CN110668465A - MeAPSO-44 molecular sieve and preparation method thereof - Google Patents
MeAPSO-44 molecular sieve and preparation method thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 81
- 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 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 51
- 235000009566 rice Nutrition 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000002425 crystallisation Methods 0.000 claims abstract description 34
- 230000008025 crystallization Effects 0.000 claims abstract description 33
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- 239000010703 silicon Substances 0.000 claims abstract description 29
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
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- 239000002244 precipitate Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
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- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 2
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- 229910052906 cristobalite Inorganic materials 0.000 claims 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- 229910052682 stishovite Inorganic materials 0.000 claims 2
- 229910052905 tridymite Inorganic materials 0.000 claims 2
- 239000010903 husk Substances 0.000 abstract description 22
- 229910052742 iron Inorganic materials 0.000 abstract description 16
- 239000010936 titanium Substances 0.000 abstract description 15
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- 239000002994 raw material Substances 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 13
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- 239000002184 metal Substances 0.000 abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 239000012071 phase Substances 0.000 abstract description 6
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- 239000002149 hierarchical pore Substances 0.000 abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000013589 supplement Substances 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 239000011148 porous material Substances 0.000 description 21
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
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- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
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- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 2
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- 101100456282 Caenorhabditis elegans mcm-4 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- 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
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a preparation method of a MeAPSO-44 molecular sieve, which comprises the following steps: pretreatment, solid phase or hydrothermal synthesis, crystallization and post-treatment, wherein the natural bauxite contains silicon element, iron element and titanium element. The technical scheme takes cheap and easily-obtained natural alumina as a raw material, the added rice husk can be used as a silicon source supplement and a hard template agent, and can promote metal heteroatoms to enter a molecular sieve framework, resources such as aluminum, silicon, iron, titanium and the like in the natural alumina are effectively utilized, and the alumina is prepared into microporous-mesoporous composite hierarchical pores with specific surface area of 303-421m and with microporous-mesoporous composite hierarchical pores by a solid phase method in one step2(ii) MeAPSO-44 molecular sieves (Me ═ Fe, Ti) per g. Oxides in natural bauxite and rice hulls are basically amorphous substances, which is beneficial to the synthesis of molecular sieves; and the bonding phenomenon can not occur in the process of adding phosphoric acid, which is beneficial to the uniformity of the solid-phase synthesis material. The MeAPSO-44 molecular sieve and the rice husk with complete crystal phase and large specific surface area can be synthesized by using natural raw materialsPromoting the metal heteroatom to enter the molecular sieve framework.
Description
Technical Field
The invention relates to the field of mineral resource processing, in particular to a MeAPSO-44 molecular sieve and a preparation method thereof.
Background
In 1998, U.S. Pat. No. 9785098 discloses a process for the preparation of SAPO-44, or substantially pure SAPO-44, comprising silicoaluminophosphates, and the use of the prepared molecular sieves for oxidative conversion to olefins. SAPO-44 belongs to a silicoaluminophosphate molecular sieve, has similar physicochemical properties to SAPO-34, and has chabazite-type pores and three-dimensional cross channels formed by four-membered rings, double six-membered rings and eight-membered rings. The molecular sieve which embeds metal atoms into SAPO-44 and is named MeAPSO-44 has the pore opening and the self-acidity, and is changed due to the entrance of metal ions, thereby showing new structure and performance.
The specific synthesis method of the MeAPSO-44 molecular sieve is similar to the synthesis method of the SAPO-44, and comprises a traditional hydrothermal synthesis method, a dry gel method, a microwave radiation crystallization method, a solid phase method and the like. The raw materials for synthesizing SAPO molecular sieves reported in the current literature mainly fall into three main categories: chemical raw materials, natural aluminosilicate minerals with low price and wide sources and solid wastes. The adoption of the latter two natural aluminosilicate minerals and the solid waste can not only effectively reduce the synthesis cost, but also make the non-renewable mineral resources be utilized with high value, and make the solid waste be changed into valuables.
The Rui et al prepared SAPO-44 molecular sieve catalyst with transition metal load has great development potential in the automobile exhaust denitration technology. Metal-supported SAPO molecular sieves have been extensively studied, Sun et Al have synthesized four different types of heteroatomic aluminum phosphate molecular sieves (MeSAPO-5, -11, -34, -44, Me ═ Fe, Ti) using traditional hydrothermal methods with bauxite to provide a single Al, Si and Me that can be used as catalysts to efficiently convert carbohydrates to HMF, and the MeSAPO is regenerated after maintaining good catalytic performance. In recent years, people pay attention to the research of synthesizing molecular sieves by using wastes, and the agricultural waste rice hulls are a renewable resource which is cheap and easy to collect in China. Most of rice hulls are incinerated or directly discarded at the present stage, so that the comprehensive utilization rate is low, and the resource is greatly wasted. In the field of catalysis, rice hull silicon serving as a silicon source is used for synthesis of microporous and mesoporous molecular sieves, and a large number of documents report that the rice hulls are subjected to activation treatment such as calcination and the like, and a hydrothermal method is adopted to prepare the P-type molecular sieve. The method comprises the steps of taking rice hulls as raw materials, extracting silicon in the rice hulls through high-temperature alkali activation to serve as a silicon source for molecular sieve synthesis, and synthesizing the Y-type molecular sieve with the hierarchical pore structure by using carbon in carbonized rice hulls as a mesoporous template. The rice hulls are acidified and calcined to obtain amorphous silica which can be used for preparing MCM-4 l.
The reports of using natural minerals to prepare SAPO molecular sieves require complex pretreatment of raw mineral materials to activate components such as aluminum, silicon, iron and the like in the minerals, and some of the raw mineral materials also need to be added with inorganic mineralizers such as HF and the like with extremely strong corrosivity. Before being used as a silicon source for synthesizing the molecular sieve, rice hull silicon also needs to be subjected to activation treatment in forms of ashing, acidification, high-temperature alkalization and the like. And the crystallization time of the hydrothermal method is long, so that environmental pollution is easily caused in the crystallization or roasting process of the molecular sieve, or a large amount of waste liquid is generated, or toxic gases such as nitric oxide and the like are released.
Disclosure of Invention
Therefore, a new method for providing a MeAPSO-44(Me ═ Fe, Ti) molecular sieve with high raw material utilization rate, safety, environmental protection, economy and high efficiency is needed. In order to achieve the above object, the inventors provide a preparation method of a MeAPSO-44 molecular sieve, comprising the steps of:
pretreatment: removing impurities from natural bauxite, and performing ball milling to obtain pretreated powdered bauxite;
solid-phase synthesis: mixing bauxite with deionized water, stirring continuously, and adding phosphorus source (P) in sequence during stirring2O5) Supplementing silicon Source (SiO)2) Mixing the template agent and the mixture uniformly, and stirring to obtain a paste mixture; the templating agent comprises Cyclohexylamine (CHA);
and (3) crystallization: crystallizing the paste mixture at 160-220 ℃ until MeAPSO-44 crystals are formed, and centrifugally washing the crystallized material until the pH value of a washing liquid is 6.3-6.5 to obtain a precipitate;
and (3) post-treatment: drying and calcining the precipitate to obtain a MeAPSO-44 molecular sieve;
the natural bauxite contains aluminum element, silicon element, iron element and titanium element, and the supplementary silicon source comprises rice husk and silica sol.
Further, the active substances contained in the alumina and the mass percentage content thereof are as follows:
Al2O3：68-73％；SiO2：8-13％；Fe2O3：16-18％；TiO2：1.6-1.8％。
further, in the pretreatment step, the ball milling speed is 500r/min, and the ball milling time is 2 h.
Further, the solid phase synthesis step is to synthesize Al in the material2O3：P2O5：SiO2：CHA：H2The molar ratio of O is 80-100: 90-110: 20-80: 180-200: 2000-4000.
Further, PEG20000 and Al are added in the solid phase synthesis step2O3The molar ratio of PEG to 20000 is 90000-110000: 4-6.
Further, in the solid phase synthesis step, the weight ratio of the pretreated bauxite to the rice hull is 1400-1600: 900-1100.
Further, in the crystallization step, the crystallization time is 2-96 h.
Further, the post-treatment step is to dry the precipitate in an oven at 110 ℃ for 4h and calcine the precipitate in a muffle furnace at 550 ℃ for 4h in a hollow atmosphere.
The inventor also provides a MeAPSO-44 molecular sieve, wherein the MeAPSO-44 molecular sieve is prepared by adopting any one of the preparation methods.
Different from the prior art, the technical scheme takes cheap and easily-obtained natural bauxite and rice husk as raw materials, effectively utilizes silicon in the rice husk and resources such as aluminum, silicon, iron, titanium and the like in the natural bauxite, and prepares the composite hierarchical pore with micropore-mesopore and the like and the specific surface area of 285-398m and 398m by one step through a solid phase method2The MeAPSO-44 molecular sieve (Me ═ Fe, Ti) has high utilization rate of raw material, low cost, high yield of product and technological processSimple and no waste liquid and waste residue. Oxides in natural bauxite and rice hulls are basically amorphous substances, which is beneficial to the synthesis of molecular sieves; and the bonding phenomenon can not occur in the process of adding phosphoric acid, which is beneficial to the uniformity of the solid-phase synthesis material. The MeAPSO-44 molecular sieve with complete crystal phase and large specific surface area can be synthesized by utilizing natural raw materials, and the rice hulls have the promotion effect on metal heteroatoms entering a molecular sieve framework. The MeAPSO-44(Me ═ Fe and Ti) molecular sieve synthesized by the method has multi-stage pores, large specific surface area and proper pore diameter, so that the molecular sieve can be used for preparing 5-hydroxymethylfurfural and N through denitration reaction and fructose dehydration in tail gas treatment2/CH4The separation, the conversion of heavy oil into light oil, the degradation of dye and the like have good application prospects.
Drawings
FIG. 1 is an XRD pattern for examples 1-8;
FIG. 2 is an XRD pattern for examples 9-17;
FIG. 3 is an SEM image of the MeAPSO-44 molecular sieve synthesized in example 1;
FIG. 4 is the isothermal adsorption-desorption curve and the pore size distribution diagram of the MeAPSO-44 molecular sieve nitrogen physical adsorption synthesized in example 1;
FIG. 5 is the isothermal adsorption-desorption curve and the pore size distribution diagram of the MeAPSO-44 molecular sieve nitrogen physical adsorption synthesized in example 4;
FIG. 6 is the isothermal adsorption-desorption curve and the pore size distribution diagram of the MeAPSO-44 molecular sieve nitrogen physical adsorption synthesized in example 5;
FIG. 7 is the isothermal adsorption-desorption curve and pore size distribution diagram of nitrogen physisorption of MeAPSO-44 molecular sieve synthesized in example 6;
FIG. 8 is a graph showing the isothermal adsorption and desorption curves and the pore size distribution of nitrogen physisorption of the MeAPSO-44 molecular sieve synthesized in example 7;
FIG. 9 is the isothermal adsorption-desorption curve and pore size distribution diagram of nitrogen physisorption of the MeAPSO-44 molecular sieve synthesized in example 8;
figure 10 is a graph of the ultraviolet diffuse reflectance spectrum of the MeAPSO-44 molecular sieve synthesized in example 1.
Detailed Description
To explain technical contents, structural features, and objects and effects of the technical solutions in detail, the following detailed description is given with reference to the accompanying drawings in conjunction with the embodiments.
In this embodiment: analyzing the element composition of the sample of the bauxite and the rice hull by a solid X-ray fluorescence spectrometer; in this embodiment, the alumina mainly comprises the following components by mass percent: al (Al)2O3：SiO2：Fe2O3：TiO269.51%: 12.18%: 17.1%: 1.71 percent; the main chemical component of the rice hull is SiO2: 10.1 wt%, hemicellulose 29.6%, cellulose 31.1%, lignin 16.0%, and small amount of other trace elements.
Example 1 preparation of MeAPSO-44 molecular sieves (Me ═ Fe, Ti)
Pretreatment: removing impurities from bauxite, and ball-milling in a ball mill with the rotation speed of 500r/min for 2h to obtain powdery bauxite;
solid-phase synthesis: weighing 1.5000g of pretreated powdered alumina in a polytetrafluoroethylene lining, and adding H3PO4(85 wt.%) is P2O5Source, silica Sol (SiO)230 wt%, alkaline), rice hulls; wherein the weight ratio of the bauxite to the rice husk is 1.5: 1.0. according to the raw material mol ratio of Al2O3：P2O5：SiO2：CHA：H2And (3) feeding the materials according to the sequence of deionized water, a phosphorus source, a silicon supplementing source and a template agent, wherein the silicon supplementing source (silica sol is added firstly and then rice husk is added), and performing magnetic stirring for 30min when one raw material is added. After the materials are added, magnetically stirring for 2 hours at normal temperature to obtain a uniform pasty mixture; and (3) crystallization: placing the paste mixture into a poly-tetraethylene reaction kettle added with 1.1084g of deionized water, and then placing the mixture into a stainless steel outer kettle; crystallizing at 200 deg.C for 24 hr. After crystallization, centrifugally washing the product in the liner until the pH value is 6.4-6.7 to obtain a precipitate;
and (3) post-treatment: drying the precipitate in a drying oven at 110 ℃ for 4h to obtain molecular sieve raw powder; and (3) roasting the molecular sieve raw powder in a muffle furnace at 550 ℃ for 4h to remove the template agent to obtain the MeAPSO-44 molecular sieve (Me ═ Fe, Ti).
Commonly used for synthesizing SAPO molecular sieves are morpholine, tetraethylammonium hydroxide, triethylamine, cyclohexylamine and the like, and Cyclohexylamine (CHA) with relatively low price is selected as a template agent in the embodiment. The rice hulls contain cellulose and have the function of expanding pores in the experiment, and in the isothermal adsorption and desorption curve and the pore size distribution diagram of nitrogen physical adsorption shown in figures 4-9, the specific surface area of the molecular sieve added with the rice hulls is obviously increased, the pore size is enlarged, and the function of a hard template agent is realized.
Example 2
The difference between example 2 and example 1 is: in the solid phase synthesis process of example 1, 1.5000g of pretreated powdered alumina was weighed; and crystallizing for 24 hours. EXAMPLE 8 solid phase Synthesis procedure, 5.0000g of pretreated powdered alumina was weighed out and crystallized for 16 h.
Example 3
The difference between example 3 and example 1 is: example 1 during solid phase synthesis, the weight ratio of alumina to rice husk was 1.5:1.0, feeding; example 3 during the solid phase synthesis, the weight ratio of the alumina to the rice husk is 1.5: 0.45 for feeding.
Example 4
The difference between example 4 and example 1 is: example 1 during solid phase synthesis, the weight ratio of alumina to rice husk was 1.5: 1.0; example 4 during solid phase synthesis, the weight ratio of alumina to rice husk was 1.5: 1.85, the rice hulls are fed, and the silicon content of the rice hulls is enough to supplement a silicon source at the moment, and silica sol is not needed to be added.
Example 5:
the difference between example 5 and example 1 is: the silicon source supplement of example 5 is silica sol (30 wt%, alkaline), no rice husk is added, both PEG and rice husk have pore-enlarging effect, PEG20000 is added, PEG20000 is the last material added, Al2O3The molar ratio to PEG20000 is 90000: 5.
Example 6
Example 6 differs from example 1 in that the ball-milled alumina was calcined at 550 ℃ for 4 hours and solid phase synthesis was carried out using calcined alumina as the starting material.
Example 7
Example 7 differs from example 1 in that the supplemental silicon source of the comparative example was silica sol (30 wt%, basic) with no rice hull component.
Example 8
Example 8 differs from example 1 in that the solid phase synthesis method of comparative example is hydrothermal synthesis, and the molar ratio of the raw materials is Al2O3：P2O5：SiO2：CHA：H2And (3) feeding the materials according to the ratio of 1.0:0.9:0.6:2.0: 60.
Example 9
Example 9 is different from example 1 in that crystallization conditions were changed from 24 hours at 200 ℃ to 2 hours at 200 ℃.
Example 10
The difference between example 10 and example 1 is that in the crystallization, the crystallization condition was changed from 24 hours at 200 ℃ to 4 hours at 200 ℃.
Example 11
Example 11 differs from example 1 in that: in the crystallization, the crystallization condition is changed from 24 hours at 200 ℃ to 8 hours at 200 ℃.
Example 12
Example 12 differs from example 1 in that: in the crystallization, the crystallization condition is changed from 24 hours at 200 ℃ to 16 hours at 200 ℃.
Example 13
Example 13 differs from example 1 in that: in the crystallization, the crystallization condition is changed from 24 hours at 200 ℃ to 48 hours at 200 ℃.
Example 14
Example 14 differs from example 1 in that: in the crystallization, the crystallization condition is changed from 24 hours at 200 ℃ to 96 hours at 200 ℃.
Example 15
The difference between example 15 and example 1 is: in the crystallization, the crystallization condition is changed from 24 hours at 200 ℃ to 24 hours at 220 ℃.
Example 16
Example 16 differs from example 1 in that: in the crystallization, the crystallization condition is changed from 24 hours at 200 ℃ to 24 hours at 180 ℃.
Example 17
Example 17 differs from example 1 in that: in the crystallization, the crystallization condition is changed from 24 hours at 200 ℃ to 24 hours at 160 ℃.
Performance evaluation:
1. mass spectrometry was performed on MeAPSO-44 molecular sieves prepared in examples 1-8 (Me ═ Fe, Ti):
as can be seen from XRD patterns of examples 1 to 8 in FIG. 1, the MeAPSO-44 molecular sieves (Me ═ Fe, Ti) prepared by the method all have characteristic peaks of SAPO-44(PDF:47-0630) at 2 theta ═ 9.5, 20.7, 30.8 and 31.2, and meanwhile, no TiO appears in the XRD pattern2And Fe2O3The diffraction peak of (A) indicates that the metal enters the framework of the SAPO-44 molecular sieve. Fig. 1 shows that the solid-phase synthesis method is compared with the traditional hydrothermal synthesis method, the solid-phase synthesis method has complete crystalline phase and good crystallinity, the preparation method can also enlarge the raw material dosage, has no pollution and high utilization rate, and the crystallinity of the synthetic sample added with rice husks which are not ashed and are used as partial silicon sources is increased, which indicates that the rice husks have the function of promoting heteroatom iron titanium to enter a molecular sieve framework.
Fig. 2, examples 11-17XRD patterns change the crystallization conditions of the sample synthesis, and it can be seen that the crystallization temperature is too low, e.g. 160 ℃, the crystallization time is too short, e.g. 2h, the crystalline phase is not complete, and the complete crystalline phase is obtained at 4h of crystallization, which has significantly reduced the synthesis time compared to the hydrothermal synthesis method. Varying the amount of rice hull added also has an effect on crystallinity, which is best in the example when the weight ratio of alumina to rice hull is 1.5.
2. SEM image:
FIG. 3 is an SEM image of the MeAPSO-44 molecular sieve synthesized in example 1, from which we can see that the morphology of the molecular sieve is cubic, consistent with that reported in the literature, thus demonstrating that the process synthesizes SAPO-44 molecular sieve; it can also be seen from the figure that the particle diameter of the synthesized molecular sieve is about 5 μm.
3、N2-adsorption/desorption characterisation:
and (3) testing conditions are as follows:
the molecular sieve nitrogen physical adsorption performance characterization is carried out by adopting a MacaASAP 2460 type specific surface and porosity analyzer. Weighing about 100mg of sample, and carrying out vacuum pretreatment for 5h at 200 ℃; with N2For the adsorbate, the adsorption-desorption curve was determined at liquid nitrogen temperature (-196 ℃). Absorption according to absorption and desorption curveThe specific surface area of a relevant sample is calculated by BET (Berrett-Emmett-Teller) in a branch, and the pore volume and the pore diameter are calculated by a Berret-Joyner-Halenda (BJH) method according to a desorption branch of an absorption and desorption curve.
| Examples | Specific surface area/(m)2/g) | Pore volume/(cm)3/g) | Pore size/nm |
| Example 1 | 398.2 | 0.216 | 2.18 |
| Example 4 | 413 | 0.224 | 2.16 |
| Example 5 | 303.1 | 0.184 | 2.43 |
| Example 6 | 421.0 | 0.257 | 2.44 |
| Example 7 | 386.7 | 0.264 | 2.73 |
| Example 8 | 322.1 | 0.247 | 3.07 |
The difference between example 1 and example 4 is that rice husk is added as a part of supplementary silicon source in example 1, only rice husk is used as the supplementary silicon source in example 4, and the characterization result of XRD shows that the synthetic sample prepared from rice husk and silica sol together as the supplementary silicon source has better crystallinity, the weight ratio of alumina to rice husk is 1.5:1.0, and the result of nitrogen physical adsorption shows that the specific surface areas of the synthetic samples in example 1 and example 4 are not very different. Comparison of examples 1, 4 and 5 shows that rice hulls have a more pronounced pore-enlarging effect on MeAPSO-44 molecular sieves than PEG. Example 6 the molecular sieve is synthesized by using calcined alumina as a raw material, and the specific surface area of the synthesized sample is increased after the natural mineral is subjected to calcination treatment, but the specific surface area is not particularly remarkable, but the technical process of the synthesis process is increased. Example 7 only silica sol was used as a supplementary silicon source, no rice husk was added, the XRD results were compared, the crystallinity of the product synthesized from molecular sieve by adding a suitable amount of rice husk was relatively high, and the results of nitrogen physical adsorption again demonstrate the pore-enlarging effect of rice husk. Example 8 the specific surface area of the molecular sieve synthesized by the traditional hydrothermal synthesis method is smaller than that of the molecular sieve synthesized by the solid phase method in example 1. In conclusion, the rice hulls can promote metal heteroatoms to enter the molecular sieve and also play a role in reaming.
Therefore, we can conclude that: oxides in natural bauxite and rice hulls are basically amorphous substances, which is beneficial to the synthesis of molecular sieves; and the bonding phenomenon can not occur in the process of adding phosphoric acid, which is beneficial to the uniformity of the solid-phase synthesis material. The MeAPSO-44 molecular sieve with complete crystal phase and large specific surface area can be synthesized by utilizing natural raw materials, and the rice hulls have the promotion effect on metal heteroatoms entering a molecular sieve framework.
Fig. 4-9 are respectively the isothermal adsorption/desorption curves and the pore size distribution curves of the MeAPSO-44(Me ═ Fe, Ti) molecular sieves synthesized in examples 1, 4, 5, 6, 7, and 8 for nitrogen physisorption, from which we can know that all the molecular sieve adsorption/desorption curves synthesized by the method have hysteresis loops, and some of the hysteresis loops are less obvious, indicating that the number of mesopores is less; the isotherms are of type IV in the IUPAC classification, and the hysteresis loop is of type H4. The adsorption capacity rapidly increases in the lower relative pressure region, at a pressure p/p0The adsorption capacity in the range of 0.01-0.6 presents a platform, which is the characteristic of a microporous substance adsorption curve; when p/p is0>At 0.6, the adsorption capacity begins to increase and has a certain difference with the desorption curve, and the isothermal curve is p/p0>After 0.98, the molecular sieve shows an infinite growth trend, thereby indicating that a certain amount of mesopores exist in the synthesized MeAPSO-44 molecular sieve crystal. The molecular sieve synthesized by the method is of a multi-stage pore structure through nitrogen adsorption and desorption characterization.
4. Diffuse reflection of ultraviolet light
And (3) testing conditions are as follows: the solid powder sample was tested using a Perkinelmer Lambda750 model UV-visible near-IR spectrophotometer, using a barium sulfate tablet press.
FIG. 10 is a graph of the UV diffuse reflectance spectrum of example 1, which shows that there is a sharp absorption in the range of 200-280nm, and no other absorption peak is observed in the visible light region (after 400 nm), indicating that the heteroatoms Fe and Ti are located at the framework position of the molecular sieve. Further proves that the doped metal heteroatoms Fe and Ti enter the molecular sieve framework.
The MeAPSO-44(Me ═ Fe and Ti) molecular sieve synthesized by the method has multi-stage pores, large specific surface area and proper pore diameter, so that the molecular sieve can be used for preparing 5-hydroxymethylfurfural and N through denitration reaction and fructose dehydration in tail gas treatment2/CH4The separation, the conversion of heavy oil into light oil, the degradation of dye and the like have good application prospects.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the phrases "comprising … …" or "comprising … …" does not exclude the presence of additional elements in a process, method, article, or terminal that comprises the element. Further, herein, "greater than," "less than," "more than," and the like are understood to exclude the present numbers; the terms "above", "below", "within" and the like are to be understood as including the number.
It should be noted that, although the above embodiments have been described herein, the invention is not limited thereto. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein, or by using equivalent structures or equivalent processes performed in the content of the present specification and the attached drawings, which are included in the scope of the present invention.
Claims (9)
1. A preparation method of a MeAPSO-44 molecular sieve is characterized by comprising the following steps:
pretreatment: removing impurities from natural bauxite, and performing ball milling to obtain powdery bauxite;
solid-phase synthesis: sequentially adding deionized water, a phosphorus source, a supplementary silicon source and a template agent into the pretreated bauxite, and uniformly mixing and stirring to obtain a paste mixture, wherein the template agent comprises cyclohexylamine;
and (3) crystallization: crystallizing the paste mixture at 160-220 ℃ until MeAPSO-44 crystals are formed, and centrifugally washing the crystallized material until the pH value of a washing liquid is 6.4-6.7 to obtain a precipitate;
and (3) post-treatment: drying and calcining the precipitate to obtain a MeAPSO-44 molecular sieve;
the natural bauxite contains aluminum element, silicon element, iron element and titanium element
The supplementary silicon source comprises rice hulls and silica sol.
2. The preparation method of claim 1, wherein the alumina comprises the following active substances in percentage by mass:
Al2O3：68-73％；SiO2：8-13％；Fe2O3：16-18％；TiO2：1.6-1.8％。
3. the preparation method according to claim 1, wherein in the pretreatment step, the ball milling is performed for 2 hours in a ball mill rotating at 500 revolutions.
4. The method according to claim 1, wherein in the step of solid-phase synthesis, Al is contained in the synthesis material2O3：P2O5：SiO2：CHA：H2The molar ratio of O is 8-10: 9-11: 2-8: 18-20: 200-400.
5. The method as claimed in claim 1, wherein the solid phase synthesis step comprises the following steps of mixing the pretreated bauxite and the rice hull in a weight ratio of 1400-1600: 900-1100.
6. The method according to claim 1, wherein the solid phase synthesis step further comprises the addition of PEG20000, Al2O3The molar ratio of PEG to 20000 is 90000-110000: 4-6.
7. The method as claimed in claim 1, wherein the crystallization step has a crystallization time of 2-96h and a crystallization temperature of 160-220 ℃.
8. The preparation method according to claim 1, wherein the post-treatment step comprises drying the precipitate in an oven at 110 ℃ for 4 hours and calcining the precipitate in a muffle furnace at 550 ℃ in a hollow atmosphere for 4 hours.
9. A MeAPSO-44 molecular sieve, characterized in that said MeAPSO-44 molecular sieve has been prepared by the preparation method according to any one of claims 1 to 8.
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