CN106000285B - It is a kind of to be modified silica sand and its application in the method for silica sand surface construction coated with silica layer, gained - Google Patents
It is a kind of to be modified silica sand and its application in the method for silica sand surface construction coated with silica layer, gained Download PDFInfo
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- CN106000285B CN106000285B CN201510788143.8A CN201510788143A CN106000285B CN 106000285 B CN106000285 B CN 106000285B CN 201510788143 A CN201510788143 A CN 201510788143A CN 106000285 B CN106000285 B CN 106000285B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/02—Pretreated ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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Abstract
The invention discloses a kind of methods in silica sand surface construction coated with silica layer and gained to be modified silica sand, and step is:Silica sand and sodium hydroxide solution are subjected to hydro-thermal reaction in confined conditions, silica sand is made to be partly dissolved;Reaction solution is cooled down, reaction solution pH to 11-11.8 is adjusted, CTAB is then added into reaction solution is reacted;Obtained solid sample is dried in reaction, and high-temperature calcination is to get the modification silica sand with coated with silica layer.The method and products obtained therefrom being modified again the present invention also provides the modification silica sand, and using gained modification silica sand adsorbing metal ions, as the application of glass raw material.Process of the present invention is simple, continuous, raw material is simple, it is at low cost, gained is modified the big promotion of silica sand large specific surface area, there is better application in water filtering and field of waste water treatment, modification silica sand after absorption can be used for glass colorant, provide convenience for the recycling (especially being recycled in glass industry) of silica sand.
Description
Technical field
The present invention relates to a kind of preparation methods of modified silica sand, especially a kind of that silicon source is not added additionally, is carried out to silica sand
Porous surface SiO2The preparation method of the modification silica sand of cladding further relates to answering for obtained modified silica sand and the modification silica sand
With.
Background technology
Silica sand is the main raw material for making silicate glass.Silica sand is additionally operable to ceramics, casting, aerospace, electronics production
The fields such as product.In addition, silica sand is used for water process as filter bed filtrate.Silica sand itself is highly stable, will not polluted source, but its
The ability for adsorbing harmful ion is very weak, and the report that metal ion is directly removed with silica sand is few.Currently, the more of research is pair
Silica sand carries out surface modification and utilizes other materials(Such as iron and its oxi or hydroxide)Synergistic effect improve silicon
The dirt-removing power of sand, these are modified silica sand often because surface composition complexity is not suitable for recycling in glass.And by
Silica sand surface construction porous silica clad can not only greatly improve the surface area of silica sand, improve it and adsorb metal in waste water
The ability of ion, while coated with silica layer will not influence the recycling of silica sand from ingredient.
Applicant has applied for two patents being modified about silica sand in 2014, and application No. is 201410763234.1 Hes
201410763848.X, using ethyl orthosilicate, waterglass as silicon source in these patents, by way of adding surfactant
Silica sand surface is coated in aqueous solution, obtains the modification silica sand of high specific area.Obtained modification silica sand without it is other at
Point, it can recycle in glass.But these methods are required for that silicon source additionally is added, and the cost is relatively high, and industrialize difficulty
Greatly.
Invention content
In order to further reduce the cost, simplify modification procedure, the present invention provides one kind in silica sand surface construction titanium dioxide
The method of silicon clad, this method can be modified silica sand, and step is simple, at low cost, easy to operation.
The present invention also provides the modification silica sands obtained according to the method described above.
Cr during the present invention also provides a kind of using the modification silica sand as the waste water of adsorbent6+Processing method.
The present invention also provides a kind of preparation methods of silicate glass raw material.
Specific technical solution of the present invention is as follows:
A method of in silica sand surface construction coated with silica layer, this approach includes the following steps:
(1)Silica sand is mixed with sodium hydroxide solution, carries out hydro-thermal reaction in confined conditions, until silica sand quality dissolves
Stop reaction when 12-50%;
(2)Reaction solution is cooled down after reaction, reaction solution pH to 11-11.8 is adjusted, hexadecane is then added into reaction solution
Base trimethylammonium bromide (CTAB) is reacted, in undissolved silica sand surface coated silica and cetyl trimethyl bromine
Change the complex of ammonium;
(3)After reaction, by step(2)Reaction solution pour out, wash obtained solid, then solid sample is dried, high temperature
Calcining removes cetyl trimethylammonium bromide to get the modification silica sand with coated with silica layer.
The present invention can dissolve the surface of silica sand using sodium hydroxide solution to a certain degree in the case where heating closed hydrothermal condition
The characteristic of layer, in step(1)In silica sand is partly dissolved first, hydro-thermal reaction refer to using water as solvent, heating, it is closed
Under conditions of the reaction that carries out.Silica sand dissolving can form the solution containing silicic acid, which is clear state, as silicon source,
Undissolved silica sand can be coated in Surfactant CTAB presence, to form changing for the layer containing coated with silica
Property silica sand, solution is become cloudy by clarifying during cladding, and the method reduce the uses of silicon source.Sodium hydroxide is in addition to dissolving silica sand
Outside, also make silica sand surface scission of link hydroxyl and defect(Such as pit, crack)Increase, activity increase, such silica sand is conducive to
The cladding of follow-up silica.
The present invention is partly dissolved obtained silicic acid as silicon source using silica sand, is coated to dissolved silica sand surface again to silicon
Sand is modified.The meltage of silica sand is equal for the performance of the modification silica sand after the thickness and cladding of the silicon dioxide layer of cladding
There is larger impact.By verification experimental verification, after silica sand dissolves the 12-50% of proper mass, dissolves silica sand for proper mass 50~
Best when 88%, the more former silica sand of specific surface area of the modified silica sand of gained has larger increase within this range.What is dissolved is very few, because
Lack silicon source in liquid phase, the specific surface area of the silica sand after cladding increases less;What is dissolved is excessive, and silicon source is not exclusively coated on sand
Grain surface, generates alone silica dioxide granule, cannot be effectively modified to silica sand.When silica sand dissolves, the concentration of sodium hydroxide is used
Amount, reaction temperature, reaction time etc. all have an impact the meltage of silica sand, naoh concentration is bigger, dosage is more, temperature more
Height, time are longer, and silica sand dissolving is got over.In practical operation, those skilled in the art can voluntarily adjust taking for these conditions
Silica sand is set to reach required meltage with situation, general sodium hydroxide is all excessive.For example, naoh concentration it is low when
It waits, dosage can be accordingly turned up, and when naoh concentration is high, dosage can be turned down accordingly, reaction temperature
When relatively low, the reaction time can be longer, and when reaction temperature is higher, the reaction time can be shorter.
In the specific embodiment of the present invention, in the mixed system of silica sand, sodium hydroxide and water, sodium hydroxide
Concentration can be 0.1 ~ 1 mol/L, reaction temperature can be 60 ~ 140 DEG C.Under this naoh concentration and reaction temperature,
The silica sand of required meltage can be readily attained by adjusting sodium hydroxide solution dosage, reaction time, in general, reaction 4-
Silica sand dissolving is can reach within 24 hours to require.In a preferred embodiment of the invention, in the mixture of silica sand, sodium hydroxide and water
In system, a concentration of 0.5mol/L of sodium hydroxide, reaction temperature are 120 DEG C.
Step(2)In, the silica sand surface scission of link, defect and hydroxyl after being partly dissolved are more, are conducive to coated with silica layer
Formation.Reaction solution after silica sand is reacted with sodium hydroxide is in highly basic state, can not directly be coated, need first to adjust pH
It could be coated well after to 11-11.8.
Above-mentioned steps(2)In, the strong acid for adjusting pH such as sulfuric acid, hydrochloric acid may be used, according to required water, sour concentration can
Voluntarily to select.
Above-mentioned steps(2)In, the cetyl trimethylammonium bromide and step of addition(1)The mass ratio of the silica sand of middle addition
It is 0.06 ~ 0.5:1.
Above-mentioned steps(2)In, concentration of the cetyl trimethylammonium bromide in the reaction solution after adjusting pH produces gained
The performance of product has certain influence, it is preferred that cetyl trimethylammonium bromide is a concentration of in the reaction solution after adjusting pH
0.0016~0.01g/ml.In practical operation, can by control dosage, concentration of acid used etc. of sodium hydroxide solution come
Concentration of the cetyl trimethylammonium bromide in system is adjusted, cetyl three can also be made by way of pure water is added
Methyl bromide ammonium reaches required concentration.
Above-mentioned steps(2)In, reaction solution is cooled down into pressure release after reaction, is then coated again.It is carried out under open environment
Cladding after cetyl trimethylammonium bromide is added, carries out the coating reaction of silica, specific at 25-65 DEG C
When operation, may be used 25 within the scope of this DEG C, 40 DEG C, 50 DEG C, the temperature such as 65 DEG C reacted, the reaction time is generally 0.5-
12h。
Above-mentioned steps(3)In, after coated with silica, the solvent portions of reaction solution are poured out, then add water washing
Solid portion filters after washing, obtains solid sample.Solid sample needs first to dry to be calcined again, in the preferred of the present invention
It in embodiment, is dried at 100 DEG C or so, drying time 4h.In practical operation, can also use other temperature and when
Between reach drying purpose.
Above-mentioned steps(3)In, the solid sample high-temperature calcination after drying removes cetyl trimethylammonium bromide, calcining temperature
Degree uses the temperature commonly used in the prior art for removing cetyl trimethylammonium bromide, such as 500-600 DEG C of calcining
Temperature.In a preferred embodiment of the invention, it is calcined at 550 DEG C, calcination time 6h.Heating rate is using routine
Heating rate, for example, 1-10 DEG C/min heating rate, in a preferred embodiment of the invention, using the heating of 1 DEG C/min
Rate.
Using above method, the modification silica sand with coated with silica layer can be obtained, is denoted as modified silica sand A, this changes
Property silica sand is also within the scope of the present invention.In the specific implementation mode of the present invention, the specific surface area of modified silica sand A is former
35-750 times of beginning silica sand specific surface area.
Further, it is also possible to be modified again on the basis of being modified silica sand A herein, method is:By 0.5-9ml aminopropyls three
Ethoxysilane is added in the mixed liquor of ethyl alcohol and water, and 5g is added after mixing and is modified silica sand A, is stirred to react at 70 DEG C
25min is filtered, washed after reaction, dries to get modification silica sand modified again, is denoted as modified silica sand B.This is modified silica sand B
Within the scope of the present invention.
In the preparation method of above-mentioned modified silica sand B, the volume ratio of second alcohol and water is 2:1.
In the preparation method of above-mentioned modified silica sand B, the ethyl alcohol of 0.5-9ml aminopropyl triethoxysilanes and 45ml or so with
The mixed liquor of water mixes.
Verified, the present invention, which is modified the more original silica sand of silica sand A, B specific surface area, has prodigious increase, adsorption capacity to have
Prodigious promotion, it is more preferable in fields application effects such as waste water absorption.
The present invention also provides Cr in a kind of waste water6+Processing method, this method includes:With above-mentioned modified silicon sand A or/and
Modified silica sand B is adsorbent, is added into waste water, by some or all of being adsorbed and removed in waste water Cr6+。
In above-mentioned processing method, Cr will be contained6+Wastewater pH adjust to 1-6 after add modified silica sand.
In above-mentioned processing method, being adsorbed at 25-65 DEG C for modified silica sand carries out.
In the specific embodiment of the present invention, as Cr in waste water6+When a concentration of 1-200mg/L, the dosage of silica sand
For 0.5-5g.
It is silica that the present invention, which is modified silica sand A and B component, has adsorbed the metal Cr in waste water6+Afterwards, contain in modified silica sand
There is a certain amount of Cr6+, a certain amount of Cr can be added when preparing coloured glass6+As colorant, individually or with other
Toner act as glass coloration together.Modification silica sand after above-mentioned absorption waste water contains silica and Cr6+, glass can be used as
Raw material is recycled.Therefore, the present invention also provides a kind of preparation method of silicate glass raw material, this method include with
Lower step:
(1)Cr will be contained6+Wastewater pH adjust to 1-6, above-mentioned modified silica sand A or/and modified silica sand B is then added, in 25-
To the Cr in waste water at 65 DEG C6+It is adsorbed;
(2)By the modification silica sand after absorption directly as the raw material of silicate glass, or by the modification silica sand after absorption
According still further to step(1)Method be repeated at least once more(Cr in post-modification silica sand is adsorbed to improve6+Content)Afterwards, it is re-used as silicic acid
The raw material of salt glass.
In the above method, because of Cr in waste water6+The amount of the difference of concentration, the modification silica sand of addition is different, reaction condition
Difference is modified the Cr adsorbed in silica sand6+Amount can exist difference.In order to make Cr6+Amount meet the requirement of glass coloration, can be with
Above-mentioned condition is adjusted, same batch silica sand can also be modified and same batch or different batches waste water is repeatedly adsorbed, or
Person repeatedly adsorbs different batches modification silica sand same batch waste water, to meet Cr6+Demand.
The present invention provides a kind of method of modifying of silica sand, this method heats confined condition using silica sand in strong base solution
The characteristic that can be dissolved down, silica sand is partly dissolved, and is silicon source using the silicic acid that silica sand dissolves, is passed through the adjusting of pH, ten
In not molten silica sand surface construction coated with silica layer, process is simple, continuous for the addition of six alkyl trimethyl ammonium bromides, raw material letter
It is single, it is at low cost.Gained is modified the big promotion of silica sand large specific surface area, directly or by being modified again, improves suction of the silica sand to ion
Attached ability has better application in water filtering and field of waste water treatment.
Cr during the present invention also provides a kind of using the modification silica sand as the waste water of adsorbent6+Processing method, and absorption
Cr6+The method that modification silica sand afterwards recycles, the present invention is modified silica sand and is greatly increased than original silica sand specific surface area, to chromium ion
Adsorption capacity promoted, can be used for remove waste water in chromium ion.Modified silica sand does not change the chemistry of original silica sand
Composition, the chromium ion of absorption can be used for glass colorant, be that the recycling of silica sand is (especially sharp again in glass industry
With) provide convenience.
Specific implementation mode
In order to be better understood from and implement, with reference to embodiment, the present invention will be described in detail.
In following embodiments, the specific surface area of original silica sand used is 0.083m2/g.The test side of silica sand specific surface area
Method is:The data measured are tested according to isothermal nitrogen adsorption desorption, and gained is calculated by BET models.
In following embodiments, the meltage of silica sand is measured in accordance with the following methods:After course of dissolution, it is cooled to room temperature,
Silica sand is filtered out, 90 DEG C is put into baking oven and dries 4 hours, takes out weighing quality, meltage=(The dissolved matter of quality-before dissolving
Amount)Quality before/dissolving.
In following embodiments, the calculation of adsorption rate is:[(Ion concentration after initial ion concentration-absorption in liquid)/
Initial ion concentration in liquid] × 100%.Liquid intermediate ion concentration is measured using diphenylcarbazide spectrophotometric standard method.
In following embodiments, the calculation of adsorbance is:Initial ion concentration × liquid volume × adsorption rate in liquid/
The addition of modified silica sand adsorbent, unit mg/g.
Embodiment 1
The NaOH solution of 6.0g silica sands and 100ml 0.5mol/L is added in reaction kettle, confined reaction at 120 DEG C
12h, test silica sand has dissolved the 28.28% of proper mass;
Above-mentioned reaction solution is cooled to 25 DEG C, 150mlH is added into solution2O is 11.0 with sulfuric acid regulation solution pH, then
1.5gCTAB, a concentration of 0.006g/mls of the CTAB in entire reaction system are added, in shaking table at 25 DEG C(200r/min)It is upper anti-
6h is answered, 550 DEG C are carried out after 100 DEG C of dry 4h(It is heated up with the rate of 1 DEG C/min)Calcine 6h, the ratio of the sample obtained afterwards after tested
Surface area is 2.945m2/ g is 35.5 times of former silica sand sample specific surface area.
Embodiment 2
6.0g silica sands and 100ml 0.5mol/L NaOH solutions are added in reaction kettle, confined reaction 12h at 120 DEG C,
Test silica sand has dissolved the 28.28% of proper mass;
Above-mentioned reaction solution is cooled to 25 DEG C, 150mlH is added into solution2O is 11.3 with sulfuric acid regulation solution pH, then
1.5gCTAB, a concentration of 0.006g/mls of the CTAB in entire reaction system are added, in shaking table at 25 DEG C(200r/min)It is upper anti-
6h is answered, 550 DEG C are carried out after 100 DEG C of dry 4h(It is heated up with the rate of 1 DEG C/min)Calcine 6h, the ratio of the sample obtained afterwards after tested
Surface area is 11.709 m2/ g is 141.1 times of former silica sand sample specific surface area.
Embodiment 3
6.0g silica sands and 100ml 0.5mol/L NaOH solutions are added in reaction kettle, confined reaction 12h at 120 DEG C,
Test silica sand has dissolved the 28.28% of proper mass;
Above-mentioned reaction solution is cooled to 25 DEG C, 150mlH is added into solution2O is 11.8 with sulfuric acid regulation solution pH, then
1.5gCTAB, a concentration of 0.006g/mls of the CTAB in entire reaction system are added, in shaking table at 25 DEG C(200r/min)It is upper anti-
6h is answered, 550 DEG C are carried out after 100 DEG C of dry 4h(It is heated up with the rate of 1 DEG C/min)Calcine 6h, the ratio of the sample obtained afterwards after tested
Surface area is 7.278 m2/ g is 87.7 times of former silica sand sample specific surface area.
Embodiment 4
6.0g silica sands and 100ml 0.5mol/L NaOH solutions are added in reaction kettle, confined reaction 12h at 120 DEG C,
Test silica sand has dissolved the 28.28% of proper mass;
Above-mentioned reaction solution is cooled to 25 DEG C, 150mlH is added into solution2O is 11.5 with sulfuric acid regulation solution pH, then
0.4gCTAB, a concentration of 0.0016g/mls of the CTAB in entire reaction system are added, in shaking table at 25 DEG C(200r/min)On
6h is reacted, 550 DEG C are carried out after 100 DEG C of dry 4h(It is heated up with the rate of 1 DEG C/min)6h is calcined, the sample obtained afterwards after tested
Specific surface area is 3.640 m2/ g is 43.9 times of former silica sand sample specific surface area.
Embodiment 5
6.0g silica sands and 100ml 0.5mol/L NaOH solutions are added in reaction kettle, confined reaction 12h at 120 DEG C,
Test silica sand has dissolved the 28.28% of proper mass;
Above-mentioned reaction solution is cooled to 25 DEG C, 150mlH is added into solution2O is 11.5 with sulfuric acid regulation solution pH, then
2.5gCTAB, a concentration of 0.01g/mls of the CTAB in entire reaction system are added, in shaking table at 25 DEG C(200r/min)It is upper anti-
6h is answered, 550 DEG C are carried out after 100 DEG C of dry 4h(It is heated up with the rate of 1 DEG C/min)Calcine 6h, the ratio of the sample obtained afterwards after tested
Surface area is 6.724 m2/ g is 81.0 times of former silica sand sample specific surface area.
Embodiment 6
6.0g silica sands and 100ml 0.5mol/L NaOH solutions are added in reaction kettle, confined reaction 12h at 120 DEG C,
Test silica sand has dissolved the 28.28% of proper mass;
Above-mentioned reaction solution is cooled to 25 DEG C, is 11.5 with sulfuric acid regulation solution pH, adds 1.5gCTAB, CTAB is whole
A concentration of 0.015g/ml in a reaction system, in shaking table at 25 DEG C(200r/min)Upper reaction 6h, 100 DEG C of dry 4h are laggard
550 DEG C of row(It is heated up with the rate of 1 DEG C/min)6h is calcined, the specific surface area of the sample obtained afterwards after tested is 3.819 m2/ g,
It is 46.0 times of former silica sand sample specific surface area.
Embodiment 7
6.0g silica sands and 100ml 0.5mol/L NaOH solutions are added in reaction kettle, confined reaction 12h at 120 DEG C,
Test silica sand has dissolved the 28.28% of proper mass;
Above-mentioned reaction solution is cooled to 25 DEG C, 150mlH is added into solution2O is 11.5 with sulfuric acid regulation solution pH, then
1.5gCTAB, a concentration of 0.006g/mls of the CTAB in entire reaction system are added, in shaking table at 25 DEG C(200r/min)It is upper anti-
6h is answered, 550 DEG C are carried out after 100 DEG C of dry 4h(It is heated up with the rate of 1 DEG C/min)Calcine 6h, the ratio of the sample obtained afterwards after tested
Surface area is 24.338 m2/ g is 293.2 times of former silica sand sample specific surface area.
Embodiment 8
6.0g silica sands and 100ml 0.5mol/L NaOH solutions are added in reaction kettle, confined reaction 12h at 120 DEG C,
Test silica sand has dissolved the 28.28% of proper mass;
Above-mentioned reaction solution is cooled to 25 DEG C, 200mlH is added into solution2O is 11.5 with sulfuric acid regulation solution pH, then
1.5gCTAB, a concentration of 0.005g/mls of the CTAB in entire reaction system are added, in shaking table at 25 DEG C(200r/min)It is upper anti-
6h is answered, 550 DEG C are carried out after 100 DEG C of dry 4h(It is heated up with the rate of 1 DEG C/min)Calcine 6h, the ratio of the sample obtained afterwards after tested
Surface area is 6.293 m2/ g is 75.8 times of former silica sand sample specific surface area.
Embodiment 9
6.0g silica sands and 100ml 0.5mol/L NaOH solutions are added in reaction kettle, confined reaction 12h at 120 DEG C,
Test silica sand has dissolved the 28.28% of proper mass;
Above-mentioned reaction solution is cooled to 25 DEG C, 150mlH is added into solution2O is 11.5 with sulfuric acid regulation solution pH, then
1.5gCTAB, a concentration of 0.006g/mls of the CTAB in entire reaction system are added, in shaking table at 45 DEG C(200r/min)It is upper anti-
6h is answered, 550 DEG C are carried out after 100 DEG C of dry 4h(It is heated up with the rate of 1 DEG C/min)Calcine 6h, the ratio of the sample obtained afterwards after tested
Surface area is 16.566 m2/ g is 199.6 times of former silica sand sample specific surface area.
Embodiment 10
6.0g silica sands and 100ml 0.5mol/L NaOH solutions are added in reaction kettle, confined reaction 12h at 120 DEG C,
Test silica sand has dissolved the 28.28% of proper mass;
Above-mentioned reaction solution is cooled to 25 DEG C, 150mlH is added into solution2O is 11.5 with sulfuric acid regulation solution pH, then
1.5gCTAB, a concentration of 0.006g/mls of the CTAB in entire reaction system are added, in shaking table at 65 DEG C(200r/min)It is upper anti-
6h is answered, 550 DEG C are carried out after 100 DEG C of dry 4h(It is heated up with the rate of 1 DEG C/min)Calcine 6h, the ratio of the sample obtained afterwards after tested
Surface area is 12.689 m2/ g is 152.9 times of former silica sand sample specific surface area.
Embodiment 11
6.0g silica sands and 100ml 0.5mol/L NaOH solutions are added in reaction kettle, confined reaction 12h at 120 DEG C,
Test silica sand has dissolved the 28.28% of proper mass;
Above-mentioned reaction solution is cooled to 25 DEG C, 150mlH is added into solution2O is 11.5 with sulfuric acid regulation solution pH, then
1.5gCTAB, a concentration of 0.006g/mls of the CTAB in entire reaction system are added, in shaking table at 25 DEG C(200r/min)It is upper anti-
0.5h is answered, 550 DEG C are carried out after 100 DEG C of dry 4h(It is heated up with the rate of 1 DEG C/min)6h is calcined, the sample obtained afterwards after tested
Specific surface area is 39.256 m2/ g is 473.0 times of former silica sand sample specific surface area.
Embodiment 12
6.0g silica sands and 100ml 0.5mol/L NaOH solutions are added in reaction kettle, confined reaction 12h at 120 DEG C,
Test silica sand has dissolved the 28.28% of proper mass;
Above-mentioned reaction solution is cooled to 25 DEG C, 150mlH is added into solution2O is 11.5 with sulfuric acid regulation solution pH, then
1.5gCTAB, a concentration of 0.006g/mls of the CTAB in entire reaction system are added, in shaking table at 25 DEG C(200r/min)It is upper anti-
12h is answered, 550 DEG C are carried out after 100 DEG C of dry 4h(It is heated up with the rate of 1 DEG C/min)6h is calcined, the sample obtained afterwards after tested
Specific surface area is 17.076 m2/ g is 205.7 times of former silica sand sample specific surface area.
Embodiment 13
3.0g silica sands and 100ml 0.5mol/L NaOH solutions are added in reaction kettle, confined reaction 12h at 120 DEG C,
Test silica sand has dissolved the 49.70% of proper mass;
Above-mentioned reaction solution is cooled to 25 DEG C, 150mlH is added into solution2O is 11.5 with sulfuric acid regulation solution pH, then
1.5gCTAB, a concentration of 0.006g/mls of the CTAB in entire reaction system are added, in shaking table at 25 DEG C(200r/min)It is upper anti-
6h is answered, 550 DEG C are carried out after 100 DEG C of dry 4h(It is heated up with the rate of 1 DEG C/min)Calcine 6h, the ratio of the sample obtained afterwards after tested
Surface area is 52.166 m2/ g is 628.5 times of former silica sand sample specific surface area.
Embodiment 14
15.0g silica sands and 100ml 0.5mol/L NaOH solutions are added in reaction kettle, confined reaction at 120 DEG C
12h, test silica sand has dissolved the 12.41% of proper mass;
Above-mentioned reaction solution is cooled to 25 DEG C, 150mlH is added into solution2O is 11.5 with sulfuric acid regulation solution pH, then
1.5g CTAB, CTAB a concentration of 0.006g/ml in entire reaction system is added, in shaking table at 25 DEG C(200r/min)On
6h is reacted, 550 DEG C are carried out after 100 DEG C of dry 4h(It is heated up with the rate of 1 DEG C/min)6h is calcined, the sample obtained afterwards after tested
Specific surface area is 15.493 m2/ g is 186.7 times of former silica sand sample specific surface area.
Embodiment 15
9.0g silica sands and 100ml 0.5mol/L NaOH solutions are added in reaction kettle, confined reaction 12h at 120 DEG C,
Test silica sand has dissolved the 19.86% of proper mass;
Above-mentioned reaction solution is cooled to 25 DEG C, 100mlH is added into solution2O is 11.5 with sulfuric acid regulation solution pH, then
1.5g CTAB, CTAB a concentration of 0.0075g/ml in entire reaction system is added, in shaking table at 25 DEG C(200r/min)On
1h is reacted, 550 DEG C are carried out after 100 DEG C of dry 4h(It is heated up with the rate of 1 DEG C/min)6h is calcined, the sample obtained afterwards after tested
Specific surface area is 61.672 m2/ g is 743.1 times of former silica sand sample specific surface area.
Comparative example 1
6.0g silica sands, 100ml 0.5mol/L NaOH solutions, 1.5gCTAB are added in reaction kettle simultaneously, at 120 DEG C
Confined reaction 12h after being cooled to 25 DEG C, filters, 550 DEG C is carried out after 100 DEG C of dry 4h(It is heated up with the rate of 1 DEG C/min)Calcining
The specific surface area of 6h, the sample obtained afterwards after tested are 0.735 m2/ g, 8.9 times of only former silica sand sample specific surface area.
Comparative example 2
The NaOH solution of 6.0g silica sands and 100ml 0.5mol/L is added in reaction kettle, confined reaction at 120 DEG C
12h, test silica sand has dissolved the 28.28% of proper mass;
Above-mentioned reaction solution is cooled to 25 DEG C, 150mlH is added into solution2O is 10.5 with sulfuric acid regulation solution pH, then
1.5gCTAB, a concentration of 0.006g/mls of the CTAB in entire reaction system are added, in shaking table at 25 DEG C(200r/min)It is upper anti-
6h, entire reaction process solution is answered to have no muddy, microscope observation is carried out after 100 DEG C of dry 4h, as a result shows and has no packet on sand
Object is covered, silica sand surface area changes unobvious.
Comparative example 3
The NaOH solution of 6.0g silica sands and 100ml 0.5mol/L is added in reaction kettle, confined reaction at 120 DEG C
12h, test silica sand has dissolved the 28.28% of proper mass;
Above-mentioned reaction solution is cooled to 25 DEG C, 150mlH is added into solution2O is 12 with sulfuric acid regulation solution pH, then adds
Enter 1.5gCTAB, a concentration of 0.006g/mls of the CTAB in entire reaction system, in shaking table at 25 DEG C(200r/min)Upper reaction
6h, entire reaction process solution have no muddy, microscope observation are carried out after 100 DEG C of dry 4h, as a result shows and has no cladding on sand
Object.
Embodiment 16
Further, modified silica sand made from above-described embodiment 1-15 can be further modified, and method is:30ml
Ethyl alcohol and 15mlH2O is added in conical flask, adds 0.5 ~ 9ml KH550(γ-aminopropyl triethoxysilane), it shakes up,
The modification silica sand that in 5g above-described embodiments 1-15 prepared by any embodiment is added, conical flask is put on shaking table, it is anti-at 70 DEG C
Answer 25min, after reaction taking-up wash filtering with ethyl alcohol, dry 2.5h at 110 DEG C, obtain further modified silica sand, be denoted as and change
Property silica sand B.
Embodiment 17
Modification silica sand prepared by 1-15 of the embodiment of the present invention is denoted as modified silica sand A, prepared by modified silica sand A and embodiment 16
Modified silica sand B can be used as adsorbent, for adsorbing the hexavalent chromium in waste water.
For the ease of statement, the modification silica sand A of embodiment 15 is denoted as modified silica sand 1, this will be changed by the following method
Property silica sand 1 do further modified obtained modification silica sand and be denoted as modified silica sand 2, method is:30ml ethyl alcohol and 15mlH2O adds
Enter into conical flask, adds 2ml KH550(γ-aminopropyl triethoxysilane), it shakes up, 5g is added and is modified silica sand 1,
Conical flask is put on shaking table, and 25min is reacted at 70 DEG C, after reaction taking-up wash filtering with ethyl alcohol, dried at 110 DEG C
2.5h obtains modified silica sand 2.
It is using the method that modified silica sand 1 and 2 adsorbs hexavalent chromium in waste water:By Cr6+A concentration of 1-100 mg/L
Wastewater pH adjust to 1-6, modified silica sand 1 or/and 2 is then added, to the Cr in waste water at 25-65 DEG C6+It is adsorbed, is inhaled
The attached time is in 30min or more, such as 30-180min.Earthquake or the lower progress of stirring are adsorbed, to accelerate the rate of absorption.
The solution of the Cr6+ prepared below using use for laboratory potassium bichromate and water verifies the suction of modified silica sand as simulated wastewater
Attached effect:
1, Cr is taken6+A concentration of 5 mg/L Cr6+Solution adjusts pH, then addition 1g modifications silica sand 1 or 2, on shaking table
120min is adsorbed at 25 DEG C.It is filtered after absorption, tests adsorbance and adsorption rate, as a result see the table below 1.
2, Cr is taken6+The different Cr of concentration6+Solution, adjustment pH be 2 then be added 1g be modified silica sand 1 or adjustment pH be 3 so
1g is added afterwards and is modified silica sand 2, solution is then adsorbed into 120min on shaking table at 25 DEG C respectively.It is filtered after absorption, test absorption
Amount and adsorption rate, as a result see the table below 2.
3, Cr is taken6+A concentration of 10mg/L Cr6+Solution, adjustment pH are 2 and then modified silica sand 1 or adjustment pH are added
Modified silica sand 2 is then added for 3, solution is then adsorbed into 90min on shaking table at 25 DEG C respectively.It is filtered after absorption, test is inhaled
Attached amount and adsorption rate, as a result see the table below 3.
4, Cr is taken6+A concentration of 10mg/L Cr6+Solution, adjustment pH are 2 then addition 1g modification silica sands 1 or adjustment
PH is 3 and then 1g modification silica sands 2 is added, and solution is then adsorbed 90min on shaking table respectively.It is filtered after absorption, test absorption
Amount and adsorption rate, as a result see the table below 4.
5, Cr is taken6+A concentration of 10 mg/L Cr6+Solution, adjustment pH are 2 then addition 1g modification silica sands 1 or adjustment
PH is 3 and then 1g modification silica sands 2 is added, and then adsorbs solution at 25 DEG C on shaking table respectively.It is filtered after absorption, test absorption
Amount and adsorption rate, as a result see the table below 5.
Embodiment 18
Contain hexavalent chromium in modification silica sand after present invention absorption, while the ingredient silica of modified silica sand is exactly
A kind of component of glass, therefore the modification silica sand after absorption can be as the raw material of glass, because chromium ion makes glass have face
Color, therefore the modification silica sand adsorbed after chromium ion can also be referred to as glass colorant.Because once in absorption post-modification silica sand
Content of chromium ion differ, therefore in practical application, according to the amount of chromium ion needed for glass, can will modified silica sand it is more
Secondary absorption waste water makes chromium ion amount meet demand.
In the following, only enumerating 2 kinds of colorants, and glass is made, to prove that the modification silica sand after adsorbing can be done in reuse well
Glass raw material.
Colorant 1:The modification silica sand 1 of 1g embodiments 17 is added in conical flask, the Cr of 100mg/L is added6+Solution 50ml,
PH=3 are adjusted, 90min is reacted at room temperature on shaking table, filtering is taken out after 90min, is dried as colorant 1.In order to meet glass raw material
Demand, repeat this operation, obtain the desired amount of colorant 1.
Colorant 2:100ml is taken to be electroplated chromyl waste water, hexavalent chromium concentration 174.16mg/l adjusts pH value to 3,
5g is added and is modified silica sand 2, is put on shaking table, adsorbs 90min at room temperature, the waste water after absorption adds new 2 weight of modification silica sand
It relapses attached 7 times, each 5g, the modification silica sand 2 after absorption filters, drying, as colorant 2.
The preparation of soda lime glass:The parent glass group of sodium silicate glass becomes(wt%):Na2O 22%、CaO
12%、SiO2 60%、MgO 4%、Al2O3 2%.Selection raw material, wherein SiO are formed according to the parent glass2Respectively by above-mentioned coloring
Agent 1, colorant 2 or unadsorbed original silica sand introduce;CaO can be introduced by calcium oxide or calcium carbonate, Na2O is drawn by sodium carbonate
Enter, MgO is introduced by magnesia or basic magnesium carbonate, Al2O3By Al (OH)3It introduces(These raw materials are known as primary raw material, similarly hereinafter).
On the basis of primary raw material, auxiliary material can also be added according to conventional ratio(Fining agent and fluxing agent), such as can add
Enter the Sb of the sum of primary raw material 0.5wt%2O3Or the NaNO of the 1.2wt% of the sum of primary raw material3As fining agent, can also be added
The CaF of the 1.03wt% of the sum of primary raw material2As fluxing agent.Above-mentioned all raw materials are put into crucible after mixing, it will
Crucible is warming up to 1350 DEG C with the heating rate of 5 DEG C/min in Muffle furnace and keeps the temperature 2h, obtains glass metal, gained glass metal composition
Glass metal is poured into die for molding and the 2h that anneals at 550 DEG C, obtains soda lime glass by uniformly, bubble-free.
Sodium silicate glass is green made from colorant 1 and colorant 2, sodium silicate glass made from original silica sand
It is colourless.Fig. 1 is the curve of spectrum of these three glass, and wherein curve a is the curve of spectrum of glass made from colorant 1, curve b
It is the curve of spectrum of glass made from colorant 2, as can be seen from the figure:Glass is in visible wavelength model made from original silica sand
In enclosing, uniform pickup, therefore glass is colourless;Have near 450nm and 650nm regardless of being glass made from colorant 1 or 2
Green is presented in selective absorbing, gained glass.
Claims (8)
1. a kind of method in silica sand surface construction coated with silica layer, it is characterized in that including the following steps:
(1)Silica sand is mixed with sodium hydroxide solution, carries out hydro-thermal reaction in confined conditions, until silica sand quality dissolves 12-50%
When stop reaction;
(2)Reaction solution is cooled down after reaction, adjusts reaction solution pH to 11-11.8, cetyl three is then added into reaction solution
Methyl bromide ammonium is reacted, in the compound of undissolved silica sand surface coated silica and cetyl trimethylammonium bromide
Body;
(3)After reaction, by step(2)Reaction solution pour out, wash obtained solid, then solid sample is dried, high-temperature calcination
Cetyl trimethylammonium bromide is removed to get the modification silica sand with coated with silica layer;
Step(1)In, the temperature of a concentration of 0.1 ~ 1 mol/L of sodium hydroxide solution, hydro-thermal reaction are 60 ~ 140 DEG C;
Step(2)In, a concentration of 0.0016 ~ 0.01g/ of the cetyl trimethylammonium bromide in the reaction solution after adjusting pH
ml;
Cetyl trimethylammonium bromide and step(1)The mass ratio of the silica sand of middle addition is 0.06 ~ 0.5:1.
2. according to the method described in claim 1, it is characterized in that:Step(2)In, after cetyl trimethylammonium bromide is added,
It is reacted at 25-65 DEG C.
3. according to the method described in claim 1, it is characterized in that:Step(3)In, the solid sample after drying is carried out at 550 DEG C
Calcining.
4. according to the method described in claim 1, it is characterized in that:Step(1)In, the time of hydro-thermal reaction is 4-24 hours;Step
Suddenly(2)In, after cetyl trimethylammonium bromide is added, react 0.5-12h.
5. a kind of modified silica sand, it is characterized in that:The modified silica sand be according to described in any one of claim 1-4 in silica sand
The method of the surface construction coated with silica layer modification silica sand obtained with coated with silica layer, or according to following
Modified silica sand made from method:0.5-9ml aminopropyl triethoxysilanes are added in the mixed liquor of ethyl alcohol and water, are uniformly mixed
Afterwards be added 5g according to described in any one of claim 1-4 made from the method for silica sand surface construction coated with silica layer
Modification silica sand with coated with silica layer is stirred to react 25min at 70 DEG C, be filtered, washed after reaction, dry to get.
6. Cr in a kind of waste water6+Processing method, it is characterized in that:Using the modification silica sand described in claim 5 as adsorbent, by it
It is added in waste water, by some or all of being adsorbed and removed in waste water Cr6+。
7. processing method according to claim 6, it is characterized in that:Cr will be contained6+Wastewater pH adjust to 1-6, then plus
Enter modified silica sand, modified silica sand, which is adsorbed at 25-65 DEG C, to carry out.
8. a kind of preparation method of silicate glass raw material, it is characterized in that:
(1)Cr will be contained6+Wastewater pH adjust to 1-6, the modification silica sand described in claim 5 is then added, it is right at 25-65 DEG C
Cr in waste water6+It is adsorbed;
(2)By the modification silica sand after absorption directly as the raw material of silicate glass, or the modification silica sand after absorption pressed again
According to step(1)Method be repeated at least once more after be re-used as the raw material of silicate glass.
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---|
硅源对合成介孔MCM-41分子筛结构、织构及其形貌的影响;许俊强 等;《硅酸盐学报》;20110228;第39卷(第2期);278-284 * |
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