CN109694079B - Method for preparing Zr-MSU mesoporous molecular sieve by using industrial zirconium-containing waste residues as raw materials and mesoporous molecular sieve - Google Patents
Method for preparing Zr-MSU mesoporous molecular sieve by using industrial zirconium-containing waste residues as raw materials and mesoporous molecular sieve Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 44
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000002699 waste material Substances 0.000 title claims abstract description 23
- 239000002994 raw material Substances 0.000 title claims abstract description 13
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 11
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- XRKBQVGBWJWJJJ-UHFFFAOYSA-N 2-aminooctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(N)C(O)=O XRKBQVGBWJWJJJ-UHFFFAOYSA-N 0.000 claims description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- CCWSOCZJHAQLCF-UHFFFAOYSA-N n-chlorododecan-1-amine Chemical compound CCCCCCCCCCCCNCl CCWSOCZJHAQLCF-UHFFFAOYSA-N 0.000 claims description 2
- XTWFYOWMGXBNGN-UHFFFAOYSA-N n-chlorooctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCl XTWFYOWMGXBNGN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- HEBRGEBJCIKEKX-UHFFFAOYSA-M sodium;2-hexadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HEBRGEBJCIKEKX-UHFFFAOYSA-M 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 239000001045 blue dye Substances 0.000 abstract description 2
- 239000002893 slag Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
-
- 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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B01J35/635—
-
- B01J35/647—
-
- 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
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
The invention discloses a method for preparing a Zr-MSU mesoporous molecular sieve with macropores (the aperture is 8.9nm), high doping amount (the silicon-zirconium ratio is 1) and high catalytic performance by taking industrial zirconium-containing waste residues as raw materials and taking a mixed solution of an anionic surfactant and a cationic surfactant as a template agent, and a corresponding Zr-MSU mesoporous molecular sieve. The method is simple to operate, environment-friendly and low in cost, the obtained material has excellent catalytic degradation performance on methyl blue dye, and 97.2% of methyl blue solution with the concentration of 100ppm (liquid-solid ratio is 400) can be degraded after being treated for 15 minutes at room temperature.
Description
Technical Field
The invention belongs to the field of preparing molecular sieve materials by utilizing solid waste materials, and particularly relates to a method for preparing a Zr-MSU mesoporous molecular sieve by taking industrial zirconium-containing waste residues as raw materials and the Zr-MSU molecular sieve.
Background
MSU is a novel mesoporous molecular sieve developed after M41S and HSM, and has attracted much attention since the past since it has the advantages of large specific surface area and pore volume, long-range ordered three-dimensional pore structure, superior diffusion performance, mechanical and thermal stability, and the like, and particularly, it is widely used in the fields of catalysis, adsorption, separation, and the like by doping transition metal ions in its framework to improve its acidity-basicity and redox properties.
At present, most reports about the synthesis of MSU mesoporous materials show that silicon sources used by the MSU mesoporous materials are pure chemical reagents, and used surfactants are generally nonionic surfactants, so that the dosage of the nonionic surfactants is large, the zirconium doping amount is limited, the obtained samples are high in cost and not ideal in stability and catalytic performance, and the large-scale production and application of the MSU mesoporous materials are limited.
The high-value utilization of solid wastes is always a great problem which puzzles the environmental problem in China. The zirconium-containing waste slag generally contains more silicon dioxide, and zirconium and silicon can carry out certain pre-reaction in the forming process, so the material is an ideal raw material for preparing the mesoporous molecular sieve.
Early pure silicon and zirconium-doped MSU are mostly synthesized by a single surfactant system, the synthesis window of the product is narrow, the zirconium doping amount is low, and the method has a large distance from industrial application. The mixed surfactant system has the mutual coupling effect of various assembly acting forces, so that the mixed surfactant system has obvious superiority compared with a single surfactant system in the synthesis of mesoporous materials such as MCM-41, MCM-48, SBA-15 and the like.
Disclosure of Invention
The invention aims to use industrial zirconium-containing waste residues regarded as solid wastes as raw materials for preparing Zr-doped mesoporous molecular sieves, and use the obtained materials for harmless treatment of industrial wastewater, thereby realizing a new environmental management idea of changing waste into valuable and treating wastes with wastes.
The typical method for synthesizing the Zr-doped mesoporous molecular sieve provided by the invention comprises the following steps:
(1) providing a mixed aqueous solution of an anionic surfactant and a cationic surfactant, and dropwise adding an alkali solution containing zirconium waste residues under stirring to obtain a mixed solution;
(2) carrying out hydrothermal reaction crystallization on the mixed solution obtained in the step (1);
(3) carrying out suction filtration, washing and drying on the mixture obtained in the step (2) to obtain synthetic raw powder;
(4) and directly roasting the synthetic raw powder in the air to obtain the product.
As a better choice for the method, Na is contained in the alkaline solution of the zirconium-containing waste residue2O:SiO2:ZrO2The mass ratio of the components is 10-15:40-60:0.46-9.2。
As a more preferable choice of the method, Na is contained in the alkaline solution of the zirconium-containing waste residue2O:SiO2:ZrO2The mass ratio of (A) to (B) is 13-15:50-60: 3-5.
As a better choice of the method, the anionic surfactant used in the step (1) comprises one or more of sodium dodecyl benzene sulfonate, sodium hexadecylbenzene sulfonate and sodium dodecyl sulfate.
As a better alternative to the above method, the cationic surfactant used in step (1) includes quaternary ammonium salt type cationic surfactant and/or non-quaternary ammonium salt type cationic surfactant, the quaternary ammonium salt type cationic surfactant includes more than one of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride and lauryl trimethyl ammonium chloride, and the non-quaternary ammonium salt type cationic surfactant includes more than one of octadecyl amino hydrochloric acid, dodecyl amino hydrochloric acid and hexadecyl amino acetic acid.
As a better alternative to the above method, in the mixed liquid obtained in step (1), the molar ratio of silicon dioxide to sodium oxide to water is SiO2：Na2O (added sodium hydroxide): h2O is 1.0: x: y, wherein: 0.25<x<0.35,40<y<70。
As a better choice of the method, the silicon-zirconium ratio in the mixed liquid obtained in the step (1) is 1: 0.8-1.1.
As a more preferable alternative of the above method, the molar ratio of the cationic surfactant to the anionic surfactant is 11/1 to 3/1.
As a better choice of the method, the mole ratio of the cationic surfactant to the silicon dioxide is 0.09-0.31.
As a better choice of the method, the crystallization temperature in the step (2) is 80-140 ℃, and the crystallization time is 1-5 days.
As a better choice of the method, the roasting temperature of the synthetic raw powder in the step (4) is 450-700 ℃, and the roasting time is 3-7 h.
Preparation of the inventionThe Zr doped mesoporous molecular sieve has the following general formula: xSiO2·yZrO2Wherein x, y is 1: 0.1-2; the aperture of the Zr-doped mesoporous molecular sieve is 3-20 nm.
As a better choice of the Zr-doped mesoporous molecular sieve, the aperture of the Zr-doped mesoporous molecular sieve is 8-9 nm.
As a more preferable selection of the Zr doped mesoporous molecular sieve, x: y is 1:0.8 to 1.1.
As a more preferable alternative to the above Zr-doped mesoporous molecular sieve, the Zr-doped mesoporous molecular sieve has an average particle diameter of 0.5 to 3.5. mu.m.
As a more preferable alternative to the above Zr-doped mesoporous molecular sieve, the Zr-doped mesoporous molecular sieve has a pore volume of 0.5 to 1cm3/g。
The invention takes industrial zirconium-containing waste residue as a raw material for the first time, takes a mixed solution of anionic surfactant (such as Sodium Dodecyl Benzene Sulfonate (SDBS), Sodium Dodecyl Sulfate (SDS) and the like) and cationic surfactant (such as Cetyl Trimethyl Ammonium Bromide (CTAB), Cetyl Trimethyl Ammonium Chloride (CTAC) and the like) as a template agent, and prepares the Zr-MSU mesoporous molecular sieve with macropore, high doping amount and high catalytic performance.
The invention prepares the Zr-MSU mesoporous molecular sieve with macropores (the aperture is 8.9nm), high doping amount (the silicon-zirconium ratio is 1) and high catalytic performance by taking industrial zirconium-containing waste residues as raw materials and taking a mixed solution of an anionic surfactant and a cationic surfactant as a template agent. The method is simple to operate, environment-friendly and low in cost, and the obtained material shows excellent catalytic degradation performance on methyl blue dye. 97.2% methyl blue was degraded by treatment at room temperature for 15 minutes for a 100ppm methyl blue solution (liquid to solid ratio of 400).
Drawings
FIG. 1 is a characteristic X-ray diffraction pattern (XRD) of a calcined Zr-MSU sample;
FIG. 2 is N of Zr-MSU sample after calcination2An adsorption-desorption curve, and an inset is a corresponding aperture distribution curve;
FIG. 3 is an ultraviolet-visible diffuse scattering spectrum (UV-vis) of a calcined Zr-MSU sample;
FIG. 4 is a Transmission Electron Micrograph (TEM) of a sample of Zr-MSU after firing.
Detailed Description
The following are examples of the present invention, which are intended to be illustrative of the invention only and not limiting.
The composition of typical zirconium-containing waste slag and its synthetic product Zr-MSU used in the present invention is shown in Table 1.
TABLE 1 composition of typical zirconium-containing slag and resulting Zr-MSU samples
The features of the invention are further described below by way of examples.
Example 1:
under the constant stirring speed, a certain amount of zirconium slag (zirconium content is 4.63Wt percent) alkali solution is dropwise added into a mixed aqueous solution of CTAB and SDBS with the molar ratio of 5:1, and the mixture is stirred for 1 hour at 40 ℃ to obtain the solution with the molar composition of 1.0SiO2:0.15CTAB:0.03SDBS:0.3Na2O:60H2A mixture of O. And transferring the mixture into a stainless steel reaction kettle, standing for 3 days at 100 ℃, washing, filtering and drying a product to obtain the synthetic Zr-MSU. The sample is directly roasted for 7h at 450 ℃ in the air to obtain the Zr-MSU mesoporous molecular sieve. Characteristic X-ray diffraction Pattern of the sample, N2The adsorption-desorption curve, the ultraviolet-visible diffuse scattering spectrum and the Transmission Electron Microscope (TEM) are shown in fig. 1, fig. 2, fig. 3 and fig. 4, respectively. The composition of the zirconium-containing slag raw material is shown in Table 1. The results of fig. 1 and 4 indicate that the sample is a high quality MSU mesoporous molecular sieve. As can be seen from FIG. 2, the pore diameter was about 8.9nm, and the specific surface area was 260m2(ii)/g; the pore volume is 0.65cm3(ii) in terms of/g. It can be seen from fig. 3 that zirconium is significantly doped into the framework of the MSU mesoporous molecular sieve, which is consistent with the results of table 1 with a silicon to zirconium ratio of 1; the sample can be degraded by 97.2 percent after being treated for 15 minutes at room temperature for 100ppm of methyl blue solution at a liquid-solid ratio of 400.
Example 2:
the process for preparing the synthetic Zr-MSU is the same as that of example 1, and the synthetic Zr-MSU is directly roasted for 3 hours at 700 ℃ in the air to obtain the Zr-MSU mesoporous molecular sieve.
Example 3:
the process for preparing the synthetic Zr-MSU is the same as that of example 1, and the synthetic Zr-MSU is directly roasted for 5 hours at 550 ℃ in the air, so that the Zr-MSU mesoporous molecular sieve is obtained.
Example 4:
the cationic and anionic surfactants in example 1 are respectively changed into SDS and CTAC, and other steps are not changed, so that the Zr-MSU mesoporous molecular sieve can be obtained.
Example 5:
dropwise adding a certain amount of zirconium slag (zirconium content is 0.46 Wt%) alkali solution into a mixed aqueous solution of CTAB and SDBS (cetyl trimethyl ammonium bromide) at a ratio of 11:1, stirring for 1 hour to obtain a mixed aqueous solution with a molar composition of 1.0SiO2:0.31CTAB:0.028SDBS:0.25Na2O:70H2A mixture of O. And transferring the mixture into a stainless steel reaction kettle, crystallizing for 5 days at 80 ℃, washing, filtering and drying the product to obtain the synthetic Zr-MSU. The sample is directly roasted for 4 hours at 600 ℃ in the air to obtain the Zr-MSU mesoporous molecular sieve.
Example 6:
dropwise adding a certain amount of zirconium slag (zirconium content is 9.2 Wt%) aqueous alkali into a mixed aqueous solution of CTAB and SDBS (cetyl trimethyl ammonium bromide) in a ratio of 3:1, stirring for 1 hour to obtain a solution with a molar composition of 1.0SiO2:0.09CTAB:0.03SDBS:0.35Na2O:40H2A mixture of O. And transferring the mixture into a stainless steel reaction kettle, crystallizing for 1 day at 140 ℃, washing, filtering and drying the product to obtain the synthetic Zr-MSU. The sample is directly roasted for 4 hours at 600 ℃ in the air to obtain the Zr-MSU mesoporous molecular sieve.
The degradation performance of the mesoporous molecular sieves obtained in examples 2-6 was tested and was similar to that of the mesoporous molecular sieve obtained in example 1, which indicates that the mesoporous molecular sieves with good degradation performance can be prepared in a wide range of zirconium slag alkali solution compositions.
Finally, it should be noted that the above examples are only used to illustrate the technical solution of the present invention and are not limited, since the impurity content in the zirconium slag varies according to the raw material and the process, but only if it satisfies the requirement of Na in the alkaline solution of the zirconium-containing waste slag2O:SiO2:ZrO2The mass ratio of the Zr-MSU mesoporous molecular sieve to the zirconium-containing waste residue is 10-15:40-60:0.46-9.2, even if the zirconium-containing waste residue contains other interfering ions such as Al, Ca, Fe, Mg and the like, the Zr-MSU mesoporous molecular sieve with obvious degradation effect on the waste water can be prepared.
Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. A method for preparing Zr-MSU mesoporous molecular sieve by taking industrial zirconium-containing waste residue as a raw material comprises the following steps:
(1) providing a mixed aqueous solution of an anionic surfactant and a cationic surfactant, and dropwise adding an alkali solution containing zirconium waste residues under stirring to obtain a mixed solution;
(2) performing hydrothermal reaction crystallization on the mixed solution obtained in the step (1), wherein the crystallization temperature is 80-140 ℃, and the crystallization time is 1-5 days;
(3) carrying out suction filtration, washing and drying on the mixture obtained in the step (2) to obtain synthetic raw powder;
(4) directly roasting the synthetic raw powder in the air to obtain a Zr-MSU mesoporous molecular sieve;
the anionic surfactant used in the step (1) comprises one or more of sodium dodecyl benzene sulfonate, sodium hexadecylbenzene sulfonate and sodium dodecyl sulfate;
the cationic surfactant used in the step (1) comprises a quaternary ammonium salt type cationic surfactant and/or a non-quaternary ammonium salt type cationic surfactant, wherein the quaternary ammonium salt type cationic surfactant comprises more than one of hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride and dodecyl trimethyl ammonium chloride, and the non-quaternary ammonium salt type cationic surfactant comprises more than one of octadecyl amino hydrochloric acid, dodecyl amino hydrochloric acid and hexadecyl amino acetic acid;
the molar ratio of the cationic surfactant to the anionic surfactant in the step (1) is 11/1-3/1;
na in the alkaline solution containing the zirconium waste residue2O:SiO2:ZrO2The mass ratio of the components is 10-15:40-60: 0.46-9.2.
2. The method for preparing Zr-MSU mesoporous molecular sieve according to claim 1, wherein the molar ratio of SiO to sodium oxide to water in the mixed solution obtained in step (1) is set as the SiO/water ratio2：Na2O：H2O is 1.0: x: y, wherein: 0.25<x<0.35,40<y<70。
3. The method for preparing Zr-MSU mesoporous molecular sieve by using industrial zirconium-containing waste residue as raw material according to claim 1, wherein the molar ratio of the cationic surfactant to the silica in the step (1) is 0.09-0.31.
4. The method for preparing Zr-MSU mesoporous molecular sieve by using industrial zirconium-containing waste residue as raw material according to claim 1, wherein the calcination temperature of the synthetic raw powder in the step (4) is 450-700 ℃, and the calcination time is 3-7 h.
5. The Zr-MSU mesoporous molecular sieve prepared by the process of any of claims 1 to 4, having the general formula: xSiO2·yZrO2Wherein x and y are 1: 0.1-2; the aperture of the Zr-doped mesoporous molecular sieve is 3-20 nm.
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| EP0101291A2 (en) * | 1982-08-16 | 1984-02-22 | Mobil Oil Corporation | Improved catalytic cracking |
| CN1460550A (en) * | 2003-04-30 | 2003-12-10 | 中国科学院山西煤炭化学研究所 | Method for quickly-synthesizing ZSM-S molecular sieve containing zirconium atom |
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| CN101948119A (en) * | 2010-09-14 | 2011-01-19 | 江苏大学 | Preparation method of MCM-48 molecular sieve containing zirconium |
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| EP0101291A2 (en) * | 1982-08-16 | 1984-02-22 | Mobil Oil Corporation | Improved catalytic cracking |
| CN1460550A (en) * | 2003-04-30 | 2003-12-10 | 中国科学院山西煤炭化学研究所 | Method for quickly-synthesizing ZSM-S molecular sieve containing zirconium atom |
| CN1636873A (en) * | 2004-10-16 | 2005-07-13 | 太原理工大学 | Mesoporous Zr-Si molecular sieve and its synthesis |
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