration according to 0.5-8.0 g/L additive capacity.
6. the preparation method of a kind of efficient dephosphorization adsorbent according to claim 1, is characterized in that, in step (3), regulates pH between 3.7 to 6.2.
7. an efficient dephosphorization adsorbent, it is characterized in that: described dephosphorization adsorbent with lanthanide rare slag for precursor, drying, remove impurity, and calcine 1-3 hour at 550-750 DEG C, get the calcining lanthanide rare slag of particle diameter between 0.1-0.25mm after screening and obtain.
8. the efficient dephosphorization adsorbent of one according to claim 7, is characterized in that: according to isotherm adsorption model, and dephosphorization adsorbent is 152 mg/g to the maximal absorptive capacity of phosphate radical.
9. the efficient dephosphorization adsorbent of one according to claim 7, is characterized in that: described calcining lanthanide rare slag comprises lanthanide series rare-earth elements oxide and other metal and metalloid element oxide; Other metal and metalloid element comprise Ba, V, Si, Y, Ca and Fe, and wherein Ba proportion is maximum.
10. the efficient dephosphorization adsorbent of one according to claim 7, is characterized in that: the BET specific area of described calcining lanthanide rare slag is 12.13 m
2/ g, pore volume is 0.062 mL/g, and aperture is 12.15 nm.
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