CN109529919B - Preparation method of modified molecular sieve special for ceramic ink - Google Patents
Preparation method of modified molecular sieve special for ceramic ink Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 62
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 230000001699 photocatalysis Effects 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 28
- 229910002900 Bi2MoO6 Inorganic materials 0.000 claims abstract description 26
- 239000002808 molecular sieve Substances 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims description 63
- 238000000498 ball milling Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 2
- 239000003086 colorant Substances 0.000 abstract description 10
- 239000011941 photocatalyst Substances 0.000 abstract description 9
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 239000000976 ink Substances 0.000 description 53
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- -1 hydroxyl free radical Chemical class 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of preparation of photocatalyst materials, and particularly relates to a preparation method of a modified molecular sieve special for ceramic ink2MoO6The two semiconductor materials are compounded in a certain proportion to obtain the GaN-Bi2MoO6A composite photocatalytic material, and then the obtained GaN-Bi2MoO6The composite photocatalytic material is loaded on the molecular sieve according to a certain proportion, and the modified molecular sieve is obtained. The modified molecular sieve disclosed by the invention is applied to ceramic ink printed on a ceramic tile, so that the ceramic tile has higher photocatalytic performance; in addition, the coloring agent can be stably developed, and the color vividness of red and yellow is improved.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of preparation of photocatalyst materials, and particularly relates to a preparation method of a modified molecular sieve special for ceramic ink.
[ background of the invention ]
With the development of science and technology and the modernization of industry, the living standard of people is obviously improved, but simultaneously, people are harmed by the following environmental pollution. Water pollution, air pollution, indoor harmful gas and the like have caused serious harm to human health. Sewage treatment and air purification are therefore important research contents for researchers in various countries. How to effectively remove toxic substances such as surfactants, dyes, heavy metal ions and the like in industrial wastewater, and organic waste gas and toxic gas in the atmosphere becomes a hot topic in various research fields. Photocatalytic oxidation is an advanced oxidation technology, and is rapidly developed in the fields of sewage treatment and organic waste gas and toxic gas removal.
Ink jet printing is one of the most prominent plateless digital printing technologies at present, and the basic principle is to directly eject ink from a fine nozzle to a designated position on a printing material according to the instruction of a computer, so as to form a pre-designed pattern. The photocatalytic performance of the ink-jet printing ceramic ink for manufacturing decorative ceramics is disclosed, but the photocatalytic performance of the ink-jet printing ceramic ink is still to be improved; in addition, the colorant of the ceramic ink mainly comprises organic metal salt which can be dissolved in a solvent, and after the ceramic ink is printed and baked, part of the colorant undergoes chemical change under high temperature, so that the colorant becomes dark or even does not develop color, especially red and yellow.
[ summary of the invention ]
In view of the above, there is a need for a method for preparing a modified molecular sieve specially used for ceramic ink, wherein the modified molecular sieve is applied to ceramic tiles printed with ceramic ink, so that the ceramic tiles have high photocatalytic performance; in addition, the coloring agent can be stably developed, and the color vividness of red and yellow is improved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a modified molecular sieve special for ceramic ink comprises the following steps:
(1) respectively taking Ga2O3Powder and Bi2MoO6Powder, mixing the two materials and uniformly mixing by a ball milling method to obtain a mixture A, wherein Ga2O3And Bi2MoO6The molar ratio of (A) to (B) is 1-2: 2-3;
(2) placing the mixture A obtained in the step (1) in a gas-filled NH3Heating the mixture for 8 to 13 hours in a muffle furnace at 850-950 ℃ to obtain the GaN-Bi2MoO6A composite photocatalytic material, wherein NH3The flow rate of (2) is 80-100 mL/min;
(3) the GaN-Bi obtained in the step (2) is treated2MoO6Mixing the composite photocatalytic material and the molecular sieve according to the weight ratio of 1:2-6 to obtain a mixture B;
(4) adding a grinding aid into the mixture B obtained in the step (3) to obtain a mixture C, wherein the mass ratio of the grinding aid to the mixture B is 5-15: 1; then ball milling the mixture C to 0.5-2 μm to obtain a mixture D; and washing and drying the mixture D to obtain the modified molecular sieve.
In this invention, it is further specified that in step (3) the molecular sieve is selected from at least one of ZSM-5, beta or Y zeolite molecular sieves.
In the invention, the grinding aid in the step (4) is one of NaCl and sucrose or a mixture mixed in any proportion.
In the present invention, further, in the step (4), the mixture C is ball-milled by a sand mill.
In the present invention, it is further explained that, in the step (4), the rotation speed of the ball mill is 2000-3000 r/min.
In the invention, further, in the step (4), the mixture D is washed for 2-3 times by using distilled water as a detergent, and then is dried in an oven at 25-60 ℃ until the water content is less than 7%.
The modified molecular sieve prepared by the method is applied to the preparation of ceramic ink.
In the present invention, Bi2MoO6The photocatalyst is a semiconductor photochemical compound, has photocatalytic activity, and can generate active species such as hydroxyl free radical, superoxide free radical and the like under the irradiation of sunlight, thereby having the functions of antibiosis, deodorization, oil stain decomposition, mildew and algae prevention and air purification; GaN is a semiconductor compound with photocatalytic properties, and is mixed with Bi2MoO6The semiconductor compound obtained by compounding the components in a certain proportion has the function of improving the photocatalytic activity, and the reason is that the GaN and the Bi are strictly mixed2MoO6The compound makes the conduction band and the valence band of different semiconductors generate difference, thereby delaying the recombination of photo-generated electron-hole pairs and achieving the effect of improving the photocatalytic activity.
In the invention, the molecular sieve is loaded with a certain proportion of GaN-Bi2MoO6The composite photocatalytic material has photocatalytic effect, and may be used as photocatalyst for ceramic ink to degrade organic pollutant on the surface of ceramic, maintain the surface of ceramic glossy, clean and beautiful, decompose harmful organic gas in air, prevent mildew and kill bacteria and purify air.
In addition, the colorant of the ceramic ink mainly comprises organic metal salt which can be dissolved in a solvent, the colorant is baked after being printed by an ink-jet printer, the colorant is converted into metal oxide which can present colors at high temperature to form patterns, however, in the baking process of the ceramic tile, the metal oxide can generate a series of chemical reactions, so that the color development of the metal oxide is unstable, even the color development of the metal oxide can not be realized, particularly red and yellow.
The invention has the following beneficial effects:
1. the invention is applied to ceramic ink printed on ceramic tiles, can enable the ceramic tiles to have higher photocatalytic performance, and can effectively degrade organic pollutants on the surface of the ceramic and decompose organic harmful gases in the air.
2. The invention is applied to ceramic ink, can stabilize the color development of the colorant and improve the color vividness of red and yellow.
[ detailed description ] embodiments
The invention provides a preparation method of a modified molecular sieve special for ceramic ink, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear and definite. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The preparation method of the special modified molecular sieve for the ceramic ink provided by the invention comprises the following steps:
a preparation method of a modified molecular sieve special for ceramic ink comprises the following steps:
(1) respectively taking Ga2O3Powder and Bi2MoO6Powder, mixing the two materials and uniformly mixing by a ball milling method to obtain a mixture A, wherein Ga2O3And Bi2MoO6In a molar ratio of 1: 2;
(2) placing the mixture A obtained in the step (1) in a gas-filled NH3Heating the mixture for 8 hours at 850 ℃ in a muffle furnace to obtain the GaN-Bi2MoO6A composite photocatalytic material, wherein NH3The flow rate of (2) is 80 mL/min;
(3) subjecting the product obtained in step (2)GaN-Bi2MoO6Mixing the composite photocatalytic material and a molecular sieve according to the weight part ratio of 1:2 to obtain a mixture B, wherein the molecular sieve is selected from ZSM-5;
(4) adding a grinding aid into the mixture B obtained in the step (3) to obtain a mixture C, wherein the mass ratio of the grinding aid to the mixture B is 5:1, and the grinding aid is NaCl; then, ball milling the mixture C to 0.5-1 μm by using a sand mill at the ball milling rotation speed of 2000r/min to obtain a mixture D; and then, washing the mixture D for 2 times by using distilled water as a washing agent, and then putting the mixture D into a drying oven at 25 ℃ for drying until the water content is less than 7%, thus obtaining the modified molecular sieve.
The modified molecular sieve prepared by the method is applied to the preparation of ceramic ink.
Example 2
The preparation method of the special modified molecular sieve for the ceramic ink provided by the invention comprises the following steps:
a preparation method of a modified molecular sieve special for ceramic ink comprises the following steps:
(1) respectively taking Ga2O3Powder and Bi2MoO6Powder, mixing the two materials and uniformly mixing by a ball milling method to obtain a mixture A, wherein Ga2O3And Bi2MoO6In a molar ratio of 1.5: 2.5;
(2) placing the mixture A obtained in the step (1) in a gas-filled NH3Heating the mixture for 10 hours at the temperature of 900 ℃ to obtain the GaN-Bi2MoO6A composite photocatalytic material, wherein NH3The flow rate of (2) is 90 mL/min;
(3) the GaN-Bi obtained in the step (2) is treated2MoO6Mixing the composite photocatalytic material and a molecular sieve according to a weight part ratio of 1:4 to obtain a mixture B, wherein the molecular sieve is selected from a mixture of ZSM-5 and beta in any proportion;
(4) adding a grinding aid into the mixture B obtained in the step (3) to obtain a mixture C, wherein the mass ratio of the grinding aid to the mixture B is 10:1, and the grinding aid is sucrose; then, ball milling the mixture C to 1-1.5 mu m by using a sand mill, wherein the ball milling rotating speed is 2500r/min, and obtaining a mixture D; and then, washing the mixture D for 2 times by using distilled water as a washing agent, and then putting the mixture D into a 45 ℃ oven to be dried until the water content is less than 7%, thus obtaining the modified molecular sieve.
The modified molecular sieve prepared by the method is applied to the preparation of ceramic ink.
Example 3
The preparation method of the special modified molecular sieve for the ceramic ink provided by the invention comprises the following steps:
a preparation method of a modified molecular sieve special for ceramic ink comprises the following steps:
(1) respectively taking Ga2O3Powder and Bi2MoO6Powder, mixing the two materials and uniformly mixing by a ball milling method to obtain a mixture A, wherein Ga2O3And Bi2MoO6In a molar ratio of 2: 3;
(2) placing the mixture A obtained in the step (1) in a gas-filled NH3Heating the mixture for 13 hours in a muffle furnace at 950 ℃ to obtain the GaN-Bi2MoO6 composite photocatalytic material, wherein NH is3The flow rate of (2) is 100 mL/min;
(3) the GaN-Bi obtained in the step (2) is treated2MoO6Mixing the composite photocatalytic material and a molecular sieve according to a weight part ratio of 1:6 to obtain a mixture B, wherein the molecular sieve is a mixture of ZSM-5, beta and Y zeolite molecular sieves in any ratio;
(4) adding a grinding aid into the mixture B obtained in the step (3) to obtain a mixture C, wherein the mass ratio of the grinding aid to the mixture B is 15:1, and the grinding aid is a mixture of NaCl and sucrose in any proportion; then, ball milling the mixture C to 1.5-2 μm by using a sand mill at the ball milling speed of 3000r/min to obtain a mixture D; and then, washing the mixture D for 3 times by using distilled water as a washing agent, and then putting the mixture D into a 60-DEG C drying oven to dry until the water content is less than 7%, thus obtaining the modified molecular sieve.
The modified molecular sieve prepared by the method is applied to the preparation of ceramic ink.
Comparative example 1
The modified molecular sieve special for the ceramic ink provided by the embodiment is as follows:
preparation method of modified molecular sieve special for ceramic ink, and in the preparation method, Bi2MoO6Does not form GaN-Bi by combination with GaN2MoO6The composite photocatalytic material was directly supported on the molecular sieve, and the rest was the same as in example 2. The modified molecular sieve prepared by the method is applied to the preparation of ceramic ink.
Comparative example 2
The modified molecular sieve special for the ceramic ink provided by the embodiment is prepared by the following steps:
a process for preparing the modified molecular sieve specially used for ceramic ink features that in its preparing process, GaN is not mixed with Bi2MoO6Recombination to form GaN-Bi2MoO6The composite photocatalytic material was directly supported on the molecular sieve, and the rest was the same as in example 2. The modified molecular sieve prepared by the method is applied to the preparation of ceramic ink.
Effect verification
(I) photocatalytic assay
After the finished products of examples 1-3 and comparative examples 1-2 were prepared, the finished products were used as 5 test finished products and applied to the preparation of ceramic inks, and the preparation method, the amount of the test finished products and the types and the amounts of other reagents of each group of ceramic inks were the same, wherein the formula of the ceramic inks was as follows: 25% of pigment, 8% of photocatalyst, 2% of magnesium carbonate, 30% of D100 solvent oil and 10% of propylene glycol methyl ether; 3% of hyperdispersant; 0.8% of a binding agent; 2% of surfactant, 0.3% of defoaming agent and 1.2% of glycerol, wherein the photocatalyst corresponds to 6 molecular sieve photocatalyst test finished products in each group of formula, 5 ceramic ink samples are prepared and sequentially marked as samples 1-5, then ceramic tiles of the same material are printed and roasted by using the samples 1-5, 5 ceramic tiles are respectively placed into 5 glass test boxes of 50cm × 50cm × 100cm, test samples corresponding to the test boxes are labeled one by one, formaldehyde is used as a simulation photocatalytic substrate, 6ml of formaldehyde is injected into each test box, the ceramic tiles are respectively taken out after standing for 24 times, the formaldehyde degradation rate in the 5 test boxes is respectively detected by using a phenol reagent spectrophotometer, and the results are recorded in table 1. The detection results are shown in table 1:
TABLE 1 photocatalytic verification and detection results of molecular sieve photocatalysts
The above data show that the 2 comparative examples were re-prepared due to GaN and Bi2MoO6Partial warp recombination into GaN-Bi2MoO6The composite photocatalytic material is directly loaded on the molecular sieve, and after the composite photocatalytic material is applied to the preparation of ceramic ink, the degradation rate of formaldehyde is obviously lower than that of 3 embodiments of the invention, and the experiment shows that the invention greatly improves the photocatalytic performance of the finished product.
(II) verification of effect of improving color vividness
After the finished products of examples 1 to 3 are used as 3 test finished products, the test finished products are respectively applied to the preparation of ceramic ink, wherein each test finished product is used for preparing a red ink and a yellow ink, the ink formula is the same as the above (1), the pigment in the red ink formula is nano iron oxide, the pigment in the yellow ink formula is praseodymium carboxylate, 3 red ink samples and 3 yellow inks are respectively prepared by the same preparation method, a red ink and a yellow ink are respectively prepared by the same preparation method of the red ink and the yellow ink to be used as comparison samples, the difference is that no molecular sieve catalyst of any type is added in the raw materials, then ceramic tiles of the same material are printed and roasted by using the ink samples prepared by the above, wherein the ink quantity printed on each ceramic tile is the same, the color and luster of the printed ceramic tiles are respectively evaluated, and the results are shown in the following table 2:
TABLE 2 influence of molecular sieve photocatalyst on color and luster vividness of ink
In the above table, the samples 1 to 3 correspond to the finished products prepared in the examples 1 to 3, and the data in the above table show that the ink in the control group has dark color and obviously less bright color than the other 3 test groups after printing and roasting the ceramic tile because no molecular sieve catalyst of any type is added, so that the application of the invention to the ceramic ink has the effect of improving the brightness of the color.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (4)
1. The preparation method of the modified molecular sieve special for the ceramic ink is characterized by comprising the following steps of:
(1) respectively taking Ga2O3Powder and Bi2MoO6Powder, mixing the two materials and uniformly mixing by a ball milling method to obtain a mixture A, wherein Ga2O3And Bi2MoO6The molar ratio of (A) to (B) is 1-2: 2-3;
(2) placing the mixture A obtained in the step (1) in a gas-filled NH3Heating the mixture for 8 to 13 hours in a muffle furnace at 850-950 ℃ to obtain the GaN-Bi2MoO6A composite photocatalytic material, wherein NH3The flow rate of (A) is 80-100 mL/min;
(3) the GaN-Bi obtained in the step (2) is treated2MoO6Mixing the composite photocatalytic material and the molecular sieve according to the weight ratio of 1:2-6 to obtain a mixture B; the molecular sieve is at least one of ZSM-5, beta or Y zeolite molecular sieve;
(4) adding a grinding aid into the mixture B obtained in the step (3) to obtain a mixture C, wherein the mass ratio of the grinding aid to the mixture B is 5-15: 1; then ball milling the mixture C to 0.5-2 μm to obtain a mixture D; then washing and drying the mixture D to obtain the modified molecular sieve; and (4) ball-milling the mixture C by using a sand mill, wherein the grinding aid in the step (4) is one of NaCl and sucrose or a mixture mixed in any proportion.
2. The preparation method of the modified molecular sieve special for the ceramic ink according to claim 1, characterized in that: in the step (4), the ball milling speed is 2000-3000 r/min.
3. The preparation method of the modified molecular sieve special for ceramic ink according to claim 1, characterized in that: and (4) washing the mixture D for 2-3 times by using distilled water as a detergent, and then putting the mixture D into an oven with the temperature of 25-60 ℃ for drying until the water content is less than 7%.
4. A modified molecular sieve specially used for ceramic ink prepared by the preparation method of any one of claims 1 to 3.
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