CN104817272A - Use of metal ion-adsorption adsorbent as coloring agent, coloring agent and preparation method and use of coloring agent - Google Patents
Use of metal ion-adsorption adsorbent as coloring agent, coloring agent and preparation method and use of coloring agent Download PDFInfo
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Abstract
The invention discloses a use of a metal ion-adsorption adsorbent as a coloring agent, a coloring agent and a preparation method and use of the coloring agent. Active components of the coloring agent are metal ions carried in the adsorbent. Preferably, the adsorbent is silica sand or modified silica sand. The use realizes recycle of the adsorbent with metal ions, does not produce secondary pollution and protects the environment. Harmful ions are immobilized by glass or ceramic glaze, the glass or ceramic glaze has high chemical stability, and after entering into the glass or ceramic glaze, the harmful metal ions are immobilized permanently so that the coloring agent is safe and has lasting action period and change of waste into valuables is realized. After entering into glass, the harmful metal ions can be recycled permanently.
Description
Technical field
The present invention relates to a kind of using the novelty teabag as tinting material after the metal ion adsorbent in water or waste liquid, also relate to a kind of tinting material and its preparation method and application.
Background technology
Purification of waste water is one of major issue of facing of current mankind social development.The employing solid adsorbent harmful ion removed in waste water is one of the important component part and effective means of wastewater treatment, but the regeneration of used sorbent material becomes a difficult problem again, i.e. enable regeneration, also often adsorption efficiency can decline gradually, finally can only abandon, the sorbent material of absorption harmful ion becomes solid waste at last and becomes secondary pollution source, the treating method that there is no at present.Because glass has very high chemical stability, harmful ion is solidified by glass network in glass, not easily leaches, and therefore harmful ion being used for glass preparation is a kind of well utilization of waste material method.
In coloured glass, ceramic glaze or Production of Ceramics process, use tinting material sometimes and carry out painted, tinting material can be single tinting material, also can be the tinting material of mixing.At present, conventional tinting material is transition metal ion, as chromium, cadmium, nickel, copper, cobalt, manganese etc., usually adopt expensive industrial chemicals to introduce, and these ions is also often the harmful ion contained in trade effluent.
In actual industrial production, the painted dosage that glass, pottery or ceramic glaze itself adds is little, tinting material not easily mixes with the admixtion of glass, pottery or ceramic glaze, therefore the method generally adopting the first premix of the bulk raw material in tinting material and glass, pottery or ceramic glaze admixtion to prepare burden again is prepared burden, but this method needs to increase batching step and equipment, adds cost and operation easier.
Summary of the invention
The present invention is based on the problem that the sorbent material after adsorbing metal ions easily causes secondary pollution, provide the novelty teabag of the sorbent material after a kind of adsorbing metal ions, these are adsorbed with metal biosorption agent and use tinting material field, to realize utilization of waste material, reduce environmental pollution.
Present invention also offers a kind of tinting material, this tinting material for effective constituent with absorption or the metal ion of load in sorbent material, is the solution that the removing of harmful metal ion in water provides thoroughly comprehensively, puts things right once and for all, achieves refuse and effectively utilize.
Present invention also offers the preparation method of this tinting material, the method is simple to operate, is easy to realize.
Present invention also offers the application of this tinting material, namely can by them for raw material prepares coloured glass or ceramic glaze or pottery.
The present invention, in order to recycle harmful metal ion, is used adsorbent, and the sorbent material after adsorbing metal ions is because of containing metal ion, therefore may be used in the preparation of glass, pottery or ceramic glaze, for product colouring, play the effect of tinting material, concrete technical scheme is as follows:
Be adsorbed with the application of metal biosorption agent as tinting material.Time in sorbent material containing metal ion, with product can be made during some product of this absorbent preparation to produce color or colour-change, therefore can use as tinting material containing metal biosorption agent.
In above-mentioned application, preferably can as the tinting material of glass, pottery or ceramic glaze.Especially, when sorbent material is the raw material being suitable as glass, pottery or ceramic glaze, such as sorbent material be silica sand or modification silica sand time.
Present invention also offers a kind of tinting material, effective constituent is the metal ion of load in sorbent material.
In above-mentioned tinting material, described metal ion is bivalent nickel ion, divalent cobalt ion, sexavalence or trivalent chromic ion, divalent cadmium ion.
In above-mentioned tinting material, described sorbent material can be any can the inorganic materials of adsorbing metal ions, such as silica sand, zeolite, molecular sieve, clay etc.It can be preferably the sorbent material that can be used as the raw material of some colored product.When sorbent material itself can raw material as colored product time, tinting material have also been introduced a certain raw material while introducing metal ion, and therefore tinting material can replace part or all of a certain raw material.When sorbent material itself is not the raw material of colored product, the consumption of tinting material is wanted suitably, can not affect the performance of product.
In above-mentioned tinting material, described sorbent material is preferably silica sand or modification silica sand.Described modification silica sand can be adopt method disclosed in prior art to carry out the silica sand of modification, such as with the modification silica sand that iron and the coated silica sand of compound thereof are formed, the modification silica sand etc. that the oxide compound of manganese, aluminium, magnesium etc. or the coated silica sand of oxyhydroxide are formed, preferred modification silica sand is the modification silica sand obtained through porous silica Si modification.
In above-mentioned tinting material, preferably, the modification silica sand through porous silica Si modification obtains according to the method for following a or b:
Method a:
(1) in the mixture of triblock polymer P123, water and acid-washed quartz sand, first add water glass to mix, then add mixed in hydrochloric acid under fast stirring evenly, obtain reaction system; Or it is even first to add mixed in hydrochloric acid in the mixture of triblock polymer P123, water and acid-washed quartz sand, then adds water glass and mix, obtain reaction system;
(2) above-mentioned reaction system stirred, at 25-80 DEG C, concussion reaction 1h ~ 24h, makes water glass react and generates silicon-dioxide and be coated on quartz sand surface;
(3), after reaction, washing, filtration, get precipitation and dry;
(4) the precipitation dinectly bruning removing triblock polymer P123 of will dry, obtains Modified Quartz Sand; Or repeat step 2-4 time of (1), (2) and (3) again, carry out repeatedly coated with silica to quartz sand, quartz sand drying, calcining removing triblock polymer P123 after repeatedly coated, obtain Modified Quartz Sand;
Method b:
(1) cetyl trimethylammonium bromide is mixed in water with silica sand at 25-80 DEG C, then adding sodium hydroxide solution makes system be alkalescence, instill tetraethyl orthosilicate again, at 25-80 DEG C, react 1-24h, make tetraethyl orthosilicate be hydrolyzed the coated with silica of formation on silica sand surface;
(2) washing, filtering reacting liquid after reaction, gets precipitation drying;
(3) by the precipitation dinectly bruning of drying removing cetyl trimethylammonium bromide, porous silica modification silica sand is obtained; Or repeat step 2-4 time of (1) and (2) again, carry out repeatedly coated with silica to silica sand, silica sand drying, calcining removing cetyl trimethylammonium bromide after repeatedly coated, obtain porous silica modification silica sand.
In aforesaid method a, each reactant as follows with magnitude relation: triblock polymer P123: water: water glass: quartz sand=0.1-0.5g:40ml:1ml:2-10g.
In aforesaid method a, when the concentration of hydrochloric acid is 1mol/L, the volume ratio of hydrochloric acid and water glass is 3.2-10:1.
In aforesaid method a, step (3) preferably dries 3h at 90 DEG C.
In aforesaid method a, step (4) preferably removes triblock polymer P123 at 550 DEG C of calcining 6h.
In aforesaid method b, cetyl trimethylammonium bromide: water: tetraethyl orthosilicate: the amount ratio of silica sand is: 0.045g-0.54g:3.7-265ml:0.5-4ml:1-10g.
In aforesaid method b, when the concentration of sodium hydroxide solution is 0.175-0.6mol/L, the volume ratio of sodium hydroxide solution and water is 10:3.7-265.
In aforesaid method b, step (3) preferably dries 3h at 90 DEG C.
In aforesaid method b, step (3) preferably removes cetyl trimethylammonium bromide at 550 DEG C of calcining 6h.
In aforesaid method, the content of metal ion in sorbent material depends on adsorptive power and the absorbing process condition of sorbent material, and the content of metal ion in sorbent material is less than or equal to the maximal absorptive capacity of sorbent material.When adopting the sorbent material that specific surface area is large, adsorptive power is good, the content of the metal ion of absorption is high.
In aforesaid method, sorbent material can adopt any means adsorbing metal ions, the most conventional method is added by sorbent material in the aqueous solution containing metal ion or waste water, loads in sorbent material by means such as stirring, concussions by metal ion, then that sorbent material is dry.Those skilled in the art can control metal biosorption amount by the condition such as concentration, adsorption temp, time of the absorption number of times of the kind of adjustment sorbent material, sorbent material, metal ion.When adopting the mode in the embodiment of the present invention to adsorb, in sorbent material, the content of metal ion is 0.024-2.04mg/g.
Tinting material of the present invention, preferably can as the tinting material of tinted shade, pottery or ceramic glaze, for making tinted shade, pottery or ceramic glaze.When preparing these products, the consumption of tinting material is chosen according to the requirement of formula.
The present invention preferably with silica sand or modification silica sand for sorbent material, for enrichment harmful metal ion, then using the silica sand of adsorbing metal ions or modification silica sand as tinting material, as the raw material of tinted shade, pottery or ceramic glaze.In order to improve the adsorptive capacity of harmful metal ion, the present invention adopts the modification silica sand through special methods modification, and its specific surface area is large, can increase metal biosorption amount.
Tinting material of the present invention for carrier with silica sand or modification silica sand, when preparing for glass, pottery or ceramic glaze, had both been brought the silica composition of product needed into, and had been in turn introduced the coloring components of price, reduce production cost.The silica sand recycling of adsorbing metal ions, can not produce secondary pollution, protect environment; And utilizing glass or ceramic glaze solidification harmful ion, the chemical stability of glass or ceramic glaze is high, and will permanently be solidified after harmful metal ion enters glass or ceramic glaze, secure persistent, turns waste into wealth; Harmful ion also can permanent loops utilize after entering glass.
Tinting material of the present invention is with silica sand or modification silica sand for carrier, and mixing is simple, does not need pre-mixing process, simplifies processing step.
Accompanying drawing explanation
Fig. 1 is the SEM photo of embodiment 7 virgin quartz sand used.
Fig. 2 is the SEM photo of embodiment 7 once coated quartz sand.
Fig. 3 is the enlarged photograph of Fig. 2.
Fig. 4 is the SEM photo of embodiment 7 three coated quartz sands.
Fig. 5 is the SEM photo of embodiment 7 five coated quartz sands.
The N that Fig. 6 is 7 acid-washed quartz sand in embodiment and 1,3,5 coated quartz sand
2adsorption isothermal curve.
Fig. 7 is the scanning electron microscope (SEM) photograph not carrying out coated silica sand in embodiment 15.
Fig. 8 is the scanning electron microscope (SEM) photograph of gained sample after coated 5 times in embodiment 15.
Fig. 9 is the surperficial enlarged view of Fig. 8 sample.
Figure 10 is the N2-adsorption isothermal line of gained sample after embodiment 15 Central Plains silica sand and coated 1,3,5 time.
Figure 11 is the curve of spectrum of nickel ion in sodium silicate glass in embodiment 16.
Figure 12 is the curve of spectrum of nickel ion in potassium silicate glass in embodiment 16.
Figure 13 is the curve of spectrum of cobalt ion in sodium silicate glass in embodiment 17.
Figure 14 is the curve of spectrum of chromium ion in sodium silicate glass in embodiment 18.
Figure 15 is the curve of spectrum of embodiment 19 gained glass.
Figure 16 is the curve of spectrum of embodiment 20 gained glass.
Embodiment
Below, by specific embodiment, the present invention will be further elaborated, and following explanation is only to explain the present invention, does not limit its content.
Employing method a prepares modification silica sand
In following embodiment 1-6, specific surface area data is the result calculated value that 11 BET test gained, is designated as S
bET, wherein acid-washed quartz sand specific surface area is 0.148m
2/ g, 200 degree of vacuum outgass 10 hours before this sample testing.
In following embodiment 1-7, water glass degree Beaume used is 35, and modulus is 2.9 ~ 3.1.
Embodiment 1
1,0.3g P123 and 40mlH2O is mixed, be uniformly dissolved under 25 DEG C of conditions, then add 2g quartz sand (i.e. silica sand, lower same);
2, in the mixture of step 1, first add 1ml water glass, stir, then add the 1M hydrochloric acid soln of 4ml under rapid stirring, stir; Or first add the 1M hydrochloric acid soln of 4ml, stir, then add 1ml water glass, stir;
3, the reaction solution of step 2 is moved on shaking table, under convolution sway condition (processional frequency 200rpm), at 25 DEG C, react 12h, washing after reaction, filtration, after being deposited in 90 DEG C of dry 3h, then at 550 DEG C of calcining 6h, obtain Modified Quartz Sand sample.The specific surface area of gained sample is as shown in the table:
| Feed way | Modified Quartz Sand S BET(m 2/g) | Modified Quartz Sand and former quartz sand S BETRatio |
| Water glass after first hydrochloric acid | 5.740 | 38.784 times |
| Hydrochloric acid after first water glass | 19.586 | 132.338 doubly |
Embodiment 2
Get the P123 of approrpiate wts according to following table respectively, P123 and 40mlH2O is mixed, is uniformly dissolved under 25 DEG C of conditions, then adds 2g quartz sand and 1ml water glass, stir 15min at 25 DEG C after, add the 1M hydrochloric acid soln of 4ml under rapid stirring; Move on shaking table by this reaction solution, under convolution sway condition (processional frequency 200rpm), at 60 DEG C, react 12h, washing after reaction, filtration, be deposited in 90 DEG C of dry 3h, then at 550 DEG C of calcining 6h, obtains Modified Quartz Sand sample.Gained sample carries out specific surface area test.The consumption of P123 and the specific surface area of gained sample as shown in the table:
| P123(g) | Modified Quartz Sand S BET(m 2/g) | Modified Quartz Sand and former quartz sand S BETRatio |
| 0.1 | 12.524 | 84.622 times |
| 0.3 | 31.747 | 214.507 doubly |
| 0.5 | 6.319 | 42.696 times |
Embodiment 3
Mixed by 0.3g P123 and 40mlH2O, be uniformly dissolved under 25 DEG C of conditions, then add 2g quartz sand and 1ml water glass, stir 15min at 25 DEG C after, the 1M salt adding different volumes is under rapid stirring acid-soluble; Move on shaking table by this reaction solution, under convolution sway condition (processional frequency 200rpm), at 25 DEG C, react 12h, washing after reaction, filtration, be deposited in 90 DEG C of dry 3h, then at 550 DEG C of calcining 6h, obtains Modified Quartz Sand sample.Gained sample carries out specific surface area test.The consumption of hydrochloric acid and the specific surface area of gained sample as shown in the table:
| 1M hydrochloric acid (ml) | Modified Quartz Sand S BET(m 2/g) | The ratio of Modified Quartz Sand and former quartz sand BET |
| 3.2 | 10.387 | 70.182 times |
| 4 | 19.586 | 132.338 doubly |
| 10 | 9.433 | 63.736 times |
Embodiment 4
0.3g P123 and 40mlH2O is mixed, is uniformly dissolved under 25 DEG C of conditions, then add 2g quartz sand and 1ml water glass, stir 15min at 25 DEG C after, add the 1M hydrochloric acid soln of 4ml under rapid stirring; Move on shaking table by this reaction solution, under convolution sway condition (processional frequency 200rpm), react 3h at different temperatures, washing after reaction, filtration, be deposited in 90 DEG C of dry 3h, then at 550 DEG C of calcining 6h, obtains Modified Quartz Sand sample.Gained sample carries out specific surface area test.The specific surface area of temperature of reaction and gained sample is as shown in the table:
| Temperature of reaction (DEG C) | Modified Quartz Sand S BET(m 2/g) | The ratio of Modified Quartz Sand and former quartz sand BET |
| 25 | 19.586 | 132.338 doubly |
| 60 | 31.747 | 214.507 doubly |
| 80 | 14.394 | 97.257 times |
Embodiment 5
0.3g P123 and 40mlH2O is mixed, is uniformly dissolved under 25 DEG C of conditions, then add 2g quartz sand and 1ml water glass, stir 15min at 25 DEG C after, add the 1M hydrochloric acid soln of 4ml under rapid stirring; Move on shaking table by this reaction solution, under convolution sway condition (processional frequency 200rpm), at 60 DEG C, react different time, washing after reaction, filtration, be deposited in 90 DEG C of dry 3h, then at 550 DEG C of calcining 6h, obtains Modified Quartz Sand sample.Gained sample carries out specific surface area test.
The specific surface area of reaction times and gained sample is as shown in the table:
| Reaction times (h) | Modified Quartz Sand S BET(m 2/g) | The ratio of Modified Quartz Sand and former quartz sand BET |
| 1 | 13.949 | 94.25 times |
| 3 | 19.882 | 134.338 doubly |
| 12 | 31.747 | 214.507 doubly |
Embodiment 6
0.3g P123 and 40mlH2O is mixed, is uniformly dissolved under 25 DEG C of conditions, add quartz sand and the 1ml water glass of different grams, stir 15min at 25 DEG C after, add the 1M hydrochloric acid soln of 4ml under rapid stirring; Move on shaking table by this reaction solution, under convolution sway condition (processional frequency 200rpm), at 60 DEG C, react 12h, washing after reaction, filtration, be deposited in 90 DEG C of dry 3h, then at 550 DEG C of calcining 6h, obtains Modified Quartz Sand sample.Gained sample carries out specific surface area test.
The consumption of quartz sand and the specific surface area of gained sample as shown in the table:
| Quartz sand (g) | Modified Quartz Sand S BET(m 2/g) | The ratio of Modified Quartz Sand and former quartz sand BET |
| 2 | 31.747 | 214.507 doubly |
| 6 | 10.112 | 68.324 times |
| 10 | 8.586 | 58.014 times |
Embodiment 7
0.3g P123 and 40mlH2O is mixed, is uniformly dissolved under 25 DEG C of conditions, add 2g quartz sand and 1ml water glass, stir 15min at 25 DEG C after, add the 1M hydrochloric acid soln of the 4ml of different volumes under rapid stirring; Move on shaking table by this reaction solution, under convolution sway condition (processional frequency 200rpm), at 60 DEG C, react different time, washing after reaction, filtration, be deposited in 90 DEG C of dry 3h;
Dried precipitation is repeated according to the method described above more repeatedly coated, after repeatedly coated, be deposited in 90 DEG C of dry 3h, then at 550 DEG C of calcining 6h, obtain Modified Quartz Sand sample.
Specific surface area (the note: the specific surface area of gained sample is by N as shown in the table of quartz sand coated number of times and gained sample altogether
2isothermal curve calculates gained according to BET model, and former quartz sand specific surface area used is 0.199m
2/ g):
| Coated number of times | Modified Quartz Sand specific surface area (m 2/g) | The ratio of Modified Quartz Sand and former quartz sand BET |
| 1 time | 27.747 | 139.432 doubly |
| 3 times | 49.865 | 250.578 doubly |
| 5 times | 131.299 | 659.794 doubly |
Fig. 1 is the electron-microscope scanning picture on not coated quartz sand particle surface, and as can be seen from the figure, acid-treated virgin quartz sand grain corner is clearly demarcated, and surface is more smooth.Fig. 2 and 3 is electron-microscope scanning pictures of coated once rear gained modification sand, as can be seen from the figure, quartz sand particle corner angle after once coated are tending towards becoming circle, there is a little crackle in surface, as can be seen from enlarged view, Modified Quartz Sand surface is made up of silica dioxide granule, gel and gel congeries.Fig. 4, Fig. 5 are the electron-microscope scanning picture of three times, five times coated rear gained modification sand, and as can be seen from the figure, quartz sand particle corner angle are tending towards oval spherical or spherical, and upper layer is obvious, and particle increases.
The N2 isothermal curve of gained sample as shown in Figure 6, result shows, the hole of porous silica is mainly nanoporous, and NLDFT the model calculation shows, and 1 time, 3 times, 5 times coated rear samples are simultaneously containing the micropore of aperture about 1.3 nanometer and the mesoporous of 2.5 ~ 7 ran.
Employing method b prepares modification silica sand
In following embodiment 8-14, the calculation result that specific surface area data is multiple spot BET surface-area test gained (is designated as S
bET), wherein the specific surface area of original silica sand is 0.058m
2/ g.200 degree of vacuum outgass 10 hours before sample testing.
Embodiment 8
(1) cetyl trimethylammonium bromide of different mass, 2.0g silica sand, 100ml water are put and on the shaking table of 60 DEG C, shaken mixing 10 minutes (processional frequency 185 ~ 225rpm), then 10ml0.3M sodium hydroxide solution is added, dropwise add 1ml tetraethyl orthosilicate again, continue shaking table concussion reaction 3h at this temperature, make tetraethyl orthosilicate be hydrolyzed the coated with silica of formation on silica sand surface;
(2), after reaction, washing, filtration, get precipitation 90 DEG C of dry 3h;
(3) precipitation of drying is warming up to 550 DEG C of calcining 6h with the temperature rise rate of 1 DEG C/min and removes cetyl trimethylammonium bromide, obtain porous silica modification silica sand;
Gained sample carries out specific surface area test.The consumption of CTAB and the specific surface area of gained sample as shown in the table:
| CTAB(g) | Modification silica sand S BET(m 2/g) | Modification silica sand and former silica sand S BETRatio |
| 0.045 | 1.415 | 24.397 times |
| 0.36 | 14.728 | 253.931 doubly |
| 0.54 | 14.070 | 242.586 doubly |
Embodiment 9
(1) 0.36g cetyl trimethylammonium bromide, 2.0g silica sand are shaken with the water of different volumes on the shaking table of 60 DEG C mix 10 minutes (processional frequency 185 ~ 225rpm), then 10ml0.3M sodium hydroxide solution is added, dropwise add 1ml tetraethyl orthosilicate again, continue shaking table concussion reaction 3h at this temperature, make tetraethyl orthosilicate be hydrolyzed the coated with silica of formation on silica sand surface;
(2), after reaction, washing, filtration, get precipitation 90 DEG C of dry 3h;
(3) precipitation of drying is warming up to 550 DEG C of calcining 6h with the temperature rise rate of 1 DEG C/min and removes cetyl trimethylammonium bromide, obtain porous silica modification silica sand;
Gained sample carries out specific surface area test.The consumption of water and the specific surface area of gained sample as shown in the table:
| Pure water (ml) | Modification silica sand S BET(m 2/g) | The ratio of modification silica sand and former silica sand BET |
| 3.7 | 4.071 | 70.190 times |
| 50 | 39.54 | 681.724 doubly |
| 265 | 0.424 | 7.310 doubly |
Embodiment 10
(1) 0.36g cetyl trimethylammonium bromide, 2.0g silica sand, 50ml water are shaken mixing 10 minutes (processional frequency 185 ~ 225rpm) on the shaking table of 60 DEG C, then the sodium hydroxide solution of 10ml different concns is added, dropwise add 1ml tetraethyl orthosilicate again, continue shaking table concussion reaction 3h at this temperature, make tetraethyl orthosilicate be hydrolyzed the coated with silica of formation on silica sand surface;
(2), after reaction, washing, filtration, get precipitation 90 DEG C of dry 3h;
(3) precipitation of drying is warming up to 550 DEG C of calcining 6h with the temperature rise rate of 1 DEG C/min and removes cetyl trimethylammonium bromide, obtain porous silica modification silica sand;
Gained sample carries out specific surface area test.The concentration of NaOH solution and the specific surface area of gained sample as shown in the table:
| NaOH solution concentration (M) | Modification silica sand S BET(m 2/g) | The ratio of modification silica sand and former silica sand BET |
| 0.175 | 1.295 | 22.328 times |
| 0.3 | 41.233 | 710.914 doubly |
| 0.6 | 4.563 | 78.672 times |
Embodiment 11
(1) 0.36g cetyl trimethylammonium bromide, 2.0g silica sand, 50ml water are shaken mixing 10 minutes (processional frequency 185 ~ 225rpm) on the shaking table of 60 DEG C, then 10ml0.3M sodium hydroxide solution is added, dropwise add the tetraethyl orthosilicate of different volumes again, continue shaking table concussion reaction 3h at this temperature, make tetraethyl orthosilicate be hydrolyzed the coated with silica of formation on silica sand surface;
(2), after reaction, washing, filtration, get precipitation 90 DEG C of dry 3h;
(3) precipitation of drying is warming up to 550 DEG C of calcining 6h with the temperature rise rate of 1 DEG C/min and removes cetyl trimethylammonium bromide, obtain porous silica modification silica sand;
Gained sample carries out specific surface area test.The consumption of TEOS and the specific surface area of gained sample as shown in the table:
| TEOS(ml) | Modification silica sand S BET(m 2/g) | The ratio of modification silica sand and former silica sand BET |
| 0.5 | 0.611 | 10.534 times |
| 1.5 | 41.233 | 710.914 doubly |
| 4 | 9.657 | 166.5 doubly |
Embodiment 12
(1) 0.36g cetyl trimethylammonium bromide, 2.0g silica sand, 50ml water are shaken mixing 10 minutes (processional frequency 185 ~ 225rpm) on the shaking table of differing temps, then 10ml0.3M sodium hydroxide solution is added, dropwise add 1.5ml tetraethyl orthosilicate again, continue shaking table concussion reaction 3h at this temperature, make tetraethyl orthosilicate be hydrolyzed the coated with silica of formation on silica sand surface;
(2), after reaction, washing, filtration, get precipitation 90 DEG C of dry 3h;
(3) precipitation of drying is warming up to 550 DEG C of calcining 6h with the temperature rise rate of 1 DEG C/min and removes cetyl trimethylammonium bromide, obtain porous silica modification silica sand;
Gained sample carries out specific surface area test.The specific surface area of temperature of reaction and gained sample is as shown in the table:
| Temperature of reaction (DEG C) | Modification silica sand S BET(m 2/g) | The ratio of modification silica sand and former silica sand BET |
| 25 | 1.228 | 21.172 times |
| 60 | 41.233 | 710.914 doubly |
| 80 | 17.297 | 298.224 doubly |
As can be seen from the above table, along with the rising of temperature, specific surface area is the trend of first increases and then decreases, and temperature more than 80 DEG C after, TEOS is gel very easily, specific surface area substantially without increase.
Embodiment 13
(1) 0.36g cetyl trimethylammonium bromide, 2.0g silica sand, 50ml water are shaken mixing 10 minutes (processional frequency 185 ~ 225rpm) on the shaking table of 60 DEG C, then 10ml0.3M sodium hydroxide solution is added, dropwise add 1.5ml tetraethyl orthosilicate again, continue shaking table concussion reaction different time at this temperature, make tetraethyl orthosilicate be hydrolyzed the coated with silica of formation on silica sand surface;
(2), after reaction, washing, filtration, get precipitation 90 DEG C of dry 3h;
(3) precipitation of drying is warming up to 550 DEG C of calcining 6h with the temperature rise rate of 1 DEG C/min and removes cetyl trimethylammonium bromide, obtain porous silica modification silica sand;
Gained sample carries out specific surface area test.The specific surface area of reaction times and gained sample is as shown in the table:
| Reaction times (h) | Modification silica sand S BET(m 2/g) | The ratio of modification silica sand and former silica sand BET |
| 1 | 41.162 | 709.690 |
| 6 | 45.694 | 787.828 doubly |
| 12 | 43.663 | 752.810 doubly |
| 24 | 51.882 | 894.517 doubly |
Embodiment 14
(1) silica sand of 0.36g cetyl trimethylammonium bromide, different mass, 50ml water are shaken mixing 10 minutes (processional frequency 185 ~ 225rpm) on the shaking table of 60 DEG C, then 10ml0.3M sodium hydroxide solution is added, dropwise add 1.5ml tetraethyl orthosilicate again, continue shaking table concussion reaction 3h at this temperature, make tetraethyl orthosilicate be hydrolyzed the coated with silica of formation on silica sand surface;
(2), after reaction, washing, filtration, get precipitation 90 DEG C of dry 3h;
(3) precipitation of drying is warming up to 550 DEG C of calcining 6h with the temperature rise rate of 1 DEG C/min and removes cetyl trimethylammonium bromide, obtain porous silica modification silica sand;
Gained sample carries out specific surface area test.The consumption of silica sand and the specific surface area of gained sample as shown in the table:
| Silica sand (g) | Modification silica sand S BET(m 2/g) | Modification silica sand BET increases multiple than former silica sand |
| 1 | 63.894 | 1101.620 doubly |
| 4 | 27.789 | 479.121 doubly |
| 6 | 26.145 | 450.776 doubly |
| 10 | 19.468 | 335.655 doubly |
As can be seen from data above, along with the increase of silica sand quality, specific surface area presents the trend reduced gradually, and when silica sand is 1g, specific surface area is maximum, but gained modification silica sand amount is too small.
Embodiment 15
(1) 0.36g cetyl trimethylammonium bromide, 2.0g silica sand, 50ml water are shaken mixing 10 minutes (processional frequency 185 ~ 225rpm) on the shaking table of 60 DEG C, then 10ml0.3M sodium hydroxide solution is added, dropwise add 1.5ml tetraethyl orthosilicate again, continue shaking table concussion reaction 3h at this temperature, make tetraethyl orthosilicate be hydrolyzed the coated with silica of formation on silica sand surface;
(2), after reaction, washing, filtration, get precipitation 90 DEG C of dryings;
(3) throw out of drying is repeated step 2-4 time of (1) and (2) again, repeatedly coated with silica is carried out to silica sand; Silica sand after repeatedly coated through 90 DEG C of dry 3h, be warming up to 550 DEG C of calcining 6h with the temperature rise rate of 1 DEG C/min and remove cetyl trimethylammonium bromides, obtain porous silica modification silica sand.
Specific surface area (the note: the specific surface area of gained sample calculates gained by N2 isothermal curve according to BET model, and former silica sand specific surface area used is 0.098m as shown in the table of silica sand coated number of times and gained sample altogether
2/ g):
| Coated number of times | Modification silica sand surface-area (m 2/g) | The ratio of modification silica sand and former silica sand BET |
| 1 time | 38.741 | 395.316 doubly |
| 3 times | 106.630 | 1088.061 doubly |
| 5 times | 176.386 | 1799.857 doubly |
Fig. 7 is the electron-microscope scanning picture on not coated silica sand particles surface, and as can be seen from the figure, only show slightly coarse before silica sand is not coated, some surfaces are even smooth, and grain corner is clearly demarcated.Fig. 8 and 9 is electron-microscope scanning pictures of gained modification silica sand after coated 5 times, as can be seen from the figure, after coated, the obviously roughen of silica sand particles surface, particle is tending towards spheroidization, and as can be seen from enlarged view, there are the compositions such as silica dioxide granule, gel and gel congeries on silica sand surface.
As shown in Figure 10, result shows the N2 isothermal curve of gained sample, and the hole of porous silica is mainly mesoporous nano, and the BJH aperture of 1 time, 3 times, 5 times coated rear samples is respectively 2.19nm, 2.19nm, 2.36nm.
The Synthesis and applications of tinting material
Embodiment 16
PH be 1 ~ 6, concentration is any one modification silica sand adding common silica sand in the nickel ion solution of 1 ~ 15mg/L or obtain according to the method for embodiment 1-15, the add-on of common silica sand or modification silica sand is 0.01 ~ 0.14g/ ml soln, at 20 ~ 50 DEG C after adding, concussion or the lower absorption 1 ~ 90min of stirring, filtration drying after primary sorption, or reach filtration drying after silica sand or modification silica sand saturated extent of adsorption through multiple adsorb, obtain a series of silica sand or the modification silica sand that are adsorbed with the nickel ion of different content.Silica sand after these absorbed Ni ions and modification silica sand can be used as the tinting material of glass, pottery or ceramic glaze.
Below, for a kind of tinting material obtained in the following manner, explain the step of tinting material when preparing glass:
PH be 6, concentration is add the coated modification silica sand (0.01g modification silica sand/ml soln) obtained for 5 times in embodiment 7 in the nickel ion aqueous solution of 15mg/l, adsorption conditions: 25 DEG C, 60min; Filtration drying after absorption, obtains tinting material.Recording nickel ion content in tinting material according to atomic absorption spectrophotometer is 0.594mg/g modification silica sand.
By above-mentioned tinting material for the preparation of sodium silicate glass, parent glass consists of (wt%): Na
2o 22%, CaO 12%, SiO
260%, MgO 4%, Al
2o
32%.Raw material, wherein SiO is selected according to this parent glass composition
2modification silica sand by above-mentioned absorbed Ni ion is introduced, and CaO can be introduced by calcium oxide or calcium carbonate, Na
2o is introduced by sodium carbonate, and MgO is introduced by magnesium oxide or magnesium basic carbonate, Al
2o
3by Al (OH)
3introduce (these raw materials are called main raw material, lower same).On the basis of main raw material, conveniently ratio can also add auxiliary material (finings and fusing assistant), such as, can add the Sb of the 0.5wt% of main raw material sum
2o
3or the NaNO of the 1.2wt% of main raw material sum
3as finings, the CaF of the 1.03wt% of main raw material sum can also be added
2as fusing assistant.Crucible is put into after being mixed by above-mentioned all raw materials, crucible is warming up to 1350 DEG C with the temperature rise rate of 5 DEG C/min in retort furnace and is incubated 2h, obtain glass metal, gained glass metal composition is even, bubble-free, pour glass metal into die for molding and the 2h that anneals at 550 DEG C, obtain yellow sodium silicate glass.Figure 11 is the curve of spectrum of nickel ion in sodium silicate glass.
By above-mentioned tinting material for the preparation of potassium silicate glass, parent glass consists of (wt%): K
2o 22%, CaO 12%, SiO
260%, MgO 4%, Al
2o
32%.Select main raw material according to composition requirement and add auxiliary material, wherein SiO
2introduce by above-mentioned tinting material.All raw materials are made glass according to the method described above, and gained potassium silicate glass is purple, and Figure 12 is the curve of spectrum of nickel ion in potassium silicate glass.
Embodiment 17
PH be 1 ~ 6, concentration is any one modification silica sand adding common silica sand in the cobalt ion solution of 3 ~ 60mg/L or obtain according to the method for embodiment 1-15, the add-on of common silica sand or modification silica sand is 0.005 ~ 0.24g/ ml soln, at 20 ~ 50 DEG C after adding, concussion or the lower absorption 1 ~ 120min of stirring, filtration drying after primary sorption, or reach filtration drying after silica sand or modification silica sand saturated extent of adsorption through multiple adsorb, obtain a series of silica sand or the modification silica sand that are adsorbed with the cobalt ion of different content.Silica sand after these adsorption of cobalt ions and modification silica sand can be used as the tinting material of glass, pottery or ceramic glaze.
Below, for a kind of tinting material obtained in the following manner, explain the step of tinting material when preparing glass:
PH be 6, concentration is add the coated modification silica sand (0.01g modification silica sand/ml soln) obtained for 5 times in embodiment 7 in the cobalt ion aqueous solution of 60mg/L, adsorption conditions: 25 DEG C, 60min; Filtration drying after absorption, obtains tinting material.Recording cobalt ion content in tinting material according to atomic absorption spectrophotometer is 2.04mg/g modification silica sand.
By this tinting material for the preparation of soda lime glass, parent glass consists of (wt%): Na
2o 22%, CaO 12%, SiO
260%, MgO 4%, Al
2o
32%.Except SiO
2by outside the modification silica sand introducing of adsorption of cobalt ion, other raw materials and preparation are all conventionally carried out, and gained glass is blue, and Figure 13 is the cobalt ion curve of spectrum in glass.
Embodiment 18
PH be 1 ~ 7, concentration is the Cr of 1 ~ 100mg/L
3+any one modification silica sand adding common silica sand in solion or obtain according to the method for embodiment 1-15, the add-on of common silica sand or modification silica sand is 0.01 ~ 0.08g/ ml soln, at 20 ~ 50 DEG C after adding, concussion or the lower absorption 1 ~ 120min of stirring, filtration drying after primary sorption, or reach filtration drying after silica sand or modification silica sand saturated extent of adsorption through multiple adsorb, obtain a series of Cr being adsorbed with different content
3+silica sand or modification silica sand.These adsorb Cr
3+after silica sand and modification silica sand can be used as the tinting material of glass, pottery or ceramic glaze.
Below, for a kind of tinting material obtained in the following manner, explain the step of tinting material when preparing glass:
PH be 6, concentration is the Cr of 5mg/L
3+the coated modification silica sand (0.01g modification silica sand/ml soln) obtained for 5 times in embodiment 15 is added, adsorption conditions: 25 DEG C, 30min in the aqueous solution; Filtration drying after absorption, obtains tinting material.Adopt colorimetry to record Cr ionic concn in solution, calculate Cr in tinting material
3+content is 0.35mg/g modification silica sand.
By this tinting material for the preparation of soda lime glass, parent glass consists of (wt%): Na
2o 22%, CaO 12%, SiO
260%, MgO 4%, Al
2o
32%.Except SiO
2by absorption Cr
3+modification silica sand introduce outside, other raw materials and preparation all conventionally carry out, gained glass is bright green, and Figure 14 is Cr
3+the curve of spectrum in glass.
Embodiment 19
Be the Cr of 5mg/L in pH=3, concentration
6+the coated modification silica sand (0.02g modification silica sand/ml soln) obtained for 5 times in embodiment 15 is added, adsorption conditions: 25 DEG C, 30min in solution; Filtration drying after absorption, obtains tinting material.Adopt colorimetry to record Cr ionic concn in solution, calculate Cr in modification silica sand
6+content is 0.024mg/g.
With above-mentioned absorption Cr
6+after modification silica sand and coloured material MnO
2together as mixed colorant, prepare purple soda lime glass.Parent glass composition is (wt%): Na
2o 22%, CaO 12%, SiO
260%, MgO 4%, Al
2o
32%.Select main raw material according to composition requirement and add auxiliary material, wherein SiO
2all by absorption Cr
6+after modification silica sand introduce, MnO
2consumption be the 3wt% of main raw material sum.All raw materials are risen to 1350 DEG C of insulation 2h with the speed of 5 DEG C/min, annealing 2h.Meanwhile, arrange contrast experiment, the glass of contrast experiment is only with MnO
2as tinting material, introduce SiO
2raw material for not adsorb Cr
6+blank modification silica sand, other conditions are all identical.
Use absorption Cr
6+modification silica sand and use the modification silica sand without absorption to make the curve of spectrum of glass as shown in figure 15, as can be seen from the figure, use absorption Cr
6+the glass of modification silica sand declines than the transmitance near 480nm with the glassy phase that do not use, illustrate and contain Cr
6+modification silica sand enhance glass coloring.
Embodiment 20
PH be 1 ~ 7, concentration is the Cd of 0.1-100mg/L
2+any one modification silica sand adding common silica sand in solution or obtain according to the method for embodiment 1-15, the add-on of common silica sand or modification silica sand is 0.005-0.01g/ ml soln, at 20 ~ 50 DEG C after adding, concussion or the lower absorption 1 ~ 210min of stirring, filtration drying after primary sorption, or reach filtration drying after modification silica sand saturated extent of adsorption through multiple adsorb, obtain a series of silica sand or the modification silica sand that are adsorbed with different content cadmium ion.Silica sand after these Adsorption of Cadmiums and modification silica sand can be used as the tinting material of glass, pottery or ceramic glaze.
Below, for the modification silica sand of a kind of Adsorption of Cadmium obtained in the following manner, explain the step of tinting material when preparing glass:
PH be 6, concentration is add the coated modification silica sand (0.01g modification silica sand/ml soln) obtained for 5 times in embodiment 7 in the cadmium ion aqueous solution of 15mg/l, adsorption conditions: 25 DEG C, 30min; Filtration drying after absorption, recording cadmium ion content in tinting material according to atomic absorption spectrophotometer is 0.74mg/g modification silica sand.
With above-mentioned absorption Cd
2+after modification silica sand together with coloured material sulphur selenium compound as mixed colorant, prepare soda lime glass.The composition of parent glass is (wt%): Na
2o 22%, CaO 12%, SiO
260%, MgO 4%, Al
2o
32%.Select main raw material according to composition requirement and add auxiliary material, wherein SiO
2all by absorption Cd
2+after modification silica sand introduce, sulphur selenium compound is introduced by selenium powder and ZnS, and the consumption of selenium powder is the 1wt% of main raw material sum, and the consumption of ZnS is the 0.03wt% of main raw material sum.Mixed by all raw materials, when rising to 1200 DEG C with the speed of 5 DEG C/min, high temperature feeds in raw material, and continues to be warming up to 1350 DEG C, insulation 2h, and annealing 2h, obtain light-yellow tinge soda lime glass, its curve of spectrum as shown in figure 16.
Above embodiment is only to explain the present invention; do not limit to therewith; under the guiding of the present invention's design, modification silica sand is changed into common silica sand or other can be used as the schemes such as other sorbent materials of glass or ceramic glaze raw material all should within scope.
Claims (10)
1. be adsorbed with the application of metal biosorption agent as tinting material.
2. a tinting material, is characterized in that: effective constituent is the metal ion of load in sorbent material.
3. tinting material according to claim 2, is characterized in that: described metal ion is Ni
2+, Co
2+, Cr
6+, Cr
3+or Cd
2+.
4. tinting material according to claim 2, is characterized in that: described sorbent material is silica sand or modification silica sand.
5. tinting material according to claim 4, is characterized in that: described modification silica sand obtains according to the method for following a or b:
method a:
(1) in the mixture of triblock polymer P123, water and acid-washed quartz sand, first add water glass to mix, then add mixed in hydrochloric acid under fast stirring evenly, obtain reaction system; Or it is even first to add mixed in hydrochloric acid in the mixture of triblock polymer P123, water and acid-washed quartz sand, then adds water glass and mix, obtain reaction system;
(2) above-mentioned reaction system is stirred, at 25-80 DEG C, shake reaction 1 h ~ 24 h, water glass is reacted and generates silicon-dioxide and be coated on quartz sand surface;
(3), after reaction, washing, filtration, get precipitation and dry;
(4) the precipitation dinectly bruning removing triblock polymer P123 of will dry, obtains Modified Quartz Sand; Or repeat step 2-4 time of (1), (2) and (3) again, carry out repeatedly coated with silica to quartz sand, quartz sand drying, calcining removing triblock polymer P123 after repeatedly coated, obtain Modified Quartz Sand;
method b:
(1) cetyl trimethylammonium bromide is mixed in water with silica sand at 25-80 DEG C, then adding sodium hydroxide solution makes system be alkalescence, instill tetraethyl orthosilicate again, at 25-80 DEG C, react 1-24 h, make tetraethyl orthosilicate be hydrolyzed the coated with silica of formation on silica sand surface;
(2) washing, filtering reacting liquid after reaction, gets precipitation drying;
(3) by the precipitation dinectly bruning of drying removing cetyl trimethylammonium bromide, porous silica modification silica sand is obtained; Or repeat step 2-4 time of (1) and (2) again, carry out repeatedly coated with silica to silica sand, silica sand drying, calcining removing cetyl trimethylammonium bromide after repeatedly coated, obtain porous silica modification silica sand.
6. tinting material according to claim 5, it is characterized in that: in method a, each reactant as follows with magnitude relation: triblock polymer P123: water: water glass: quartz sand=0.1-0.5g:40ml:1ml:2-10g, when the concentration of hydrochloric acid is 1mol/L, the volume ratio of hydrochloric acid and water glass is 3.2-10:1.
7. tinting material according to claim 5, is characterized in that: in method b, cetyl trimethylammonium bromide: water: tetraethyl orthosilicate: the amount ratio of silica sand is: 0.045g-0.54g:3.7-265ml:0.5-4 ml:1-10 g; When the concentration of sodium hydroxide solution is 0.175-0.6 mol/L, the volume ratio of sodium hydroxide solution and water is 10:3.7-265.
8. tinting material according to claim 2, is characterized in that: the content of metal ion in sorbent material is 0.024-2.04mg/g.
9. the preparation method of the tinting material according to any one of a claim 2-8, it is characterized in that comprising the following steps: get aqueous metallic ions or the waste water containing metal ion, add adsorbent metal ion wherein wherein, after absorption, sorbent material is dry, obtain tinting material.
10. tinted shade, pottery or a ceramic glaze, is characterized in that: raw material comprises the tinting material according to any one of claim 2-8.
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| WO2019104460A1 (en) * | 2017-11-28 | 2019-06-06 | 桑胜伟 | Method for preparing composite conductive paste |
| CN109529919A (en) * | 2018-12-26 | 2019-03-29 | 桂林理工大学 | A kind of preparation method of the dedicated modified molecular sieve of ceramic ink |
| CN109529919B (en) * | 2018-12-26 | 2022-07-08 | 桂林理工大学 | Preparation method of modified molecular sieve special for ceramic ink |
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