CN103877941A - Spherical silicon-based organic-inorganic hybrid boron adsorbent and preparation method thereof - Google Patents
Spherical silicon-based organic-inorganic hybrid boron adsorbent and preparation method thereof Download PDFInfo
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- CN103877941A CN103877941A CN201410104368.2A CN201410104368A CN103877941A CN 103877941 A CN103877941 A CN 103877941A CN 201410104368 A CN201410104368 A CN 201410104368A CN 103877941 A CN103877941 A CN 103877941A
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- 229910052796 boron Inorganic materials 0.000 title claims abstract description 102
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000003463 adsorbent Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 13
- 229910052710 silicon Inorganic materials 0.000 title abstract description 6
- 239000010703 silicon Substances 0.000 title abstract description 6
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- 239000002243 precursor Substances 0.000 claims abstract description 39
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Abstract
The invention discloses a spherical silicon-based organic-inorganic hybrid boron adsorbent. The main component of the adsorbent is an inorganic substance; the adsorbent is good in mechanical property and the finished product of the adsorbent is a sphere good in uniformity. The invention further discloses a preparation method of the adsorbent. The preparation method comprises the following steps: (1) dissolving meglumine and organosilane with an epoxy group into polar solvent, reacting, distilling and purifying to obtain a precursor; (2) dissolving the precursor obtained in the step (1) and organosilane with a methoxy group or an ethoxy group in a water solution of alcohol in the molar ratio of (0.25-10):1, adding dilute acid to adjust the pH value to 1-4, and carrying out hydrolysis and condensation polymerization to obtain sol; and (3) adding the sol obtained in the step (2) and a surfactant with the volume accounting for 0.02-1% of the volume of the sol into dispersing solvent with the volume 1-20 times the volume of the sol while stirring to obtain a reaction system, carrying out cross-linking reaction at aging temperature, carrying out solid-liquid separation after the cross-linking reaction, washing and drying the separated solid to obtain the spherical silicon-based organic-inorganic hybrid boron adsorbent.
Description
Technical field
The present invention relates to boron adsorbent technology of preparing, relate in particular to a kind of spherical silica-based hybrid inorganic-organic boron and preparation method thereof.
Background technology
Boron is very important metals resources, has very high economic worth in many fields such as national defence, building materials, machinery, chemical industry, medicine, agriculturals.But boron resource is day by day in short supply, and solid boron rock is day by day exhausted through exploitation, and therefore from liquid boron rock, particularly, in salt lake bittern, separation and Extraction boron has great researching value.In addition, boron element is the indispensable element in the life such as plant and animal, but needs scope can produce murder by poisoning side effect when content exceedes.In IDWS, in regulation drinking water, boron content is no more than 1.0mg/L." Drinking Water hygienic quality standard " regulation that the Ministry of Public Health of China calendar year 2001 is issued, the higher limit of boron in Drinking Water is 0.5mg/L.Therefore from water, remove boron the reproducible utilization of desalinization and water resource is had to important meaning.
The method of extracting boron from B solution mainly contains acidization, the precipitation method, floatation, fractionation crystallization, solvent extraction, absorption method, hyperfiltration, membrane separation process etc.Wherein absorption method is extracted the high and rate of recovery of boron efficiency and can be reached more than 90%, technology maturation, simple to operate.Be applicable to low boracic system, be applicable to attracts boron from the low solution of the boron contents such as seawater, waste water and bittern.
The principle of boron adsorbent is: boron adsorbent has the functional group containing the active two hydroxyl structures in ortho position, utilizes the electron deficient characteristic of boron, becomes four tooth complex compounds with boric acid chelating, this complex compound can be from boron-containing solution attracts boron optionally.This adsorption mechanism is complexing, with respect to the hydrophobic sucking action of static and hydrogen bonding effect, and the adsorption capacity of this mechanism and selective better.
Publication number is that the Chinese patent literature of CN101642700A discloses one take silica gel-polyamine composite as skeleton, reacts the adsorbent of preparing high selectivity and high-adsorption-capacity at area load functional group by functional graft.
Publication number is that the Chinese patent literature of CN102336856A discloses a kind of Special effect boron adsorption resin, synthetic method and application, belongs to macromolecule and field of waste water treatment.Its general structure is:
Wherein n=1000～2000.Carry out in accordance with the following steps: the preparation of (1) 2-amino-1,3-propanediol;
(2) preparation of chloromethylation styrene-divinylbenzene copolymerization spheroid; (3) be prepared into boron special efficacy polymeric adsorbent by 2-amino-1,3-propanediol and chloromethylation styrene-divinylbenzene copolymerization spheroid.
Above-mentioned two kinds of patent documentations disclose the boron adsorbent forming as skeleton grafting functional functional group take organic material, and the density of its functional group is lower, and adsorbance is less, and because skeleton is resin, after repeatedly using, macromolecular scaffold can be broken.
In existing market or the boron adsorbent absorption property of bibliographical information poor, some relatively preferably boron specific adsorbents mostly be organic polymer resin.Its technological difficulties comprise: 1) mechanical strength of resinae adsorbent is poor; 2) its adsorption equilibrium speed is slower; 3) its Functional group density is lower, and adsorbance is lower; 4) its pH to adsorbent solution is more responsive, be more suitable for attracts boron in alkaline solution, and the Acidity Range of more B solution is faintly acid, very not applicable.
Trace it to its cause, organic polymer resin class boron adsorbent be copolymer by styrene or divinylbenzene as skeleton, first synthetic resin, then boron selective functional group bonding or grafting are got on to be prepared from.Such as XSC-700, Amberlite743, D564 resin etc., by styrene/divinylbenzene copolymer, modification obtains.1) because this type of adsorbent mostly is organic high molecular polymer, under strong acid and strong base environment, easily swelling and contraction after multiple adsorb-regeneration cycle, causes adsorbent fragmentation, and mechanical performance is poor, is difficult for repeatedly regeneration recycling.2) organic polymer resin, its skeleton is many to be made up of the copolymer of polystyrene or divinylbenzene, hydrophobicity is stronger, especially in structure, contain phenyl ring, its nonpolar structure strengthens hydrophobicity, be unfavorable for the mass transfer diffusion of solute in water environment, therefore effective mass transfer in boric acid aqueous solution, and then affect adsorption dynamics adsorption kinetics and equilibrium adsorption capacity.3) this type of adsorbent is by the group modified generation of macromolecular scaffold grafting functional, and groups density is uncontrollable, and therefore groups density can be lower, causes adsorbance lower.4), in the aqueous solution, boron can be with B (OH)
3, B (OH)
4 -, B
3o
3(OH)
4 -, B
4o
5(OH)
4 2-various ways exists, and their ratio is affected by the pH value of solution.Work as pH<6, mainly with B (OH)
3form exists; Work as pH>10, mainly with B (OH)
4 -form exists; When pH is between 6～10, various forms all exists.Most of organic polymer resins are applicable to adsorb in alkaline environment.For example XSC-700 resin can only be in the solution of pH=6～12 attracts boron; Amberlite743 resin can only adsorb B (OH)
4 -, more applicable in the solution of pH>10.This type of macromolecule resin class boron adsorbent is not acidproof.
Publication number be the Chinese patent literature of CN101549280A disclose a kind of by organosilan with containing compound synthesized gel rubber predecessor in organic solvent of polyhydroxy functional groups, then make this predecessor and organosilicon obtain the boron selective gel adsorbent that contains polyhydroxy functional groups by hydrolysis-condensation reaction, adsorption capacity can reach 1.15mmol/g.Its advantage is, the boron selective gel adsorbent that the method makes is compared with boron special efficacy polymeric adsorbent, and its gel, in the recycling of absorption and wash-out, shrinks with expansion littlely, and not cracky, has good mechanical strength.But the form of this silica-based boron adsorbent is by will grinding the amorphous granular forming after block gel drying, can affecting fluid and distribute and adsorption dynamics adsorption kinetics.In adsorption process, unbodied form can obviously change the linear speed of fluid and the state of laminar flow, makes fluid skewness weighing apparatus, forms channelling effect, mass transfer is impacted, so that the sudden change of Dynamic Adsorption amount or reduction, and adsorption equilibrium rate reduction.Unbodied form is easy to wear simultaneously, so that bed pressure drop rising, is not easy to Separation of Solid and Liquid, is unfavorable for industrial applications.
Summary of the invention
The invention provides a kind of spherical silica-based hybrid inorganic-organic boron adsorbent and preparation method thereof.Boron adsorbent is prepared in main employing meglumine and organosilan reaction.The boron adsorbent main component obtaining is inorganic matter, good mechanical property; And the finished product of this adsorbent is spherical, adsorbance is large, good stability, be convenient to industrial applications.
Spherical silica-based hybrid inorganic-organic boron adsorbent provided by the invention is that main component is the spherical boron adsorbent of hybrid silicon sill.The finished product spherical diameter of this boron adsorbent can regulate and control within the scope of 0.01～5mm, and dimensional homogeneity is good, and sphericity is better, and diameter is mainly by the addition control of surfactant.
Compared with unbodied hybrid silicon sill boron adsorbent, it is stable that spherical morphology can maintain adsorption dynamics adsorption kinetics and fluid distributing equilibrium, so that Dynamic Adsorption amount can not reduce and suddenly change, and the rate of adsorption is very fast, shortening time of equilibrium adsorption; Be convenient to Separation of Solid and Liquid, loss is little simultaneously, is more conducive to industrial applications.
Compared with organic polymer resin: 1) its organosilan exists as skeleton using silica inorganic constituents after hydrolytie polycondensation is crosslinked, be difficult for swelling, swelling less with contraction after multiple adsorb-regeneration cycle under strong acid and strong base environment, be difficult for broken, mechanical strength is better, the recycling of can repeatedly regenerating.2) while inorganic silicon skeleton acid and alkali-resistance, all can use under acid-base condition, and mechanical strength and chemical stability are better.3) methoxyl group of silane component is hydrolyzed into polyhydroxy structure except crosslink part, and polyhydroxy had both had stronger hydrophily, is beneficial to the mass transfer diffusion of boron in water environment, makes adsorption dynamics adsorption kinetics faster, shortens time of equilibrium adsorption; From boron absorption principle, be conducive to again the chelating suction-operated of boron at adsorbent surface simultaneously.4) can adjust by the ratio of regulatory function precursor and organosilan the density of functional adsorption group, thereby effectively improve the density of adsorption function base in unit mass adsorbent (the present invention provides adsorption function base by meglumine), improve adsorption capacity, adsorbance reaches as high as 2mmol/g.
The present invention also provides a kind of preparation method of spherical silica-based hybrid inorganic-organic boron adsorbent, comprises the following steps:
(1) prepare precursor: meglumine and the organosilan with epoxy radicals are dissolved in to polar solvent, at 60～100 ℃, react after 2～6 hours and obtain precursor through distillation and purification process, wherein meglumine is 1:0.8～1.2 with the mol ratio of the organosilan with epoxy radicals;
(2) prepare colloidal sol: the precursor that step (1) is made is dissolved according to mol ratio 0.25～10:1 in the aqueous solution of alcohol with the organosilan with methoxy or ethoxy, regulates pH value to 1～4, makes colloidal sol through hydrolysis and polycondensation reaction;
(3) prepare spherical silica-based boron adsorbent: under stirring, the colloidal sol that step (2) is made adds in dispersion solvent with the surfactant that accounts for sol volume 0.02%～1%, obtain reaction system, under aging temperature, carry out cross-linking reaction, after cross-linking reaction, carry out Separation of Solid and Liquid, the solid of separating is washed and be drying to obtain spherical silica-based hybrid inorganic-organic boron adsorbent, wherein dispersion solvent volume is sol volume 1～20 times.
Wherein, the described polar solvent of step (1) can adopt DMF or DMA.Described purification process preferably adopts soxhlet extraction, purification process 24～48 hours.
While distillation in step (1), polar solvent is more difficult evaporation sometimes, causes distillation time longer.Preferably adopt and revolve steaming, by reducing pressure and rotating, make solution form liquid film, expand disengagement area, improve distillation efficiency, shorten distillation time.
Step (1) Semi-polarity solvent is for dissolving meglumine and the organosilan with epoxy radicals, polar solvent does not participate in reaction, thereby the consumption of polar solvent dissolves meglumine and the organosilan with epoxy radicals completely as long as can meet, but the consumption of polar solvent can not be too many, otherwise can cause meglumine and there is the organosilan concentration of epoxy radicals too low, affect meglumine and the reaction rate of organosilan with epoxy radicals.Polar solvent is preferably meglumine and has 2～4 times of the organosilan cumulative volumes of epoxy radicals.
The described organosilan with methoxy or ethoxy of step (2) is specially at least one in γ-aminopropyl front three (second) TMOS, γ-(methacryloxy) propyl group front three (second) TMOS, γ-chloropropyl front three (second) TMOS, γ-(2,3-epoxy the third oxygen) propyl group front three (second) TMOS, methyl trimethoxy (second) TMOS, tetramethyl (second) TMOS.Organosilan provides inorganic silicon composition, makes material skeleton have stronger mechanical strength, and the adsorbent of preparing is reused in process at absorption-desorption, can be not broken.In addition, contain multiple hydroxyls after thering is the organosilan hydrolysis of multiple methoxy or ethoxies, be easier to crosslinked polycondensation, and the polyhydroxy structure that does not wherein participate in polycondensation is also beneficial to the absorption to boron.
Precursor described in step (2) is 0.25～10:1 with the mol ratio with methoxy or ethoxy organosilan.Because prepare in the process of colloidal sol in step (2), the ratio of precursor is larger, and mechanical strength is poorer, but its contained boron selective functional group densities can be larger, and absorption property is higher, but the ratio of precursor and organosilan can not be excessive.If the mol ratio of precursor and organosilan is greater than 10:1, mechanical strength is poor, may not can form colloidal sol; If be less than 0.25:1, because boron selective functional group is less, the adsorption capacity to boron of the adsorbent making is poor.
As preferably, precursor described in step (2) is 0.25～8:1 with the mol ratio of the organosilan with methoxy or ethoxy.
The consumption of the aqueous solution of the alcohol described in step (2) is precursor and organosilan cumulative volume 1～15 times.Because alcohol solution consumption is less than precursor and organosilan cumulative volume, can not be hydrolyzed completely, directly separate out, so that can not form colloidal sol; The amount of aqueous solution used of alcohol is too much, makes precursor and organosilan concentration too low, easily forms clear solution, but not collosol and gel.
As preferably, the aqueous solution of alcohol described in step (2) is precursor and the organosilan cumulative volume with methoxy or ethoxy 4～10 times.
In the aqueous solution of the alcohol described in step (2), alcohol accounts for 30%～80%(volume ratio), alcohol used can be at least one in methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, propane diols, n-butanol.The aqueous solution of alcohol is as the solvent of hydrolysis and polycondensation reaction.The product of sol-gel hydrolysis is also alcohol, and the aqueous solution of alcohol can suppress collosol and gel hydrolysis, and polycondensation is controlled to proper level.
In step (2), hydrolysis temperature is 60～100 ℃, hydrolysis time 8～24 hours.If hydrolysis temperature is less than 8h lower than 60 ℃ or reaction, follow-up balling-up reaction is slower, and productive rate is lower; If higher than 100 ℃ or reaction exceed 24 hours, easily make colloidal sol be solidified into piece, be unfavorable for follow-up dispersion balling-up.Within the scope of 60～100 ℃, the higher reaction time of temperature is more of a specified duration, is more beneficial to speed and the conversion ratio of the aging balling-up reaction of follow-up crosslinked polycondensation.Hydrolysis time occurring polycondensation send out should, thereby temperature when polycondensation is 60～100 ℃, 8～24 hours polycondensation time.
As preferably, in step (2), the temperature of hydrolysis is 80～90 ℃, 10～15 hours time of hydrolysis.
PH value while hydrolysis in step (2) is 1～4.Because pH can affect hydrolytie polycondensation speed, and then affect productive rate.Along with the increase of pH value, acidity reduces, and hydrolytie polycondensation speed slows down, and productive rate declines.Mainly that during for faintly acid or alkalescence, the chemical property of hydrolyzate changes, and by separating out with flocculent deposit or gluey form, is unfavorable for follow-up dispersion balling-up process because excessive when pH value; Too small when pH value, acidity is excessive, and hydrolysis rate is too fast, and reactant is hydrolyzed to little molecule more, is unfavorable for polycondensation balling-up, reduces polycondensation speed.Wherein regulate pH value can use sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid or other organic acids.
As preferably, in step (2), pH value is 2～3 when hydrolysis.PH value is that 2～3 o'clock hydrolysis rates are moderate, is beneficial to polycondensation balling-up.
The described dispersion solvent of step (3) is oil-soluble non-polar organic solvent.Be specially at least one in atoleine, pentane, isopentane, n-hexane, cyclohexane, normal heptane, normal octane, isooctane, benzinum, dichloroethanes, chloroform.
As preferably, the nonionic surface active agent that the described surfactant of step (3) is oleophylic, its hydrophilic lipophilic balance is between 3～8.The English full name of hydrophilic lipophilic balance is Hydrophile-Lipophile Balance Number, is called for short HLB value.The HLB value of the nonionic surface active agent of oleophylic, between 3～8, is applicable to do water-in-oil type (W/O) type emulsifying agent.If the HLB value >8 of this nonionic surface active agent, hydrophily is stronger, is applicable to do oil-in-water type (O/W) emulsifying agent, if HLB value <3 is applicable to do defoamer.
As preferably, the described surfactant of step (3) is sol volume 0.1%～0.5%.The effect of surfactant is to prevent drop poly-and reduction surface tension, makes colloidal sol become drop.Average grain diameter, particle diameter that surfactant concentration affects product distribute and particle shape.Surfactant concentration is larger, and the drop being dispersed into is less, the particle diameter less (0.01～5.00 millimeter) of the spherical adsorbent of generation.If but surfactant concentration is excessive, easily generate powdery product (100～130 microns), but not spherical products; If surfactant concentration is too small, the micellar concentration of its formation can not, by its effectively parcel of drop surface, cannot play effect stable, that protect and disperse.In addition can be as required, within the scope of appeal, the consumption of reconciliation statement surface-active agent is controlled product cut size size.
Concrete, the described surfactant of step (3) is polyoxyethylene sorbitol beeswax derivative, polyoxyethylene dioleate, polyoxyethylene (2EO) oleyl alcohol ether, methyl glycol fatty acid ester, propylene glycol monostearate, PGML, glycol fatty acid ester, polyoxyethylene sorbitol oleate, glycerin monostearate, hydroxylated lanolin, sorbitan sesquioleate, sorbitan monooleate, sorbitan monostearate, anhydrous sorbitol monopalmitate, diethylene glycol monolaurate, diethylene glycol monoleate, diethylene glycol fatty acid ester, diethylene glycol monostearate, methyl glucoside sesquialter stearic acid junket, at least one in TEG monostearate and TEG monoleate.
Colloidal sol in step (3) and the volume ratio of dispersion solvent are 1:1～20.The concentration of colloidal sol is larger, and dispersion solvent is not enough to be full of the space between particle or drop, causes the viscosity of suspension system to increase severely, and stirring, Flow of Goods and Materials and heat transfer all can be difficult, more easily occur and gather, and will make polymerization out of control, affect granulating; The concentration of colloidal sol is less, and polymerisation itself be there is no to harm, just can reduce utilization rate or production capacity, and industrial cost increases, so the concentration of colloidal sol optimum selecting in production cost and balling-up effect as required.
As preferably, the colloidal sol in step (3) and the volume ratio of dispersion solvent are 1:5～15.
In step (3), mixing speed is 200～800r/min.Within the scope of 200～800r/min, rotating speed is higher, and spherical product particle diameter is less; But when rotating speed exceedes 800r/min, make and gather aggravation, viscosity strengthens, and can cause particle diameter to increase.So as required, find equalization point, control rotating speed and adjust particle diameter.
As preferably, in step (3), mixing speed is 300～600r/min.
Inventor finds through repetition test, stir except can settlement prevention, augmentation of heat transfer and affect liquid-liquid dispersions and particle characteristics, the shape and size difference of paddle, the fluid producing in the time stirring distributes different, and the form of product is also had to certain influence.Preferably, in step (3), stirring the paddle adopting is the one in fine jade formula oar after pusher paddle, turbine type paddle and oar formula, flat oar, oblique oar and three leaves.
Aging temperature in step (3) is 40 ℃～120 ℃, and cross-linking reaction time is 24～96 hours.Temperature affects balling-up speed and finished product molecular weight, and temperature is higher, and balling-up speed is faster, and the reaction time is shorter.Along with the lengthening in reaction time, particle can occur and gather, and bead is also polymerized to large ball, and product cut size can increase, but the reaction time long after, the ball collision that easily makes to make is broken, productive rate reduces.The optimum selecting reaction time according to actual needs.
As preferably, the aging temperature in step (3) is 60～100 ℃, and cross-linking reaction time is 40～80 hours.
While washing in step (3), first adopt oil-soluble organic solvent washing, then with alcohol washing, finally wash residual alcohol with water.Mainly utilize alcohol to dissolve each other with organic solvent, the characteristic that can dissolve each other with water again.Oil-soluble organic solvent is specially at least one in n-hexane, cyclohexane, ether, benzinum etc.This washing step alcohol used is at least one in methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, propane diols and n-butanol.
In step (3), baking temperature is more than 30 ℃, and be 1～8 hour drying time.
The functional group in method of the present invention with the organosilan of methoxy or ethoxy is very easily hydrolyzed into hydroxyl, can there is polycondensation on the one hand, the hydroxyl that does not participate on the other hand reaction has stronger hydrophily, is conducive to the mass transfer diffusion of boric acid, is more conducive to the chelating of boron.An advantage of hybrid inorganic-organic boron adsorbent is to adjust by regulatory function precursor and the ratio with methoxy or ethoxy organosilan the density of functional adsorption group, thereby effectively improve the density of adsorption function base in unit mass adsorbent, improve adsorption capacity, reach as high as 2mmol/g; Another advantage is, the boron adsorbent of preparing is have inorganic skeleton spherical, and mechanical strength is high, do not affect fluid and distributes, and mass transfer diffusion effect is good, and dynamic adsorption is good.
Preparation method of the present invention is simple, and cost is lower, easy and simple to handle, and without gas shield and pressurized high-temperature reaction, dispersion solvent is recyclable to be reused, and safe green environmental protection, has broad application prospects.
Accompanying drawing explanation
Fig. 1 is the photo in kind of the spherical silica-based hybrid inorganic-organic boron adsorbent prepared according to the embodiment of the present invention 1;
Fig. 2 is the adsorption isotherm of the spherical silica-based hybrid inorganic-organic boron adsorbent prepared according to the embodiment of the present invention 5.
The specific embodiment
Below in conjunction with the preparation method of boron adsorbent and test result, the present invention is further described.
Embodiment 1
(1) prepare precursor: using meglumine as polyhydroxy functional groups compound and γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 1:1 mixing in molar ratio, add N, dinethylformamide solvent molten until its dissolve completely, stirring reaction 4 hours at 80 ℃, reacted solution is imported and revolves steaming instrument, at 60 ℃, 200r/min revolves and steams 20min to remove desolventizing, residue extracts (take methyl alcohol as reflux extracting liquid through Soxhlet, at 70 ℃, extract) after 48 hours, obtain the precursor that contains boron selective functional group;
(2) prepare colloidal sol: get 0.5 gram of precursor, 2.0 grams of tetramethoxy-silicanes that step (1) makes, be dissolved in 10 milliliter of 50% methanol aqueous solution, salt adding acid for adjusting pH value to 2, gained mixture reacts 12 hours at 80 ℃, after reaction finishes, makes colloidal sol;
(3) prepare spherical silica-based boron adsorbent: under agitation (rotating speed 500r/min), the colloidal sol that step (2) is made adds in 100mL atoleine, add again the sorbitan monooleate that accounts for sol volume 0.2%, obtain reaction system, 80 ℃ of the aging temperatures of control reaction system, continue stirring reaction 72 hours, now there is spheric granules to separate out, filter, gained solid n-hexane, ethanol, water washs successively, at 30 ℃, be dried and within 2 hours, obtain white spherical solid particle, this white spherical solid particle is exactly spherical silica-based hybrid inorganic-organic boron adsorbent.
After tested, solid particle sphericity is better, particle diameter is even, and grain size is about 4～5mm, and the adsorbance of boron is reached to 1.32mmol/g.
From Fig. 1, we can find out that the boron adsorbent that adopts the inventive method to prepare is spherical for white, and sphericity is better, particle diameter is even, and actual measurement grain size is between 4～5mm.
Embodiment 2
(1) prepare precursor: using meglumine as polyhydroxy functional groups compound, with γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 1:1 mixing in molar ratio, add N, dinethylformamide solvent molten until its dissolve completely, stirring reaction 4 hours at 80 ℃, reacted solution is imported and revolves steaming instrument, at 60 ℃, 200r/min revolves and steams 20min to remove desolventizing, residue extracts (take methyl alcohol as reflux extracting liquid, at 70 ℃, extracting) after 48 hours through Soxhlet, obtains the precursor that contains boron selective functional group;
(2) prepare colloidal sol: get 1.0 grams of precursors, 1.0 grams of tetramethoxy-silicanes that step (1) makes, be dissolved in 10 milliliter of 50% methanol aqueous solution, salt adding acid for adjusting pH to 2, gained mixture reacts 12 hours at 80 ℃, after reaction finishes, makes colloidal sol;
(3) prepare spherical silica-based boron adsorbent: under agitation (rotating speed 500r/min), the colloidal sol that step (2) is made adds in 100mL atoleine, add again the sorbitan monooleate that accounts for sol volume 0.2%, obtain reaction system, 80 ℃ of the aging temperatures of control reaction system, continue stirring reaction 72 hours, now there is spheric granules to separate out, filter, gained solid n-hexane, ethanol, water washs successively, at 30 ℃, be dried and within 2 hours, obtain white spherical solid particle, this white spherical solid particle is exactly spherical silica-based hybrid inorganic-organic boron adsorbent.
After tested: the sphericity of solid particle is better, particle diameter is even, and grain size is about 4～5mm.Boric acid adsorbance is reached to 1.75mmol/g.
Embodiment 3
(1) prepare precursor: using meglumine as polyhydroxy functional groups compound, with γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane in molar ratio 1:1 be dissolved at N, in dinethylformamide solvent, stirring reaction 4 hours at 80 ℃, reacted solution is imported and revolves steaming instrument, at 60 ℃, 200r/min revolves and steams 20min to remove desolventizing, residue extracts (take methyl alcohol as reflux extracting liquid through Soxhlet, at 70 ℃, extract) after 48 hours, obtain the precursor that contains boron selective functional group;
(2) prepare colloidal sol: get 2.5 grams of precursors, 0.5 gram of tetramethoxy-silicane that step (1) makes, be dissolved in 10 milliliter of 50% methanol aqueous solution, salt adding acid for adjusting pH to 2, gained mixture reacts 12 hours at 80 ℃, after reaction finishes, makes colloidal sol;
(3) prepare spherical silica-based boron adsorbent: under agitation (rotating speed 500r/min), the colloidal sol that step (2) is made adds in 100mL atoleine, add again the sorbitan monooleate that accounts for sol volume 0.2%, obtain reaction system, 80 ℃ of the aging temperatures of control reaction system, continue stirring reaction 72 hours, now there is spheric granules to separate out, filter, gained solid n-hexane, ethanol, water washs successively, at 30 ℃, be dried and within 2 hours, obtain white spherical solid particle, this white spherical solid particle is exactly spherical silica-based hybrid inorganic-organic boron adsorbent.
After tested, sphericity is better, particle diameter is even, and grain size is about 4～5mm, and boric acid adsorbance is reached to 2.13mmol/g.
Embodiment 4
(1) prepare precursor: using meglumine as polyhydroxy functional groups compound, with γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane in molar ratio 1:1 be dissolved at N, in dinethylformamide solvent, stirring reaction 4 hours at 80 ℃, reacted solution is imported and revolves steaming instrument, at 60 ℃, 200r/min revolves and steams 20min to remove desolventizing, residue extracts (take methyl alcohol as reflux extracting liquid through Soxhlet, at 70 ℃, extract) after 48 hours, obtain the precursor that contains boron selective functional group;
(2) prepare colloidal sol: get 0.5 gram of precursor, 2.0 grams of tetramethoxy-silicanes that step (1) makes, be dissolved in 10 milliliter of 50% methanol aqueous solution, salt adding acid for adjusting pH to 2, gained mixture reacts 12 hours at 80 ℃, after reaction finishes, makes colloidal sol;
(3) prepare spherical silica-based boron adsorbent: under agitation (rotating speed 500r/min), the colloidal sol that step (2) is made adds in 100mL atoleine, add again the sorbitan monooleate that accounts for sol volume 0.5%, obtain reaction system, 80 ℃ of the aging temperatures of control reaction system, continue stirring reaction 72 hours, now there is spheric granules to separate out, filter, gained solid n-hexane, ethanol, water washs successively, at 30 ℃, be dried and within 2 hours, obtain white spherical solid particle, this white spherical solid particle is exactly spherical silica-based hybrid inorganic-organic boron adsorbent.
After tested, sphericity is better, particle diameter is even, and grain size is about 1～2mm, and boric acid adsorbance is reached to 1.21mmol/g.
Embodiment 5
(1) prepare precursor: using meglumine as polyhydroxy functional groups compound, with γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane in molar ratio 1:1 be dissolved at N, in dinethylformamide solvent, stirring reaction 4 hours at 80 ℃, reacted solution is imported and revolves steaming instrument, at 60 ℃, 200r/min revolves and steams 20min to remove desolventizing, residue extracts (take methyl alcohol as reflux extracting liquid through Soxhlet, at 70 ℃, extract) after 48 hours, obtain the precursor that contains boron selective functional group;
(2) prepare colloidal sol: get 1.0 grams of precursors, 1.0 grams of tetramethoxy-silicanes that step (1) makes, be dissolved in 10 milliliter of 50% methanol aqueous solution, salt adding acid for adjusting pH to 2, gained mixture reacts 12 hours at 80 ℃, after reaction finishes, makes colloidal sol;
(3) prepare spherical silica-based boron adsorbent: under agitation (500rpm), the colloidal sol that step (2) is made adds in 100mL atoleine, add again the sorbitan monooleate that accounts for sol volume 0.5%, obtain reaction system, 80 ℃ of the aging temperatures of control reaction system, continue stirring reaction 72 hours, now there is spheric granules to separate out, filter, gained for solid n-hexane, ethanol, water wash successively, at 30 ℃, be dried and within 2 hours, obtain white spherical solid particle, this white spherical solid particle is exactly spherical silica-based hybrid inorganic-organic boron adsorbent.
After tested: sphericity is better, particle diameter is even, and grain size is about 1～2mm.
Fig. 2 is the adsorption isotherm of the spherical silica-based boron adsorbent that makes of the present embodiment, and abscissa is concentration C (ppm), and ordinate is the equilibrium adsorption capacity Q(mmol/g under equilibrium concentration).Take C/Q as ordinate, take C as abscissa, carry out Lang Gemiaoer linear fit, the maximal absorptive capacity Qm that can calculate spherical silica-based boron adsorbent prepared by the present embodiment by formula C/Q=1/ (Ks*Qm)+C/Qm is 1.67mmol/g.
Embodiment 6
(1) prepare precursor: using meglumine as polyhydroxy functional groups compound, with γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane in molar ratio 1:1 be dissolved at N, in dinethylformamide solvent, stirring reaction 4 hours at 80 ℃, reacted solution is imported and revolves steaming instrument, at 60 ℃, 200r/min revolves and steams 20min to remove desolventizing, residue extracts (take methyl alcohol as reflux extracting liquid through Soxhlet, at 70 ℃, extract) after 48 hours, obtain the precursor that contains boron selective functional group;
(2) prepare colloidal sol: get 2.5 grams of precursors, 0.5 gram of tetramethoxy-silicane that step (1) makes, be dissolved in 10 milliliter of 50% methanol aqueous solution, salt adding acid for adjusting pH to 2, gained mixture reacts 12 hours at 80 ℃, after reaction finishes, makes colloidal sol;
(3) prepare spherical silica-based boron adsorbent: under agitation (500rpm), the colloidal sol that step (2) is made adds in 100mL atoleine, add again the sorbitan monooleate that accounts for sol volume 0.5%, obtain reaction system, 80 ℃ of the aging temperatures of control reaction system, continue stirring reaction 72 hours, now there is spheric granules to separate out, filter, gained for solid n-hexane, ethanol, water wash successively, at 30 ℃, be dried and within 2 hours, obtain white spherical solid particle, this white spherical solid particle is exactly spherical silica-based hybrid inorganic-organic boron adsorbent.
After tested, sphericity is better, particle diameter is even, and grain size is about 1～2mm, and boric acid adsorbance is reached to 2.24mmol/g.
Boron adsorbance method of testing
Above embodiment all adopts the adsorbance of following methods test boron.
Adopt azomethine-H ultraviolet spectrophotometry to measure the boric acid concentration (mg/L) in solution, the preferred 415nm of wavelength, the boric acid concentration before adsorbing by computational analysis and after absorption, comparing calculation obtains the adsorbance (mmol/g) of this adsorbent to boron.
In the present invention, the computational methods of the adsorbance of adsorbent are as follows:
The quality of the molal weight/adsorbent of adsorbance=(the residue boric acid concentration after original solution boric acid concentration-adsorption equilibrium) * liquor capacity/boric acid.
Compound concentration is 1000ppm(=1g/L) BAS 1000mL, weigh the BAS that the about 0.1g of adsorbent, 0.2g, 0.3g, 0.4g, 0.5g, 0.6g, 0.7g, 0.8g, 0.9g, the 1.0g that make in embodiment are placed in respectively the 1000ppm that 50mL is above-mentioned joined, constant temperature oscillation 48 hours at 25 ℃, rotating speed is 150r/min.After reaching adsorption equilibrium, sample, analyze respectively after absorption remaining boric acid concentration in solution with azomethine-H AAS, so calculate respectively this adsorbent in different equilibrium concentrations the equilibrium adsorption capacity to boric acid.Then successively take equilibrium concentration as abscissa, equilibrium adsorption capacity is ordinate, draws equilibrium adsorption thermoisopleth by point.
Measuring mechanical property
The mechanical performance of boron adsorbent is mainly reflected in that to be repeatedly used rear adsorbent not damaged.
Table 1
As shown in table 1, the spherical silica-based hybrid inorganic-organic boron adsorbent of preparing in 6 embodiment of the present invention is repeated to 10 times (using 10 times) of absorption-parsing, have no boron adsorbent breakage occurs, good mechanical property is described.
Claims (10)
1. a preparation method for spherical silica-based hybrid inorganic-organic boron adsorbent, comprises the following steps:
(1) prepare precursor: meglumine and the organosilan with epoxy radicals are dissolved in to polar solvent, at 60～100 ℃, react after 2～6 hours and obtain precursor through distillation and purification process, wherein meglumine is 1:0.8～1.2 with the mol ratio of the organosilan with epoxy radicals;
(2) prepare colloidal sol: the precursor that step (1) is made is dissolved according to mol ratio 0.25～10:1 in the aqueous solution of alcohol with the organosilan with methoxy or ethoxy, regulates pH value to 1～4, makes colloidal sol through hydrolysis and polycondensation reaction;
(3) prepare spherical silica-based boron adsorbent: under stirring, the colloidal sol that step (2) is made adds in dispersion solvent with the surfactant that accounts for sol volume 0.02%～1%, obtain reaction system, under aging temperature, carry out cross-linking reaction, after cross-linking reaction, carry out Separation of Solid and Liquid, the solid of separating is washed and be drying to obtain spherical silica-based hybrid inorganic-organic boron adsorbent, wherein dispersion solvent volume is sol volume 1～20 times.
2. the preparation method of spherical silica-based hybrid inorganic-organic boron adsorbent as claimed in claim 1, is characterized in that: precursor described in step (2) is 0.25～8:1 with the mol ratio of the organosilan with methoxy or ethoxy.
3. the preparation method of spherical silica-based hybrid inorganic-organic boron adsorbent as claimed in claim 1, is characterized in that: the aqueous solution of alcohol described in step (2) is precursor and the organosilan cumulative volume with methoxy or ethoxy 4～10 times.
4. the preparation method of spherical silica-based hybrid inorganic-organic boron adsorbent as claimed in claim 1, is characterized in that: in step (2), the temperature of hydrolysis is 80～90 ℃, 10～15 hours time of hydrolysis.
5. the preparation method of spherical silica-based hybrid inorganic-organic boron adsorbent as claimed in claim 1, is characterized in that: while hydrolysis in step (2), pH value is 2～3.
6. the preparation method of spherical silica-based hybrid inorganic-organic boron adsorbent as claimed in claim 1, is characterized in that: the nonionic surface active agent that the described surfactant of step (3) is oleophylic, its hydrophilic lipophilic balance is between 3～8.
7. the preparation method of spherical silica-based hybrid inorganic-organic boron adsorbent as claimed in claim 1, is characterized in that: the described surfactant of step (3) is sol volume 0.1%～0.5%.
8. the preparation method of spherical silica-based hybrid inorganic-organic boron adsorbent as claimed in claim 1, is characterized in that: the colloidal sol in step (3) and the volume ratio of dispersion solvent are 1:5～15.
9. the preparation method of spherical silica-based hybrid inorganic-organic boron adsorbent as claimed in claim 1, is characterized in that: in step (3), mixing speed is 300～600r/min.
10. a spherical silica-based hybrid inorganic-organic boron adsorbent, is characterized in that: the preparation method described in the arbitrary claim of employing claim 1～9 makes.
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| CN111921505A (en) * | 2020-08-06 | 2020-11-13 | 同济大学 | O-diol functionalized macroporous through hole material, preparation method thereof and boric acid adsorption application |
| CN113000028A (en) * | 2021-04-27 | 2021-06-22 | 临沂海普新材料科技有限公司 | Preparation method of adsorbent for recovering phosphoric acid in waste acid |
| CN113304724A (en) * | 2021-06-03 | 2021-08-27 | 徐州禹慧环境科技研究院有限公司 | Preparation method of functional inorganic silica-based adsorption material |
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| US20020108912A1 (en) * | 1999-11-10 | 2002-08-15 | Tsutomu Taira | Method and apparatus for processing biologically hardly degradable waste water capable of reducing ozone |
| CN102407099A (en) * | 2011-09-08 | 2012-04-11 | 中南大学 | Preparation method of silica gel loaded polyhydroxyl chelating resin for highly effective boron removal |
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| US20020108912A1 (en) * | 1999-11-10 | 2002-08-15 | Tsutomu Taira | Method and apparatus for processing biologically hardly degradable waste water capable of reducing ozone |
| CN102407099A (en) * | 2011-09-08 | 2012-04-11 | 中南大学 | Preparation method of silica gel loaded polyhydroxyl chelating resin for highly effective boron removal |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111921505A (en) * | 2020-08-06 | 2020-11-13 | 同济大学 | O-diol functionalized macroporous through hole material, preparation method thereof and boric acid adsorption application |
| CN113000028A (en) * | 2021-04-27 | 2021-06-22 | 临沂海普新材料科技有限公司 | Preparation method of adsorbent for recovering phosphoric acid in waste acid |
| CN113304724A (en) * | 2021-06-03 | 2021-08-27 | 徐州禹慧环境科技研究院有限公司 | Preparation method of functional inorganic silica-based adsorption material |
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