CN104817272B - The adsorbent of metal ion is adsorbed with as the application of colouring agent, gained colouring agent and its preparation and application - Google Patents
The adsorbent of metal ion is adsorbed with as the application of colouring agent, gained colouring agent and its preparation and application Download PDFInfo
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Abstract
The invention discloses a kind of adsorbent for being adsorbed with metal ion as the application of colouring agent, gained colouring agent and its preparation and application, colouring agent active ingredient is the metal ion being supported in adsorbent, and adsorbent is preferably silica sand or modified silica sand.The present invention recycles the adsorbent of adsorbing metal ions, will not produce secondary pollution, protects environment；And using glass or ceramic glaze solidification harmful ion, the chemical stability of glass or ceramic glaze is high, and harmful metal ion will permanently be solidified after entering glass or ceramic glaze, and secure persistent turns waste into wealth；After harmful ion enters glass, can also permanent loops utilization.
Description
Technical field
As the new application of colouring agent after being adsorbed with adsorbent the present invention relates to a kind of metal ion using in water or waste liquid,
Further relate to a kind of colouring agent and its preparation method and application.
Background technology
Purification of waste water is one of major issue that current mankind social development faces.Using in solid absorbent removing waste water
Harmful ion be one of important component and effective means of wastewater treatment, but the regeneration of used adsorbent turns into again
Problem, that is, enable regeneration, and also tending to adsorption efficiency can be gradually reduced, and can only finally abandon, and adsorbs the adsorbent end of harmful ion
Solid waste will be changed into and turn into pollution source, the treating method that there is no at present.Because glass has change very high
Stability is learned, harmful ion is solidified by glass network in glass, be difficult to leach, therefore be for glass preparation by harmful ion
A kind of good twice laid method.
During coloured glass, ceramic glaze or Production of Ceramics, coloured using to colouring agent sometimes, colouring agent can
Being the colouring agent of single colouring agent, or mixing.At present, conventional colouring agent is transition metal ions, such as chromium,
Cadmium, nickel, copper, cobalt, manganese etc., are generally introduced using expensive industrial chemicals, and these ions are contained in industrial wastewater
Harmful ion.
In actual industrial production, seldom, colouring agent is difficult and glass the amount of colorant that glass, ceramics or ceramic glaze are added in itself
The batch of glass, ceramics or ceramic glaze is mixed, therefore is typically coordinated with glass, ceramics or ceramic glaze using colouring agent
The method that bulk raw material in material first premixes again dispensing carries out dispensing, but this method needs to increase batching step and equipment, increases
Cost and operation difficulty are added.
The content of the invention
The present invention easily causes the problem of secondary pollution based on the adsorbent after adsorbing metal ions, there is provided one kind absorption
These adsorbents for being adsorbed with metal ion are used colouring agent field by the new application of the adsorbent after metal ion, to realize
Twice laid, reduces environmental pollution.
Present invention also offers a kind of colouring agent, the colouring agent is to adsorb or be supported on the metal ion in adsorbent to have
Effect composition, for the removing of harmful metal ion in water provides solution thoroughly comprehensively, once and for all, realizing waste has
Effect is utilized.
Present invention also offers the preparation method of the colouring agent, the method is simple to operate, it is easy to accomplish.
Present invention also offers the application of the colouring agent, you can with by they as raw material prepare coloured glass or ceramic glaze or
Ceramics.
The present invention is adsorbed it with adsorbent, the suction after adsorbing metal ions to recycle harmful metal ion
Attached dose, because containing metal ion, therefore can be used in prepared by glass, ceramics or ceramic glaze, be product colouring, play colouring agent
Effect, concrete technical scheme is as follows：
The adsorbent of metal ion is adsorbed with as the application of colouring agent.When containing metal ion in adsorbent, this is used
Adsorbent can make product produce color or color change when preparing some products, therefore the adsorbent containing metal ion can make
For colouring agent is used.
In above-mentioned application, preferably can be as the colouring agent of glass, ceramics or ceramic glaze.Especially, when adsorbent is suitable
Cooperate during for the raw material of glass, ceramics or ceramic glaze, such as when adsorbent is silica sand or modified silica sand.
Present invention also offers a kind of colouring agent, active ingredient is the metal ion being supported in adsorbent.
In above-mentioned colouring agent, the metal ion is bivalent nickel ion, divalent cobalt ion, sexavalence or trivalent chromic ion, two
Valency cadmium ion.
In above-mentioned colouring agent, the adsorbent can be any inorganic material for being capable of adsorbing metal ions, such as silica sand,
Zeolite, molecular sieve, clay etc..It is preferred that can be the adsorbent of the raw material that can act as some colored products.When adsorbent in itself
Can as the raw material of colored product when, colouring agent have also been introduced a certain raw material while metal ion is introduced, therefore coloring
Agent can replace all or part of a certain raw material.When adsorbent is not in itself the raw material of colored product, the consumption of colouring agent
It is appropriate, it is impossible to influence the performance of product.
In above-mentioned colouring agent, the adsorbent is preferably silica sand or modified silica sand.The modified silica sand can be using existing
There is the silica sand that the method disclosed in technology is modified, such as with iron and its modified silica sand of compound cladding silica sand formation, manganese,
Modified silica sand that oxide or hydroxide the cladding silica sand of aluminium, magnesium etc. are formed etc., preferably modified silica sand is through porous dioxy
SiClx is modified the modified silica sand for obtaining.
In above-mentioned colouring agent, it is preferred that through porous silica Si modification modified silica sand according to following a or b method system
：
Method a：
(1) to first added in the mixture of triblock polymer P123, water and acid-washed quartz sand waterglass be well mixed, then
Add mixed in hydrochloric acid uniform under fast stirring, obtain reaction system；Or to triblock polymer P123, water and acid-washed quartz sand
Mixture in first add mixed in hydrochloric acid uniform, add waterglass and be well mixed, obtain reaction system；
(2) above-mentioned reaction system is stirred, concussion reaction 1h~24h at 25-80 DEG C makes waterglass react generation
Silica is simultaneously coated on quartz sand surface；
(3) after reacting, washing, filtering take precipitation drying；
(4) the precipitation dinectly bruning that will be dried removes triblock polymer P123, obtains Modified Quartz Sand；Or repeat
(1), the step of (2) and (3) 2-4 times, multiple coated with silica is carried out to quartz sand, and repeatedly the quartz sand after cladding is through drying
Dry, calcining removes triblock polymer P123, obtains Modified Quartz Sand；
Method b：
(1) cetyl trimethylammonium bromide is mixed in water with silica sand at 25-80 DEG C, is subsequently adding NaOH
Solution makes system in alkalescence, then instills tetraethyl orthosilicate, and 1-24h is reacted at 25-80 DEG C, tetraethyl orthosilicate is hydrolyzed shape
Into coated with silica on silica sand surface；
(2) washing, filtering reacting liquid, take precipitation drying after reacting；
(3) dry precipitation dinectly bruning is removed into cetyl trimethylammonium bromide, obtains porous silica modified silicon
Sand；Or 2-4 times the step of repeat (1) and (2), multiple coated with silica is carried out to silica sand, the multiple silica sand after cladding
Cetyl trimethylammonium bromide is removed through drying, calcining, porous silica modified silica sand is obtained.
In above method a, each reactant it is as follows with magnitude relation：Triblock polymer P123：Water：Waterglass：Quartz sand
=0.1-0.5g：40ml：1ml：2-10g.
In above method a, when the concentration of hydrochloric acid is 1mol/L, hydrochloric acid is 3.2-10 with the volume ratio of waterglass:1.
In above method a, step (3) preferably dries 3h at 90 DEG C.
In above method a, step (4) is preferably calcined 6h and removes triblock polymer P123 at 550 DEG C.
In above 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 above method b, when the concentration of sodium hydroxide solution is 0.175-0.6mol/L, sodium hydroxide solution and water
Volume ratio is 10：3.7-265.
In above method b, step (3) preferably dries 3h at 90 DEG C.
In above method b, step (3) is preferably calcined 6h and removes cetyl trimethylammonium bromide at 550 DEG C.
In the above method, content of the metal ion in adsorbent depends on the adsorption capacity and absorbing process bar of adsorbent
Part, maximal absorptive capacity of content of the metal ion in adsorbent less than or equal to adsorbent.Using specific surface area is big, adsorption capacity
During the adsorbent got well, the content of the metal ion of absorption is high.
In the above method, adsorbent can use any means adsorbing metal ions, and most conventional methods are by adsorbent
Add in the aqueous solution containing metal ion or waste water, metal ion is loaded into adsorbent by means such as stirring, concussions
In, then adsorbent is dried.Those skilled in the art can by adjust the species of adsorbent, the absorption number of times of adsorbent,
The conditions such as concentration, adsorption temp, the time of metal ion control the adsorbance of metal ion.Using the side in the embodiment of the present invention
When formula is adsorbed, the content of metal ion is 0.024-2.04mg/g in adsorbent.
Colouring agent of the present invention, preferably can be as the colouring agent of coloured glass, ceramics or ceramic glaze, for being made coloured glass
Glass, ceramics or ceramic glaze.When these products are prepared, the consumption of colouring agent is chosen according to the requirement of formula.
The present invention preferably with silica sand or modified silica sand as adsorbent, for being enriched with harmful metal ion, then by ADSORPTION OF GOLD
Belong to the silica sand or modified silica sand of ion as colouring agent, the raw material as coloured glass, ceramics or ceramic glaze.It is harmful in order to improve
The adsorbance of metal ion, using the modified silica sand being modified by specific process, its specific surface area is big, can increase gold for the present invention
Belong to the adsorbance of ion.
Colouring agent of the present invention when being prepared for glass, ceramics or ceramic glaze, was both brought into silica sand or modified silica sand as carrier
The silica composition of product needed, introduces the coloring components of price again, reduces production cost.Adsorbing metal ions
Silica sand recycle, secondary pollution will not be produced, protect environment；And using glass or ceramic glaze solidification harmful ion, glass
Or the chemical stability of ceramic glaze is high, harmful metal ion will permanently be solidified after entering glass or ceramic glaze, be held safely
Long, turn waste into wealth；Harmful ion can also permanent loops utilization after entering glass.
, with silica sand or modified silica sand as carrier, mixing is simple, it is not necessary to pre-mixing process, simplifies technique for colouring agent of the present invention
Step.
Brief description of the drawings
Fig. 1 is the SEM photograph of virgin quartz sand used by embodiment 7.
Fig. 2 is the SEM photograph that embodiment 7 once coats quartz sand.
Fig. 3 is the enlarged photograph of Fig. 2.
Fig. 4 is 7 three SEM photographs of cladding quartz sand of embodiment.
Fig. 5 is 7 five SEM photographs of cladding quartz sand of embodiment.
Fig. 6 for 7 acid-washed quartz sand in embodiment and 1,3,5 times coat quartz sand N2Adsorption isothermal curve.
Fig. 7 is the scanning electron microscope (SEM) photograph of silica sand coated in embodiment 15.
The scanning electron microscope (SEM) photograph of Fig. 8 samples obtained by being coated in embodiment 15 after 5 times.
Fig. 9 is the surface enlarged drawing of Fig. 8 samples.
Figure 10 is the Central Plains silica sand of embodiment 15 and the N2- adsorption isotherms for coating gained sample after 1,3,5 times.
Figure 11 is the curve of spectrum of the nickel ion in sodium silicate glass in embodiment 16.
Figure 12 is the curve of spectrum of the nickel ion in potassium silicate glass in embodiment 16.
Figure 13 is the curve of spectrum of the cobalt ions in sodium silicate glass in embodiment 17.
Figure 14 is the curve of spectrum of the chromium ion in sodium silicate glass in embodiment 18.
Figure 15 is the curve of spectrum of the gained glass of embodiment 19.
Figure 16 is the curve of spectrum of the gained glass of embodiment 20.
Specific embodiment
Below, by specific embodiment, the present invention will be further elaborated, and the description below is merely to explain this hair
It is bright, its content is not limited.
Modified silica sand is prepared using method a
In following embodiment 1-6, specific surface area data is the result calculated value obtained by 11 point BET tests, is designated as SBET,
Wherein acid-washed quartz sand specific surface area is 0.148m2/ g, 200 degree of vacuum outgas 10 hours before the sample testing.
In following embodiment 1-7, waterglass Baume degrees used is 35, and modulus is 2.9~3.1.
Embodiment 1
1st, 0.3g P123 and 40mlH2O are mixed, are uniformly dissolved under the conditions of 25 DEG C, add 2g quartz sands (i.e. silica sand,
Similarly hereinafter)；
2nd, to 1ml waterglass is first added in the mixture of step 1, stir, then add under rapid stirring
The 1M hydrochloric acid solutions of 4ml, stir；Or first add 4ml 1M hydrochloric acid solutions, stir, add 1ml waterglass,
Stir；
3rd, the reaction solution of step 2 is moved on shaking table, it is anti-at 25 DEG C under convolution sway condition (cyclotron frequency 200rpm)
Answer 12h, after reaction wash, filtering, be deposited in 90 DEG C dry 3h after, then 550 DEG C calcine 6h, obtain Modified Quartz Sand sample.
The specific surface area of gained sample is as shown in the table：
| Feed way | ||
| Waterglass after first hydrochloric acid | 5.740 | 38.784 times |
| Hydrochloric acid after first waterglass | 19.586 | 132.338 times |
Embodiment 2
Take the P123 of approrpiate wts respectively according to following table, P123 and 40mlH2O mixed, be uniformly dissolved under the conditions of 25 DEG C,
2g quartz sands and 1ml waterglass are added, after stirring 15min at 25 DEG C, the 1M salt of 4ml is added under rapid stirring
Acid solution；This reaction solution is moved on shaking table, under convolution sway condition (cyclotron frequency 200rpm), 12h is reacted at 60 DEG C, instead
Should after wash, filter, be deposited in 90 DEG C and dry 3h, then calcine 6h at 550 DEG C, obtain Modified Quartz Sand sample.Gained sample enters
Row specific surface area is tested.The consumption of P123 and the specific surface area of gained sample are as shown in the table：
| P123(g) | ||
| 0.1 | 12.524 | 84.622 times |
| 0.3 | 31.747 | 214.507 times |
| 0.5 | 6.319 | 42.696 times |
Embodiment 3
0.3g P123 and 40mlH2O are mixed, is uniformly dissolved under the conditions of 25 DEG C, add 2g quartz sands and 1ml water glass
Glass, after stirring 15min at 25 DEG C, adds the 1M hydrochloric acid of different volumes molten under rapid stirring；This reaction solution is moved
To shaking table, under sway condition of circling round (cyclotron frequency 200rpm), 12h is reacted at 25 DEG C, washed after reaction, filtered, precipitation
3h is dried at 90 DEG C, then 6h is calcined at 550 DEG C, Modified Quartz Sand sample is obtained.Gained sample carries out specific surface area test.Hydrochloric acid
Consumption and gained sample specific surface area it is as shown in the table：
| 1M hydrochloric acid (ml) | The ratio between Modified Quartz Sand and former quartz sand BET | |
| 3.2 | 10.387 | 70.182 times |
| 4 | 19.586 | 132.338 times |
| 10 | 9.433 | 63.736 times |
Embodiment 4
0.3g P123 and 40mlH2O are mixed, is uniformly dissolved under the conditions of 25 DEG C, add 2g quartz sands and 1ml water glass
Glass, after stirring 15min at 25 DEG C, adds the 1M hydrochloric acid solutions of 4ml under rapid stirring；This reaction solution is moved to and is shaken
On bed, under sway condition of circling round (cyclotron frequency 200rpm), 3h is reacted at different temperatures, washed after reaction, filtered, be deposited in
90 DEG C dry 3h, then calcine 6h at 550 DEG C, obtain Modified Quartz Sand sample.Gained sample carries out specific surface area test.Reaction temperature
The specific surface area of degree and gained sample is as shown in the table：
| Reaction temperature (DEG C) | The ratio between Modified Quartz Sand and former quartz sand BET | |
| 25 | 19.586 | 132.338 times |
| 60 | 31.747 | 214.507 times |
| 80 | 14.394 | 97.257 times |
Embodiment 5
0.3g P123 and 40mlH2O are mixed, is uniformly dissolved under the conditions of 25 DEG C, add 2g quartz sands and 1ml water glass
Glass, after stirring 15min at 25 DEG C, adds the 1M hydrochloric acid solutions of 4ml under rapid stirring；This reaction solution is moved to and is shaken
On bed, under sway condition of circling round (cyclotron frequency 200rpm), different time is reacted at 60 DEG C, washed after reaction, filtered, precipitation
3h is dried at 90 DEG C, then 6h is calcined at 550 DEG C, Modified Quartz Sand sample is obtained.Gained sample carries out specific surface area test.
The specific surface area of reaction time and gained sample is as shown in the table：
| Reaction time (h) | The ratio between Modified Quartz Sand and former quartz sand BET | |
| 1 | 13.949 | 94.25 times |
| 3 | 19.882 | 134.338 times |
| 12 | 31.747 | 214.507 times |
Embodiment 6
0.3g P123 and 40mlH2O are mixed, is uniformly dissolved under the conditions of 25 DEG C, add the quartz sand and 1ml of different grams
Waterglass, after stirring 15min at 25 DEG C, adds the 1M hydrochloric acid solutions of 4ml under rapid stirring；This reaction solution is moved
To shaking table, under sway condition of circling round (cyclotron frequency 200rpm), 12h is reacted at 60 DEG C, washed after reaction, filtered, precipitation
3h is dried at 90 DEG C, then 6h is calcined at 550 DEG C, Modified Quartz Sand sample is obtained.Gained sample carries out specific surface area test.
The consumption of quartz sand and the specific surface area of gained sample are as shown in the table：
| Quartz sand (g) | The ratio between Modified Quartz Sand and former quartz sand BET | |
| 2 | 31.747 | 214.507 times |
| 6 | 10.112 | 68.324 times |
| 10 | 8.586 | 58.014 times |
Embodiment 7
0.3g P123 and 40mlH2O are mixed, are uniformly dissolved under the conditions of 25 DEG C, add 2g quartz sands and 1ml waterglass,
After stirring 15min at 25 DEG C, the 1M hydrochloric acid solutions of the 4ml of different volumes are added under rapid stirring；This is reacted
Liquid is moved on shaking table, under convolution sway condition (cyclotron frequency 200rpm), different time is reacted at 60 DEG C, washed after reaction,
Filtering, is deposited in 90 DEG C and dries 3h；
Dried precipitation is repeated into cladding repeatedly according to the method described above, repeatedly 90 DEG C of dryings is deposited in after cladding
3h, then calcines 6h at 550 DEG C, obtains Modified Quartz Sand sample.
Quartz sand coats the specific surface area of number of times and gained sample (note as shown in the table altogether：The ratio table of gained sample
Area is by N2Isothermal curve calculates gained according to BET models, and former quartz sand specific surface area used is 0.199m2/g)：
| Cladding number of times | The ratio between Modified Quartz Sand and former quartz sand BET | |
| 1 time | 27.747 | 139.432 times |
| 3 times | 49.865 | 250.578 times |
| 5 times | 131.299 | 659.794 times |
Fig. 1 is the electron-microscope scanning picture on uncoated quartz sand particle surface, it can be seen that acid treatment is original
Quartz sand particle corner angle are clearly demarcated, and surface is more smooth.Fig. 2 and 3 is the electron-microscope scanning picture of the modified sand of gained after coating once, from figure
In as can be seen that quartz sand particle corner angle after once coating tend to being rounded, there is a little crackle in surface, can from enlarged drawing
To find out, Modified Quartz Sand surface is made up of silica dioxide granule, gel and gel congeries.Fig. 4, Fig. 5 are three times, five bags
The electron-microscope scanning picture of the modified sand of gained after covering, it can be seen that quartz sand particle corner angle tend to oval spherical or spherical,
Substantially, particle increases superficial layer.
As shown in fig. 6, result shows, the hole of porous silica is mainly nano-pore for the N2 isothermal curves of gained sample,
NLDFT the model calculations show, 1 time, 3 times, after 5 claddings sample simultaneously the micropore containing about 1.3 nanometers of aperture and 2.5~
7 rans it is mesoporous.
Modified silica sand is prepared using method b
In following embodiment 8-14, the result of calculation that specific surface area data is obtained by the test of multiple spot BET surface area (is designated as
SBET), wherein the specific surface area of original silica sand is 0.058m2/g.200 degree of vacuum outgas 10 hours before sample testing.
Embodiment 8
(1) cetyl trimethylammonium bromide of different quality, 2.0g silica sands, 100ml water are put on 60 DEG C of shaking table
Concussion 10 minutes (185~225rpm of cyclotron frequency) of mixing, is subsequently adding 10ml0.3M sodium hydroxide solutions, then be added dropwise over
1ml tetraethyl orthosilicates, continue shaking table concussion reaction 3h at this temperature, make the silica that tetraethyl orthosilicate is hydrolyzed to form
It is coated on silica sand surface；
(2) after reacting, washing, filtering take 90 DEG C of precipitation and dry 3h；
(3) dry precipitation is warming up to 550 DEG C of calcining 6h with the heating rate of 1 DEG C/min and removes cetyl trimethyl
Ammonium bromide, obtains porous silica modified silica sand；
Gained sample carries out specific surface area test.The consumption of CTAB and the specific surface area of gained sample are as shown in the table：
| CTAB(g) | ||
| 0.045 | 1.415 | 24.397 times |
| 0.36 | 14.728 | 253.931 times |
| 0.54 | 14.070 | 242.586 times |
Embodiment 9
(1) water of 0.36g cetyl trimethylammonium bromides, 2.0g silica sands and different volumes is shaken on 60 DEG C of shaking table
10 minutes (185~225rpm of cyclotron frequency) of mixing is swung, 10ml0.3M sodium hydroxide solutions is subsequently adding, then be added dropwise over 1ml
Tetraethyl orthosilicate, continues shaking table concussion reaction 3h at this temperature, makes the silica bag that tetraethyl orthosilicate is hydrolyzed to form
Overlay on silica sand surface；
(2) after reacting, washing, filtering take 90 DEG C of precipitation and dry 3h；
(3) dry precipitation is warming up to 550 DEG C of calcining 6h with the heating rate of 1 DEG C/min and removes cetyl trimethyl
Ammonium bromide, obtains porous silica modified silica sand；
Gained sample carries out specific surface area test.The consumption of water and the specific surface area of gained sample are as shown in the table：
| Pure water (ml) | The ratio between modified silica sand and former silica sand BET |
| 3.7 | 4.071 | 70.190 times |
| 50 | 39.54 | 681.724 times |
| 265 | 0.424 | 7.310 times |
Embodiment 10
(1) 0.36g cetyl trimethylammonium bromides, 2.0g silica sands, 50ml water are shaken into mixing on 60 DEG C of shaking table
10 minutes (185~225rpm of cyclotron frequency), is subsequently adding the sodium hydroxide solution of 10ml various concentrations, then be added dropwise over 1ml
Tetraethyl orthosilicate, continues shaking table concussion reaction 3h at this temperature, makes the silica bag that tetraethyl orthosilicate is hydrolyzed to form
Overlay on silica sand surface；
(2) after reacting, washing, filtering take 90 DEG C of precipitation and dry 3h；
(3) dry precipitation is warming up to 550 DEG C of calcining 6h with the heating rate of 1 DEG C/min and removes cetyl trimethyl
Ammonium bromide, obtains porous silica modified silica sand；
Gained sample carries out specific surface area test.The concentration of NaOH solution and the specific surface area of gained sample such as following table institute
Show：
| NaOH solution concentration (M) | The ratio between modified silica sand and former silica sand BET | |
| 0.175 | 1.295 | 22.328 times |
| 0.3 | 41.233 | 710.914 times |
| 0.6 | 4.563 | 78.672 times |
Embodiment 11
(1) 0.36g cetyl trimethylammonium bromides, 2.0g silica sands, 50ml water are shaken into mixing on 60 DEG C of shaking table
10 minutes (185~225rpm of cyclotron frequency), is subsequently adding 10ml0.3M sodium hydroxide solutions, then be added dropwise over different volumes
Tetraethyl orthosilicate, continues shaking table concussion reaction 3h at this temperature, makes the silica bag that tetraethyl orthosilicate is hydrolyzed to form
Overlay on silica sand surface；
(2) after reacting, washing, filtering take 90 DEG C of precipitation and dry 3h；
(3) dry precipitation is warming up to 550 DEG C of calcining 6h with the heating rate of 1 DEG C/min and removes cetyl trimethyl
Ammonium bromide, obtains porous silica modified silica sand；
Gained sample carries out specific surface area test.The consumption of TEOS and the specific surface area of gained sample are as shown in the table：
| TEOS(ml) | The ratio between modified silica sand and former silica sand BET | |
| 0.5 | 0.611 | 10.534 times |
| 1.5 | 41.233 | 710.914 times |
| 4 | 9.657 | 166.5 times |
Embodiment 12
(1) 0.36g cetyl trimethylammonium bromides, 2.0g silica sands, 50ml water are shaken on the shaking table of different temperatures
10 minutes (185~225rpm of cyclotron frequency) of mixing, is subsequently adding 10ml0.3M sodium hydroxide solutions, then be added dropwise over 1.5ml
Tetraethyl orthosilicate, continues shaking table concussion reaction 3h at this temperature, makes the silica bag that tetraethyl orthosilicate is hydrolyzed to form
Overlay on silica sand surface；
(2) after reacting, washing, filtering take 90 DEG C of precipitation and dry 3h；
(3) dry precipitation is warming up to 550 DEG C of calcining 6h with the heating rate of 1 DEG C/min and removes cetyl trimethyl
Ammonium bromide, obtains porous silica modified silica sand；
Gained sample carries out specific surface area test.The specific surface area of reaction temperature and gained sample is as shown in the table：
| Reaction temperature (DEG C) | The ratio between modified silica sand and former silica sand BET | |
| 25 | 1.228 | 21.172 times |
| 60 | 41.233 | 710.914 times |
| 80 | 17.297 | 298.224 times |
As can be seen from the above table, with the rising of temperature, specific surface area is in the trend of first increases and then decreases, and temperature is super
Cross after 80 DEG C, TEOS easily gels, specific surface area is substantially without increase.
Embodiment 13
(1) 0.36g cetyl trimethylammonium bromides, 2.0g silica sands, 50ml water are shaken into mixing on 60 DEG C of shaking table
10 minutes (185~225rpm of cyclotron frequency), is subsequently adding 10ml0.3M sodium hydroxide solutions, then be added dropwise over the positive silicon of 1.5ml
Sour tetra-ethyl ester, continues shaking table concussion reaction different time at this temperature, makes the silica that tetraethyl orthosilicate is hydrolyzed to form
It is coated on silica sand surface；
(2) after reacting, washing, filtering take 90 DEG C of precipitation and dry 3h；
(3) dry precipitation is warming up to 550 DEG C of calcining 6h with the heating rate of 1 DEG C/min and removes cetyl trimethyl
Ammonium bromide, obtains porous silica modified silica sand；
Gained sample carries out specific surface area test.The specific surface area of reaction time and gained sample is as shown in the table：
| Reaction time (h) | The ratio between modified silica sand and former silica sand BET | |
| 1 | 41.162 | 709.690 |
| 6 | 45.694 | 787.828 times |
| 12 | 43.663 | 752.810 times |
| 24 | 51.882 | 894.517 times |
Embodiment 14
(1) 0.36g cetyl trimethylammonium bromides, the silica sand of different quality, 50ml water are shaken on 60 DEG C of shaking table
10 minutes (185~225rpm of cyclotron frequency) of mixing is swung, 10ml0.3M sodium hydroxide solutions is subsequently adding, then be added dropwise over
1.5ml tetraethyl orthosilicates, continue shaking table concussion reaction 3h at this temperature, make the titanium dioxide that tetraethyl orthosilicate is hydrolyzed to form
Silicon is coated on silica sand surface；
(2) after reacting, washing, filtering take 90 DEG C of precipitation and dry 3h；
(3) dry precipitation is warming up to 550 DEG C of calcining 6h with the heating rate of 1 DEG C/min and removes cetyl trimethyl
Ammonium bromide, obtains porous silica modified silica sand；
Gained sample carries out specific surface area test.The consumption of silica sand and the specific surface area of gained sample are as shown in the table：
| Silica sand (g) | Modified silica sand BET increases multiple than former silica sand | |
| 1 | 63.894 | 1101.620 times |
| 4 | 27.789 | 479.121 times |
| 6 | 26.145 | 450.776 times |
| 10 | 19.468 | 335.655 times |
From data above as can be seen that with the increase of silica sand quality, specific surface area is presented the trend being gradually reduced, silicon
Specific surface area is maximum when sand is 1g, but the modified silica sand amount of gained is too small.
Embodiment 15
(1) 0.36g cetyl trimethylammonium bromides, 2.0g silica sands, 50ml water are shaken into mixing on 60 DEG C of shaking table
10 minutes (185~225rpm of cyclotron frequency), is subsequently adding 10ml0.3M sodium hydroxide solutions, then be added dropwise over the positive silicon of 1.5ml
Sour tetra-ethyl ester, continues shaking table concussion reaction 3h at this temperature, and the coated with silica for hydrolyzing to form tetraethyl orthosilicate exists
Silica sand surface；
(2) after reacting, washing, filtering take 90 DEG C of dryings of precipitation；
(3) the step of dry sediment being repeated into (1) and (2) 2-4 times, multiple silica bag is carried out to silica sand
Cover；Repeatedly the silica sand after cladding is dried 3h, 550 DEG C of calcining 6h removings 16 is warming up to the heating rate of 1 DEG C/min through 90 DEG C
Alkyl trimethyl ammonium bromide, obtains porous silica modified silica sand.
Silica sand coats the specific surface area of number of times and gained sample (note as shown in the table altogether：The specific surface of gained sample
Product calculates gained by N2 isothermal curves according to BET models, and former silica sand specific surface area used is 0.098m2/g)：
| Cladding number of times | The ratio between modified silica sand and former silica sand BET | |
| 1 time | 38.741 | 395.316 times |
| 3 times | 106.630 | 1088.061 times |
| 5 times | 176.386 | 1799.857 times |
Fig. 7 is the electron-microscope scanning picture on uncoated silica sand particles surface, it can be seen that before silica sand is uncoated only
Show slightly coarse, some surfaces are even smooth, and grain corner is clearly demarcated.Fig. 8 and 9 is that the Electronic Speculum for coating the modified silica sand of gained after 5 times is swept
Tracing piece, it can be seen that by after cladding, silica sand particles surface is substantially roughening, and particle tends to spheroidization, from amplification
Figure is as can be seen that there are the compositions such as silica dioxide granule, gel and gel congeries on silica sand surface.
The N2 isothermal curves of gained sample as shown in Figure 10, as a result show that the hole of porous silica is mainly nanometer Jie
Hole, 1 time, 3 times, the BJH apertures of sample are respectively 2.19nm, 2.19nm, 2.36nm after 5 claddings.
The preparation and application of colouring agent
Embodiment 16
Common silica sand is added in pH is the nickel ion solution that 1~6, concentration is 1~15mg/L or according to embodiment 1-15
Any one modified silica sand for obtaining of method, the addition of common silica sand or modified silica sand is molten for 0.01~0.14g/ milliliters
Liquid, at 20~50 DEG C after addition, 1~90min of absorption under concussion or stirring, filtration drying after once adsorbing, or by multiple
Absorption reaches filtration drying after silica sand or modified silica sand saturated extent of adsorption, obtains a series of nickel ions for being adsorbed with different content
Silica sand or modified silica sand.These absorption nickel ions after silica sand and modified silica sand can serve as glass, ceramics or ceramic glaze
Toner.
Below, by taking a kind of colouring agent for obtaining as follows as an example, the step of colouring agent is when glass is prepared is explained：
The modified silicon that cladding is obtained for 5 times in embodiment 7 is added during pH is the nickel ion aqueous solution that 6, concentration is 15mg/l
Sand (0.01g be modified silica sand/milliliter solution), adsorption conditionses：25 DEG C, 60min；Filtration drying after absorption, obtains colouring agent.According to original
Nickel ion content is the modified silica sands of 0.594mg/g during sub- absorption spectrophotometer measures colouring agent.
Above-mentioned colouring agent is used to prepare sodium silicate glass, parent glass composition is (wt%)：Na2O 22%, CaO
12%th, SiO260%th, MgO 4%, Al2O32%.According to parent glass composition selection raw material, wherein SiO2By above-mentioned absorption
The modified silica sand of nickel ion is introduced, and CaO can be introduced by calcium oxide or calcium carbonate, Na2O is introduced by sodium carbonate, and MgO is by magnesia
Or basic magnesium carbonate is introduced, Al2O3By Al (OH)3Introduce (these raw materials are referred to as primary raw material, similarly hereinafter).In the base of primary raw material
On plinth, auxiliary material (fining agent and flux) can also be added according to conventional ratio, for example, can add primary raw material sum
0.5wt% Sb2O3Or the NaNO of the 1.2wt% of primary raw material sum3As fining agent, can also add primary raw material it
The CaF of the 1.03wt% of sum2As flux.It is put into crucible after above-mentioned all raw materials are well mixed, by crucible in Muffle
With the heating rate of 5 DEG C/min 1350 DEG C being warming up in stove and being incubated 2h, obtain glass metal, gained glass metal composition is uniform, without gas
Bubble, die for molding is poured into and the 2h that anneals at 550 DEG C by glass metal, obtains yellow sodium silicate glass.Figure 11 is nickel ion
The curve of spectrum in sodium silicate glass.
Above-mentioned colouring agent is used to prepare potassium silicate glass, parent glass composition is (wt%)：K2O 22%, CaO
12%th, SiO260%th, MgO 4%, Al2O32%.Primary raw material is selected according to composition requirement and add auxiliary material, wherein SiO2
Introduced by above-mentioned colouring agent.All raw materials are made glass according to the method described above, gained potassium silicate glass is purple, Figure 12
It is the curve of spectrum of the nickel ion in potassium silicate glass.
Embodiment 17
Common silica sand is added in pH is the cobalt ions solution that 1~6, concentration is 3~60mg/L or according to embodiment 1-15
Any one modified silica sand for obtaining of method, the addition of common silica sand or modified silica sand is molten for 0.005~0.24g/ milliliters
Liquid, at 20~50 DEG C after addition, 1~120min of absorption under concussion or stirring, filtration drying after once adsorbing, or by multiple
Absorption reaches filtration drying after silica sand or modified silica sand saturated extent of adsorption, obtains a series of cobalt ions for being adsorbed with different content
Silica sand or modified silica sand.These absorption cobalt ions after silica sand and modified silica sand can serve as glass, ceramics or ceramic glaze
Toner.
Below, by taking a kind of colouring agent for obtaining as follows as an example, the step of colouring agent is when glass is prepared is explained：
The modified silicon that cladding is obtained for 5 times in embodiment 7 is added during pH is the cobalt ions aqueous solution that 6, concentration is 60mg/L
Sand (0.01g be modified silica sand/milliliter solution), adsorption conditionses：25 DEG C, 60min；Filtration drying after absorption, obtains colouring agent.According to original
Cobalt ions content is the modified silica sands of 2.04mg/g during sub- absorption spectrophotometer measures colouring agent.
The colouring agent is used to prepare soda lime glass, parent glass composition is (wt%)：Na2O 22%, CaO
12%th, SiO260%th, MgO 4%, Al2O32%.Except SiO2Introduce outer by the modified silica sand of absorption cobalt ions, other raw materials with
And preparation is conventionally carried out, gained glass is blueness, and Figure 13 is the cobalt ions curve of spectrum in glass.
Embodiment 18
It is the Cr that 1~7, concentration is 1~100mg/L in pH3+Common silica sand is added in solion or according to embodiment 1-
The addition of any one modified silica sand that 15 method is obtained, common silica sand or modified silica sand is 0.01~0.08g/ milliliters molten
Liquid, at 20~50 DEG C after addition, 1~120min of absorption under concussion or stirring, filtration drying after once adsorbing, or by multiple
Absorption reaches filtration drying after silica sand or modified silica sand saturated extent of adsorption, obtains a series of Cr for being adsorbed with different content3+Silicon
Sand or modified silica sand.These absorption Cr3+Silica sand and modified silica sand afterwards can serve as the colouring agent of glass, ceramics or ceramic glaze.
Below, by taking a kind of colouring agent for obtaining as follows as an example, the step of colouring agent is when glass is prepared is explained：
It is the Cr that 6, concentration is 5mg/L in pH3+The modified silica sand that cladding is obtained for 5 times in addition embodiment 15 in the aqueous solution
(0.01g be modified silica sand/milliliter solution), adsorption conditionses：25 DEG C, 30min；Filtration drying after absorption, obtains colouring agent.Using colorimetric
Method measures Cr ion concentrations in solution, is calculated Cr in colouring agent3+Content is the modified silica sands of 0.35mg/g.
The colouring agent is used to prepare soda lime glass, parent glass composition is (wt%)：Na2O 22%, CaO
12%th, SiO260%th, MgO 4%, Al2O32%.Except SiO2By absorption Cr3+Modified silica sand introduce outer, other raw materials and
Preparation is conventionally carried out, and gained glass is bright green, and Figure 14 is Cr3+The curve of spectrum in glass.
Embodiment 19
It is the Cr of 5mg/L in pH=3, concentration6+The modified silica sand that cladding is obtained for 5 times in addition embodiment 15 in solution
(0.02g be modified silica sand/milliliter solution), adsorption conditionses：25 DEG C, 30min；Filtration drying after absorption, obtains final product colouring agent.Using than
Color method measures Cr ion concentrations in solution, is calculated Cr in modified silica sand6+Content is 0.024mg/g.
With above-mentioned absorption Cr6+Modified silica sand afterwards and coloured material MnO2Together as mixed colorant, purple sodium is prepared
Calcium-silicate glass.Parent glass composition is (wt%)：Na2O 22%, CaO 12%, SiO260%th, MgO 4%,
Al2O32%.Primary raw material is selected according to composition requirement and add auxiliary material, wherein SiO2All by adsorbing Cr6+Afterwards modified
Silica sand is introduced, MnO2Consumption for primary raw material sum 3wt%.All raw materials are risen to 1350 DEG C with the speed of 5 DEG C/min
Insulation 2h, anneal 2h.Meanwhile, contrast experiment is set, the glass of contrast experiment is only with MnO2As colouring agent, SiO is introduced2Original
Material is not adsorb Cr6+The modified silica sand of blank, other conditions all same.
Use absorption Cr6+Modified silica sand and the curve of spectrum of glass that is made using the modified silica sand without absorption as schemed
Shown in 15, it can be seen that using absorption Cr6+Modified silica sand glass it is attached in 480nm compared with the glass not used
Near transmitance declines, and illustrates containing Cr6+Modified silica sand enhance glass coloration.
Embodiment 20
It is the Cd that 1~7, concentration is 0.1-100mg/L in pH2+Common silica sand is added in solution or according to embodiment 1-15's
The addition of any one modified silica sand that method is obtained, common silica sand or modified silica sand is 0.005-0.01g/ milliliters of solution,
At 20~50 DEG C after addition, 1~210min of absorption under concussion or stirring, filtration drying after once adsorbing, or by repeatedly inhaling
It is attached to reach filtration drying after modified silica sand saturated extent of adsorption, obtain a series of silica sands for being adsorbed with different content cadmium ion or modified
Silica sand.Silica sand and modified silica sand after these Adsorption of Cadmium can serve as the colouring agent of glass, ceramics or ceramic glaze.
Below, by taking a kind of modified silica sand of the Adsorption of Cadmium for obtaining as follows as an example, explain colouring agent in system
The step of during standby glass：
The modified silicon that cladding is obtained for 5 times in embodiment 7 is added during pH is the cadmium ion aqueous solution that 6, concentration is 15mg/l
Sand (0.01g be modified silica sand/milliliter solution), adsorption conditionses：25 DEG C, 30min；Filtration drying after absorption, according to Atomic absorption point
Cadmium ion content is the modified silica sands of 0.74mg/g during light photometer measures colouring agent.
With above-mentioned absorption Cd2+Rear modified silica sand and coloured material sulphur selenium compound are prepared together as mixed colorant
Soda lime glass.The composition of parent glass is (wt%)：Na2O 22%, CaO 12%, SiO260%th, MgO 4%,
Al2O32%.Primary raw material is selected according to composition requirement and add auxiliary material, wherein SiO2All by adsorbing Cd2+Afterwards modified
Silica sand is introduced, and sulphur selenium compound is introduced by selenium powder and ZnS, and the consumption of selenium powder is the 1wt% of primary raw material sum, the consumption of ZnS
It is the 0.03wt% of primary raw material sum.All raw materials are well mixed, high temperature adds when rising to 1200 DEG C with the speed of 5 DEG C/min
Material, is continuously heating to 1350 DEG C, is incubated 2h, and anneal 2h, obtains light-yellow tinge soda lime glass, its curve of spectrum such as Figure 16 institutes
Show.
Above example merely to explain the present invention, limitation and this, under the guiding of present inventive concept, will be modified
Silica sand change into common silica sand or other can serve as the schemes such as other adsorbents of glass or ceramic glaze raw material all should be
Within the scope of the present invention.
Claims (9)
1. the adsorbent of metal ion is adsorbed with as the application of coloured glass, ceramics or ceramic glaze stains yu, it is characterized in that：Institute
It is modified silica sand to state adsorbent, and the modified silica sand is obtained according to the method for following a or b：
Method a：
（1）To first adding waterglass to be well mixed in the mixture of triblock polymer P123, water and acid-washed quartz sand, then fast
Speed stirring is lower to add mixed in hydrochloric acid uniform, obtains reaction system；Or to the mixed of triblock polymer P123, water and acid-washed quartz sand
First add mixed in hydrochloric acid uniform in compound, add waterglass and be well mixed, obtain reaction system；
（2）Above-mentioned reaction system is stirred, h ~ 24 h of concussion reaction 1 at 25-80 DEG C makes waterglass react generation two
Silica is simultaneously coated on quartz sand surface；
（3）After reaction, washing, filtering take precipitation drying；
（4）The precipitation dinectly bruning that will be dried removes triblock polymer P123, obtains Modified Quartz Sand；Or repeat（1）、
（2）With（3）The step of 2-4 times, multiple coated with silica is carried out to quartz sand, repeatedly cladding after quartz sand drying, forge
Burn off removes triblock polymer P123, obtains Modified Quartz Sand；
Method b：
（1）Cetyl trimethylammonium bromide is mixed in water with silica sand at 25-80 DEG C, sodium hydroxide solution is subsequently adding
Make system in alkalescence, then instill tetraethyl orthosilicate, 1-24 h are reacted at 25-80 DEG C, hydrolyze to form tetraethyl orthosilicate
Coated with silica on silica sand surface；
（2）Washing, filtering reacting liquid, take precipitation drying after reaction；
（3）Dry precipitation dinectly bruning is removed into cetyl trimethylammonium bromide, porous silica modified silica sand is obtained；Or
Person repeats（1）With（2）The step of 2-4 times, multiple coated with silica is carried out to silica sand, repeatedly the silica sand after cladding is through dry
Dry, calcining removes cetyl trimethylammonium bromide, obtains porous silica modified silica sand.
2. the colouring agent of a kind of coloured glass, ceramics or ceramic glaze, it is characterized in that：Active ingredient is the gold being supported in adsorbent
Category ion, the adsorbent is modified silica sand, and the modified silica sand is obtained according to the method for following a or b：
Method a：
（1）To first adding waterglass to be well mixed in the mixture of triblock polymer P123, water and acid-washed quartz sand, then fast
Speed stirring is lower to add mixed in hydrochloric acid uniform, obtains reaction system；Or to the mixed of triblock polymer P123, water and acid-washed quartz sand
First add mixed in hydrochloric acid uniform in compound, add waterglass and be well mixed, obtain reaction system；
（2）Above-mentioned reaction system is stirred, h ~ 24 h of concussion reaction 1 at 25-80 DEG C makes waterglass react generation two
Silica is simultaneously coated on quartz sand surface；
（3）After reaction, washing, filtering take precipitation drying；
（4）The precipitation dinectly bruning that will be dried removes triblock polymer P123, obtains Modified Quartz Sand；Or repeat（1）、
（2）With（3）The step of 2-4 times, multiple coated with silica is carried out to quartz sand, repeatedly cladding after quartz sand drying, forge
Burn off removes triblock polymer P123, obtains Modified Quartz Sand；
Method b：
（1）Cetyl trimethylammonium bromide is mixed in water with silica sand at 25-80 DEG C, sodium hydroxide solution is subsequently adding
Make system in alkalescence, then instill tetraethyl orthosilicate, 1-24 h are reacted at 25-80 DEG C, hydrolyze to form tetraethyl orthosilicate
Coated with silica on silica sand surface；
（2）Washing, filtering reacting liquid, take precipitation drying after reaction；
（3）Dry precipitation dinectly bruning is removed into cetyl trimethylammonium bromide, porous silica modified silica sand is obtained；Or
Person repeats（1）With（2）The step of 2-4 times, multiple coated with silica is carried out to silica sand, repeatedly the silica sand after cladding is through dry
Dry, calcining removes cetyl trimethylammonium bromide, obtains porous silica modified silica sand.
3. colouring agent according to claim 2, it is characterized in that：The metal ion is Ni2+、Co2+、Cr6+、Cr3+Or Cd2+。
4. colouring agent according to claim 2, it is characterized in that：In method a, each reactant it is as follows with magnitude relation：Three is embedding
Section polymer P 123：Water：Waterglass：Quartz sand=0.1-0.5g：40ml：1ml：2-10g, when the concentration of hydrochloric acid is 1mol/L,
Hydrochloric acid is 3.2-10 with the volume ratio of waterglass:1.
5. colouring agent according to claim 2, it is characterized in that：In method b, cetyl trimethylammonium bromide：Water：Positive silicon
Sour tetra-ethyl ester：The amount ratio of silica sand is：0.045g-0.54g：3.7-265ml：0.5- 4 ml：1-10 g；When NaOH is molten
When the concentration of liquid is 0.175-0.6 mol/L, sodium hydroxide solution is 10 with the volume ratio of water：3.7-265.
6. colouring agent according to claim 2, it is characterized in that：Content of the metal ion in adsorbent is 0.024-
2.04mg/g。
7. a kind of coloured glass, it is characterized in that：Raw material include claim 2-6 any one of coloured glass, ceramics or
Ceramic glaze stains yu.
8. a kind of ceramic, it is characterized in that：Raw material includes coloured glass, the ceramics or ceramic any one of claim 2-6
Glaze stains yu.
9. a kind of ceramic glaze, it is characterized in that：Raw material includes coloured glass, the ceramic or pottery any one of claim 2-6
Enamel colouring agent.
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| CN105693079B (en) * | 2016-01-19 | 2018-06-01 | 济南大学 | The preparation method and products obtained therefrom of the green glass of a kind of green colourant and shielding ultraviolet rays |
| CN107638868B (en) * | 2016-07-22 | 2019-11-12 | 济南大学 | A kind of porous carbon adsorbent and its preparation method and application |
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