CN113491998A - Method for synthesizing ZSM-5 adsorbent by aid of seed crystals - Google Patents
Method for synthesizing ZSM-5 adsorbent by aid of seed crystals Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 38
- 239000003463 adsorbent Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 22
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010457 zeolite Substances 0.000 claims abstract description 22
- 239000002808 molecular sieve Substances 0.000 claims abstract description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- 230000008025 crystallization Effects 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 91
- 239000000377 silicon dioxide Substances 0.000 claims description 48
- 229910052681 coesite Inorganic materials 0.000 claims description 39
- 229910052906 cristobalite Inorganic materials 0.000 claims description 39
- 229910052682 stishovite Inorganic materials 0.000 claims description 39
- 229910052905 tridymite Inorganic materials 0.000 claims description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 229910052593 corundum Inorganic materials 0.000 claims description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 16
- 229910001868 water Inorganic materials 0.000 claims description 14
- 229910000144 sodium(I) superoxide Inorganic materials 0.000 claims description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 21
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- -1 ammonium ions Chemical class 0.000 abstract description 3
- 238000005342 ion exchange Methods 0.000 abstract description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 239000001164 aluminium sulphate Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000149 chemical water pollutant Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
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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
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- 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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- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
- C02F2101/30—Organic compounds
Abstract
The invention discloses a method for synthesizing a ZSM-5 adsorbent by seed crystal assistance, which comprises the following steps: adding an aluminum source into deionized water, uniformly stirring, sequentially adding NaOH and a silicon source, and stirring for 15-30 min; adding the seeds A and stirring for 2-3h to obtain mixed gel; heating to 170-180 ℃ for crystallization for 24-48 h; after filtering, washing with deionized water, and drying to obtain the ZSM-5 molecular sieve; the seed A is one of all-silicon zeolite (Silicate-1), Y-type zeolite and ZSM-11. The ZSM-5 zeolite synthesized by the aid of the seed crystals has the advantages of large specific surface area, more ammonia nitrogen and VOC adsorbed in unit area, small crystal size, effective reduction of diffusion length in adsorption, increase of adsorption performance, and increase of ion exchange volume by changing of silicon-aluminum ratio, so that more ammonium ions can be adsorbed, and the adsorption effect on the ammonia nitrogen is enhanced.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a method for synthesizing a ZSM-5 adsorbent by using a seed crystal in an auxiliary manner.
Background
The sources of the ammonia nitrogen wastewater can be divided into a natural source and an artificial source. The natural sources are mainly degradation of some nitrogenous organic matters in nature, such as animal excrement, animal and plant debris and plant nitrogen nutrient loss, although a large amount of ammonia nitrogen comes from the natural sources every year, the ammonia nitrogen is highly dispersed and has low concentration, and the degree of harming human health is not reached; the artificial sources mainly include: although the total ammonia nitrogen content of metallurgy, coking, pharmacy, food, chemical fertilizer, landfill leachate and the like is less than that of natural sources, the concentration is generally higher due to high concentration, water eutrophication is caused, the quality of drinking water is reduced, and direct damage is caused to human health.
The traditional method for synthesizing ZSM-5 is to add a certain amount of template agent in a hydrothermal system to promote the growth of ZSM-5 nanocrystals, which can be divided into organic and inorganic template agents according to the difference of the template agent, and the organic template agent is relatively easy to regulate and control the grain size and the apparent morphology of the synthesized product, but the organic templates are expensive and have complex structures and must be removed by high-temperature calcination to form pores. This process consumes energy and produces environmentally unfriendly gases, such as carbon dioxide. Although the inorganic template agent can obviously reduce the cost and the environmental pollution, the product has the problems of large amount of mixed crystals, uneven grain size, low crystallinity and the like, so the template-free seed crystal method has good application prospect.
Disclosure of Invention
The invention aims to provide a method for synthesizing nano ZSM-5 without using an organic template, which can effectively remove ammonia nitrogen and VOC in wastewater and reach the emission standard; meanwhile, the preparation process is simplified, the energy consumption is low, the pollution is low, and the method can be applied to the removal of ammonia nitrogen and VOC on a large scale.
In order to achieve the purpose, the technical scheme is as follows:
a method for synthesizing a ZSM-5 adsorbent by using seed crystal assistance comprises the following steps:
adding an aluminum source into deionized water, uniformly stirring, sequentially adding NaOH and a silicon source, and stirring for 15-30 min;
adding the seeds A and stirring for 2-3h to obtain mixed gel; heating to 170-180 ℃ for crystallization for 24-48 h;
after filtering, washing with deionized water, and drying to obtain the ZSM-5 molecular sieve;
the seed A is one of all-silicon zeolite (Silicate-1), Y-type zeolite and ZSM-11.
According to the scheme, the particle size of the all-silica zeolite is 100-300 nm; the Y-type zeolite SiO has the Si/Al ratio2/Al2O3Is 3-6.
According to the scheme, the aluminum source is one of aluminum sulfate, sodium metaaluminate and aluminum isopropoxide.
According to the scheme, the silicon source is one of fumed silica and liquid silica sol.
According to the scheme, NaOH is added to adjust the pH value to 9-12.
According to the scheme, SiO in the seeds A2Mass accounts for SiO in the mixed gel2The mass ratio is 4-32 wt%.
According to the scheme, the molar ratio of each substance in the mixed gel is SiO2/Al2O3＝40-100，SiO2/NaO2＝1.5-15，SiO2/H2O＝0.02-0.04。
According to the scheme, the drying condition is drying for 12-24h at 80-100 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the ZSM-5 molecular sieve with uniform particle size and regular appearance is prepared by using a seed crystal assisted hydrothermal synthesis method, and the specific surface area is 300-340 m2G, pore volume of 0.15-0.20cm3(ii)/g; the adsorbent has larger specific surface area and pore volume, and has stronger adsorption effect on ammonia nitrogen and VOC; the removal rate of ammonia nitrogen in the ammonia nitrogen wastewater reaches 80-95 percent, and the removal rate of VOC in the VOC wastewater reaches 85-95 percent.
The ZSM-5 zeolite synthesized by the aid of the seed crystals has the advantages of large specific surface area, more ammonia nitrogen and VOC adsorbed in unit area, small crystal size, effective reduction of diffusion length in adsorption, increase of adsorption performance, and increase of ion exchange volume by changing of silicon-aluminum ratio, so that more ammonium ions can be adsorbed, and the adsorption effect on the ammonia nitrogen is enhanced.
The method adopts the seed crystal to assist in synthesizing the ZSM-5 adsorbent, has simple preparation process, low energy consumption and little pollution, and can be widely applied to removing ammonia nitrogen in ammonia nitrogen wastewater.
Drawings
FIG. 1: an XRD characterization pattern of the ZSM-5 molecular sieve obtained in example 1.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
The invention provides a method for synthesizing a ZSM-5 adsorbent by using a seed crystal in an auxiliary manner, which comprises the following specific steps:
adding an aluminum source into deionized water, uniformly stirring, sequentially adding NaOH and a silicon source, and stirring for 15-30 min; adjusting the pH value to 9-12; the aluminum source is one of aluminum sulfate, sodium metaaluminate and aluminum isopropoxide; the silicon source is one of gas-phase silicon dioxide and liquid silica sol;
adding the seeds A and stirring for 2-3h to obtain mixed gel; heating to 170-180 ℃ for crystallization for 24-48 h; SiO in the seed A2Mass accounts for SiO in the mixed gel2The mass ratio is 4-32 wt%; the molar ratio of each substance in the mixed gel is SiO2/Al2O3＝40-100，SiO2/NaO2＝1.5-15，SiO2/H2O＝0.02-0.04；
Filtering, washing with deionized water, and drying at 80-100 deg.C for 12-24h to obtain ZSM-5 molecular sieve;
the seed A is one of all-silicon zeolite (Silicate-1), Y-type zeolite and ZSM-11; the particle size of the all-silicon zeolite is 100-300 nm; the Y-type zeolite SiO has the Si/Al ratio2/Al2O3Is 3-6.
Example 1
Adding a certain amount of sodium metaaluminate into deionized water, stirring uniformly, sequentially adding NaOH and silica sol, stirring for 15min, then adding crystal seed full-silica zeolite (Silicate-1), stirring for 2h, wherein the mass fraction of the crystal seed is 4% wt, obtaining mixed gel, and the molar ratio of each substance in the mixed gel is SiO2/Al2O3＝40，SiO2/NaO2＝6，SiO2/H2O is 0.02; crystallizing at 170 deg.C for 24h, filtering, washing the product with deionized water for 3 times, and drying at 100 deg.C for 12h to obtain ZSM-5 molecular sieve labeled L1.
The XRD characterization pattern of the ZSM-5 molecular sieve obtained in the example is shown in figure 1, is consistent with the characteristic peak of ZSM-5, has no other characteristic peaks of crystal forms, and indicates that the seed crystal assisted synthesis of the ZSM-5 zeolite is successful, and the XRD characterization pattern shows very low background signals and sharp reflection, and indicates that the sample has excellent crystallinity.
Example 2
Adding a certain amount of sodium metaaluminate into deionized water, stirring uniformly, sequentially adding NaOH, 2Gas phase SiOStirring for 15min, adding crystal seed NaY, and stirring for 3h, wherein the mass fraction of the crystal seed is 4 wt%, to obtain mixed gel, and the molar ratio of each substance in the mixed gel is SiO2/Al2O3＝40，SiO2/NaO2＝7，SiO2/H2O is 0.03; crystallizing at 170 deg.C for 48h, filtering, washing the product with deionized water for 3 times, and drying at 90 deg.C for 24h to obtain ZSM-5 molecular sieve labeled L2.
Example 3
Will measure a certain amountAluminium sulphateAdding the mixture into deionized water, stirring uniformly, sequentially adding NaOH and silica sol, stirring for 30min, adding seed crystal ZSM-11, and stirring for 2h, wherein the mass fraction of the seed crystal is 8 wt%, so as to obtain mixed gel, and the molar ratio of substances in the mixed gel is SiO2/Al2O3＝40，SiO2/NaO2＝8，SiO2/H2O is 0.04; crystallizing at 180 deg.C for 24h, filtering, washing the product with deionized water for 3 times, and drying at 100 deg.C for 24h to obtain ZSM-5 molecular sieve labeled L3.
Example 4
Will measure a certain amountAluminium sulphateAdding into deionized water, stirring, sequentially adding NaOH, 2Gas phase SiOStirring for 15min, adding seed crystal all-silica zeolite (Silicate-1) with mass fraction of seed crystal of 16 wt%, stirring for 3h to obtain mixed gel with molar ratio of substances in the mixed gel of SiO2/Al2O3＝40，SiO2/NaO2＝9，SiO2/H2O is 0.02; crystallizing at 170 deg.C for 24h, filtering, washing the product with deionized water for 3 times, and drying at 80 deg.C for 12h to obtain ZSM-5 molecular sieve labeled L4.
Example 5
Will measure a certain amountAluminium isopropoxideAdding the mixture into deionized water, stirring the mixture evenly, adding NaOH and silica sol in sequence, stirring the mixture for 30min, then adding crystal seed NaY, and stirring the mixture for 2h, wherein the mass fraction of the crystal seed is 32 wt%, so as to obtain mixed gel, and the molar ratio of substances in the mixed gel is SiO2/Al2O3＝40，SiO2/NaO2＝10，SiO2/H2O is 0.03; crystallizing at 180 deg.C for 24h, filtering, washing the product with deionized water for 3 times, and drying at 80 deg.C for 24h to obtain ZSM-5 molecular sieve labeled L5.
Example 6
Will measure a certain amountAluminium isopropoxideAdding into deionized water, stirring, sequentially adding NaOH, 2Gas phase SiOStirring for 15min, adding seed crystal ZSM-11 with mass fraction of 16% wt, stirring for 3h to obtain mixed gel with molar ratio of each substance in the mixed gel being SiO2/Al2O3＝50，SiO2/NaO2＝12，SiO2/H2O is 0.04; crystallizing at 180 deg.C for 24h, filtering, washing the product with deionized water for 3 times, and drying at 90 deg.C for 24h to obtain ZSM-5 molecular sieve labeled L6.
Example 7
Adding a certain amount of sodium metaaluminate into deionized water, stirring uniformly, sequentially adding NaOH and silica sol, stirring for 15min, then adding crystal seed full-silica zeolite (Silicate-1), stirring for 2h, wherein the mass fraction of the crystal seed is 4% wt, obtaining mixed gel, and the molar ratio of each substance in the mixed gel is SiO2/Al2O3＝50，SiO2/NaO2＝6，SiO2/H2O is 0.02; crystallizing at 170 deg.C for 24h, washing the filtered product with deionized water for 3-5 times, and drying at 100 deg.C for 12h to obtain ZSM-5 molecular sieve labeled as L7.
Example 8
Adding a certain amount of sodium metaaluminate into deionized water, stirring uniformly, sequentially adding NaOH and silica sol, stirring for 15min, then adding crystal seed full-silica zeolite (Silicate-1), stirring for 2h, wherein the mass fraction of the crystal seed is 4% wt, obtaining mixed gel, and the molar ratio of each substance in the mixed gel is SiO2/Al2O3＝60，SiO2/NaO2＝6，SiO2/H2O is 0.02; crystallizing at 170 deg.C for 24h, washing the filtered product with deionized water for 3-5 times, and drying at 100 deg.C for 12h to obtain ZSM-5 molecular sieve labeled as L8.
Example 9
Adding a certain amount of sodium metaaluminate into deionized water, stirring uniformly, sequentially adding NaOH and silica sol, stirring for 15min, then adding crystal seed full-silica zeolite (Silicate-1), stirring for 2h, wherein the mass fraction of the crystal seed is 8% wt, obtaining mixed gel, and the molar ratio of each substance in the mixed gel is SiO2/Al2O3＝40，SiO2/NaO2＝8，SiO2/H2O is 0.02; crystallizing at 170 deg.C for 24h, washing the filtered product with deionized water for 3-5 times, and drying at 100 deg.C for 12h to obtain ZSM-5 molecular sieve labeled as L9.
Example 10
Adding a certain amount of sodium metaaluminate into deionized water, stirring uniformly, sequentially adding NaOH and silica sol, stirring for 15min, then adding crystal seed full-silica zeolite (Silicate-1), stirring for 2h, wherein the mass fraction of the crystal seed is 16% wt, obtaining mixed gel, and the molar ratio of each substance in the mixed gel is SiO2/Al2O3＝40，SiO2/NaO2＝6，SiO2/H2O is 0.03; crystallizing at 170 deg.C for 24h, washing the filtered product with deionized water for 3-5 times, and drying at 100 deg.C for 12h to obtain ZSM-5 molecular sieve labeled as L10.
The molecular sieves obtained in examples 1-10 were characterized and the specific surface areas, pore volumes, and ammonia nitrogen and VOC removal rates are shown in Table 1.
TABLE 1
As can be seen from Table 1, the ammonia nitrogen removal rate of examples 1 to 10 is substantially between 80% and 95%, the VOC removal rate is between 80% and 90%, and the adsorption effect on ammonia nitrogen and VOC is strong. Examples 1 to 6, mainly comparing the influences of silicon source and aluminum source, seed crystal type and synthesis parameters on the specific surface area and pore volume of the ZSM-5 molecular sieve, the results show that the factors have no influence on the ammonia nitrogen and VOC removal rate. Comparing examples 1, 7 and 8, it is found that the ammonia nitrogen adsorption effect is the best when the silica alumina ratio is 40, because the ion exchange capacity is large, more ammonium ions can be adsorbed. As can be seen from the results in table 1, example 9 is the best example of the present invention, with the best ammonia nitrogen and VOC removal.
Claims (8)
1. The method for synthesizing the ZSM-5 adsorbent by the aid of the seed crystals is characterized by comprising the following steps of:
adding an aluminum source into deionized water, uniformly stirring, sequentially adding NaOH and a silicon source, and stirring for 15-30 min;
adding the seeds A and stirring for 2-3h to obtain mixed gel; heating to 170-180 ℃ for crystallization for 24-48 h;
after filtering, washing with deionized water, and drying to obtain the ZSM-5 molecular sieve;
the seed A is one of all-silicon zeolite (Silicate-1), Y-type zeolite and ZSM-11.
2. The method for seed crystal assisted synthesis of ZSM-5 adsorbent as claimed in claim 1, wherein the full silicalite has a particle size of 100-300 nm; the Y-type zeolite SiO has the Si/Al ratio2/Al2O3Is 3-6.
3. The seed assisted synthesis of ZSM-5 adsorbent as claimed in claim 1, wherein the aluminum source is one of aluminum sulfate, sodium metaaluminate and aluminum isopropoxide.
4. The seed-assisted synthesis of ZSM-5 adsorbent as claimed in claim 1, wherein the source of silicon is one of fumed silica and liquid silica sol.
5. The seed assisted synthesis of ZSM-5 adsorbent as claimed in claim 1, wherein NaOH is added to adjust the pH to 9-12.
6. The seed-assisted synthesis of ZSM-5 adsorbent as claimed in claim 1, wherein the SiO in the seed a2Mass accounts for SiO in the mixed gel2The mass ratio is 4-32 wt%.
7. The seed-assisted synthesis of ZSM-5 adsorbent as claimed in claim 1, wherein the molar ratio of the materials in the mixed gel is SiO2/Al2O3＝40-100，SiO2/NaO2＝1.5-15，SiO2/H2O＝0.02-0.04。
8. The seed assisted synthesis ZSM-5 adsorbent of claim 1, wherein the drying conditions are drying at 80-100 ℃ for 12-24 hours.
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