CN110902692A - Synthetic method capable of improving wettability of ZSM-5 zeolite molecular sieve - Google Patents
Synthetic method capable of improving wettability of ZSM-5 zeolite molecular sieve Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 93
- 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 93
- 239000010457 zeolite Substances 0.000 title claims abstract description 71
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 67
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000010189 synthetic method Methods 0.000 title claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 80
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 80
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 48
- 239000003513 alkali Substances 0.000 claims abstract description 36
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000012265 solid product Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 38
- 239000000377 silicon dioxide Substances 0.000 claims description 34
- 229910052593 corundum Inorganic materials 0.000 claims description 30
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 30
- 229910052681 coesite Inorganic materials 0.000 claims description 29
- 229910052906 cristobalite Inorganic materials 0.000 claims description 29
- 229910052682 stishovite Inorganic materials 0.000 claims description 29
- 229910052905 tridymite Inorganic materials 0.000 claims description 29
- 239000011734 sodium Substances 0.000 claims description 25
- 238000001308 synthesis method Methods 0.000 claims description 25
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 23
- 229910000077 silane Inorganic materials 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 150000001282 organosilanes Chemical class 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 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 11
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 11
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 9
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical group CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims description 4
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 3
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 3
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 claims description 3
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 claims description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 35
- 238000010438 heat treatment Methods 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 238000009736 wetting Methods 0.000 abstract description 2
- 229910052573 porcelain Inorganic materials 0.000 description 26
- 125000000962 organic group Chemical group 0.000 description 14
- 238000001354 calcination Methods 0.000 description 11
- 230000001276 controlling effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 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 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 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
- C01B39/02—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
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a synthetic method capable of improving wettability of a zeolite molecular sieve, which comprises the following steps: grinding and mixing the template agent or the seed crystal and a solid raw material, namely a silicon source, an alkali source and/or an aluminum source; putting the ground mixture into a reaction kettle, and crystallizing for 24-44 hours at the temperature of 160-190 ℃; taking out the crystallized solid product and drying; and roasting the obtained molecular sieve to obtain the ZSM-5 molecular sieve material with the required wetting property. The roasting process is temperature programming, and the roasting conditions are as follows: the temperature is 400-800 ℃, the heating rate is 1-10 ℃/min, and the roasting time is 1-24 h. The target control of the wettability of the molecular sieve is realized by controlling the roasting condition, the adsorption and catalysis performances of the molecular sieve on a substrate can be changed, the controllable synthesis of ZSM-5 is realized, and the method has strong application value.
Description
Technical Field
The invention relates to the field of preparation of ZSM-5 zeolite molecular sieves, in particular to a synthesis method capable of improving the wettability of a ZSM-5 zeolite molecular sieve, which can improve the wettability in the synthesis process of a solid-phase molecular sieve.
Background
The zeolite molecular sieve is an aluminosilicate mineral of a clean bench and has a spatial network structure formed by staggered arrangement of silicon-oxygen tetrahedra and aluminum-oxygen tetrahedra. The structural characteristics make the zeolite molecular sieve have three characteristics of selective adsorption separation, ion exchange and catalysis. At present, zeolite has been widely used in the fields of petrochemical industry, coal conversion, fine chemical industry, etc., and zeolite has become the technical core of these fields and brings great economic benefits. Advances in zeolite synthesis technology are also closely related to industrial development. The exploration of a new synthesis route of the molecular sieve and the regulation and control of the performance are one of the hot points concerned by researchers.
Molecular sieves were first synthesized by hydrothermal methods, and industrially important molecular sieves such as ZSM-5 and Beta were synthesized by these methods. Although water is one of the greenest solvents, the use of a large amount of water still causes a series of problems in actual industrial production. First, water occupies a large amount of reactor space, the autogenous pressure of water creates a high pressure hazard, the treatment of large amounts of alkali-containing wastewater, and the separation of zeolite products from water all increase the cost of zeolite production. In addition, hydrothermal synthesis in the presence of alkali liquor can also cause the defects that the template agent, a silicon source and an aluminum source are dissolved in water, the utilization rate of raw materials is low and the like. In recent years, the solvent-free solid phase synthesis of zeolitic molecular sieves has become an emerging technology that has attracted considerable attention, such as the synthesis of zeolites such as ZSM-5, Beta and Y. The route solves the problems of waste water and raw material utilization rate and the like in the traditional hydrothermal synthesis process, and reduces the production cost.
However, in different catalytic reactions, substrate molecules have different adsorption and desorption properties in molecular sieve pore channels, so that the mass transfer efficiency of the substrate is greatly influenced, and further the problems of low reaction activity, poor selectivity, carbon deposition of a catalyst and the like are caused. The mass transfer efficiency of the substrate molecules is closely related to the wettability of the catalyst, namely the hydrophilicity and hydrophobicity of the catalyst. It is very difficult to control the wettability of the zeolite in the synthesis process according to application requirements.
The traditional method is used for regulating and controlling the wettability of zeolite materials by controlling the silica-alumina ratio of a zeolite framework, high-silica zeolite often shows hydrophobic property, and low-silica zeolite shows hydrophilic property. However, the control range of the wettability of the zeolite through the silicon-aluminum ratio is limited, and the acidity of the zeolite is influenced by the change of the silicon-aluminum ratio, so that the method has limitation. For example: hydrophobic (high silica to alumina ratio required) zeolites with high acid density (low silica to alumina ratio required) are not possible to obtain by this method. Therefore, it is particularly important to develop new methods for controlling the wettability of zeolites.
In previous patent applications, we have found that the hydrophobicity of zeolitic materials can be increased by using organosilanes in the zeolite synthesis to introduce organic groups into the zeolite framework without changing the silica to alumina ratio. After high-temperature roasting, the organic group is converted into silicon hydroxyl, so that the hydrophilicity of the material can be improved. However, the method is mostly suitable for a template-free synthesis system without roasting, and the wide application of the method is limited.
In a synthesis system containing a template or a seed crystal, organic groups are often removed at the same time as the template or the seed crystal is removed by calcination. It is very challenging to remove the templating agent or seed while selectively retaining or removing the organic groups therein.
Disclosure of Invention
In view of the above problems, the present invention provides a synthesis method capable of improving the wettability of a molecular sieve of a ZSM-5 zeolite, which can remove a template or a seed while selectively retaining or removing an organic group therein.
Therefore, the invention provides a synthesis method capable of improving the wettability of a ZSM-5 zeolite molecular sieve, which comprises the following steps:
s1, grinding and mixing the structure directing agent and the solid raw material to obtain a ground mixture;
s2, placing the ground mixture into a reaction kettle, and carrying out crystallization reaction for 24-44 hours at 160-190 ℃ to obtain a crystallized solid product;
s3, drying and roasting the crystallized solid product to obtain the required zeolite molecular sieve,
wherein the structure directing agent is selected from at least one of a templating agent and a seed; the solid raw materials are a silicon source, an alkali source and an aluminum source; the roasting conditions are as follows: the roasting atmosphere is at least one of oxygen and nitrogen, the temperature is raised to 400-800 ℃ at the speed of 1-10 ℃/min, and the roasting time is 1-24 h.
The synthesis method capable of improving the wettability of the ZSM-5 zeolite molecular sieve is characterized in that the roasting atmosphere preferably consists of oxygen and nitrogen, wherein the volume content of the oxygen is preferably 1-100%.
In the synthesis method capable of improving the wettability of the ZSM-5 zeolite molecular sieve, in step S1, preferably, the structure directing agent is used as a template agent, and the silicon source is SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by Na2Calculated by O, the molar ratio of each component is SiO2:Al2O3:Na2O is 1: 0.004-0.03: 0.1-0.5: 0.1-0.3 of a template agent.
According to the synthesis method capable of improving the wettability of the ZSM-5 zeolite molecular sieve, in the step S1, the structure directing agent is preferably seed crystals, and the adding amount of the seed crystals is preferably 4-10% of the mass of a silicon source.
The synthesis method capable of improving the wettability of the ZSM-5 zeolite molecular sieve, disclosed by the invention, is characterized in that the silicon source is preferably composed of inorganic silicon and organic silicon prepared by hydrolyzing organic silane.
The synthetic method capable of improving the wettability of the ZSM-5 zeolite molecular sieve, disclosed by the invention, is characterized in that the organosilane is preferably one or more selected from dimethyl dimethoxysilane, methyl trimethoxysilane, diethyl diethoxysilane, propyl triethoxysilane, n-dodecyl trimethoxysilane, n-hexadecyl trimethoxysilane, phenyl trimethoxysilane and diphenyl dimethoxysilane.
The synthesis method capable of improving the wettability of the ZSM-5 zeolite molecular sieve, disclosed by the invention, is characterized in that the inorganic silicon is preferably selected from one or more of sodium silicate nonahydrate, solid silica gel and white carbon black.
The synthesis method capable of improving the wettability of the ZSM-5 zeolite molecular sieve is characterized in that preferably, the organic silicon accounts for 10-40% of the mass of the silicon source, and the inorganic silicon accounts for 60-90% of the mass of the silicon source.
The synthesis method capable of improving the wettability of the ZSM-5 zeolite molecular sieve, disclosed by the invention, is characterized in that the aluminum source is preferably selected from one or more of aluminum sulfate, sodium metaaluminate and nano alumina.
The synthesis method capable of improving the wettability of the ZSM-5 zeolite molecular sieve is characterized in that the template agent is preferably tetrapropylamine salt.
The synthesis method capable of improving the wettability of the ZSM-5 zeolite molecular sieve, disclosed by the invention, wherein the tetrapropylamine salt is preferably selected from one or more of tetrapropylammonium hydroxide, tetrapropylammonium bromide and tetrapropylammonium chloride.
The synthesis method capable of improving the wettability of the ZSM-5 zeolite molecular sieve is characterized in that the seed crystal is preferably ZSM-5 zeolite.
The synthesis method capable of improving the wettability of the ZSM-5 zeolite molecular sieve is characterized in that the alkali source is preferably sodium hydroxide.
The method of the invention aims at a synthesis system containing a template agent or a seed crystal, and organic groups are often removed while the template agent is roasted. However, the organic group in the ZSM-5 zeolite molecular sieve can control the wettability of the material, and the higher the content of the organic group, the stronger the hydrophobicity of the material, and the lower the content of the organic group, the higher the corresponding hydroxyl content, the stronger the hydrophilicity of the material, so if the template agent or the seed crystal is removed while a part of the organic group is selectively retained, the wettability of the material can be controlled.
The invention adjusts the silicon source from single type to inorganic silicon and organic silicon, and limits the roasting condition, to remove the template agent or crystal seed and selectively keep part of organic group, to burn the template agent and keep relative organic group, to adjust the molecular sieve wetting property in needed range. The method realizes the preparation of the high-performance ZSM-5 zeolite by a green synthetic route, and has strong application value.
The invention has the beneficial effects that: in the invention, partial alkyl is converted into hydroxyl to a certain extent through controlling roasting conditions, so that the hydrophilic/hydrophobic properties of the molecular sieve are adjusted. The control method is simple, has universal applicability, and has easily controlled roasting conditions, and the wettability of the material can be obviously changed after roasting, so that the catalytic performance of the material is improved.
Drawings
Fig. 1 is a contact angle of a sample obtained by the method of example 1.
Figure 2 is an XRD spectrum of the sample obtained by the method of example 1.
Fig. 3 is a contact angle of a sample obtained by the method of example 3.
Figure 4 is an XRD spectrum of the sample obtained by the method of example 3.
Fig. 5 is a contact angle of a sample obtained by the method of example 6.
Figure 6 is an XRD spectrum of the sample obtained by the method of example 6.
Fig. 7 is a contact angle of a sample obtained by the method of example 8.
Figure 8 is an XRD spectrum of the sample obtained by the method of example 8.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The synthesis method capable of improving the wettability of the ZSM-5 zeolite molecular sieve comprises the following steps:
step one, grinding and mixing a template agent or seed crystal and a solid raw material (a silicon source, an alkali source and/or an aluminum source);
step two, placing the ground mixture into a reaction kettle, and crystallizing for 24-44 hours at 160-190 ℃ to obtain a crystallized solid product;
taking out the crystallized solid product, drying and roasting to obtain the required zeolite molecular sieve;
wherein, the roasting process is temperature programming, the temperature programming condition is 1 ℃/min-10 ℃/min, and the roasting condition is as follows: the roasting time is 1-24 hours at 400-800 ℃, and the content of oxygen in the roasting atmosphere is 1-100%.
Example 1
The method comprises the steps of taking organic silicon hydrolyzed by dimethyl dimethoxy silane and sodium silicate nonahydrate as silicon sources, adding a template agent of tetrapropyl ammonium hydroxide, aluminum source aluminum sulfate and alkali source sodium hydroxide into the silicon sources, wherein the organic silicon source accounts for 10% of the total mass of the silane. Silicon source of SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by Na2Calculated by O, the molar ratio of each component is SiO2:Al2O3:Na2O is template agent 1:0.004:0.1: 0.1. Fully grinding the raw materials to obtain a mixture;
putting the mixture into a reaction kettle, crystallizing for 24 hours at 160 ℃, taking out a crystallized solid product, and drying to obtain a ZSM-5 molecular sieve material containing organosilane;
taking the ZSM-5 molecular sieve material containing the organic silane into a porcelain boat, and putting the porcelain boat into a muffle furnace, wherein the temperature control conditions are as follows: heating to 400 deg.C at a rate of 1 deg.C/min, and calcining at 400 deg.C in 100% oxygen for 1h to obtain zeolite molecular sieve with improved wettability.
Referring to fig. 1 and 2, the obtained zeolite molecular sieve is a ZSM-5 molecular sieve, and the contact angle thereof is 59 °.
Example 2
Organic silicon hydrolyzed by methyltrimethoxysilane and white carbon black are used as silicon sources, wherein the organic silicon source accounts for 15% of the total mass of the silane, and then template agents of tetrapropyl ammonium bromide, aluminum source sodium metaaluminate and alkali source sodium hydroxide are added. Silicon source of SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by Na2Calculated by O, the molar ratio of each component is SiO2:Al2O3:Na2And O is a template agent which is 1:0.008:0.15: 0.12. Fully grinding the raw materials to obtain a mixture;
putting the mixture into a reaction kettle, crystallizing for 30 hours at 170 ℃, taking out a crystallized solid product, and drying to obtain a ZSM-5 molecular sieve material containing organosilane;
taking the ZSM-5 molecular sieve material containing the organic silane into a porcelain boat, and putting the porcelain boat into a muffle furnace, wherein the temperature control conditions are as follows: heating to the roasting temperature of 450 ℃ at the speed of 2 ℃/min, roasting for 4h at the temperature of 450 ℃ under the condition of 100 percent oxygen, and finally obtaining the zeolite molecular sieve with improved wettability.
Example 3
Organic silicon hydrolyzed by methyl triethoxysilane and solid silica gel are used as silicon sources, wherein the organic silicon source accounts for 20% of the total mass of the silane, and then template agents of tetrapropylammonium chloride, aluminum source sodium metaaluminate and alkali source sodium hydroxide are added. Silicon source of SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by Na2Calculated by O, the molar ratio of each component is SiO2:Al2O3:Na2O template agent 1:0.012:0.2: 0.14. Fully grinding the raw materials to obtain a mixture;
putting the mixture into a reaction kettle, crystallizing at 180 ℃ for 36 hours, taking out a crystallized solid product, and drying to obtain an organosilane-containing ZSM-5 molecular sieve material;
taking the ZSM-5 molecular sieve material containing the organic silane into a porcelain boat, and putting the porcelain boat into a muffle furnace, wherein the temperature control conditions are as follows: heating to 500 deg.C at 3 deg.C/min, and calcining at 500 deg.C in 50% oxygen for 6 hr to obtain zeolite molecular sieve with improved wettability.
Referring to fig. 3 and 4, the obtained zeolite molecular sieve is a ZSM-5 molecular sieve having a contact angle of 45 °.
Example 4
Organic silicon hydrolyzed by dimethyl diethoxy silane and sodium silicate nonahydrate are used as silicon sources, wherein the organic silicon source accounts for 25% of the total mass of silane, and then template agents of tetrapropyl ammonium hydroxide, aluminum source nano aluminum oxide and alkali source sodium hydroxide are added. Silicon source of SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by Na2Calculated by O, the molar ratio of each component is SiO2:Al2O3:Na2And O is 1:0.016:0.25: 0.16. Fully grinding the raw materials to obtain a mixture;
putting the mixture into a reaction kettle, crystallizing for 40 hours at 190 ℃, taking out a crystallized solid product, and drying to obtain a ZSM-5 molecular sieve material containing organosilane;
taking the ZSM-5 molecular sieve material containing the organic silane into a porcelain boat, and putting the porcelain boat into a muffle furnace, wherein the temperature control conditions are as follows: heating to 550 deg.C at 4 deg.C/min, and calcining at 550 deg.C under 50% oxygen for 8 hr to obtain zeolite molecular sieve with improved wettability.
Example 5
Organosilicon hydrolyzed by propyl triethoxysilane and white carbon black are used as silicon sources, wherein the organic silicon source accounts for 30% of the total mass of the silane, and then template agents of tetrapropyl ammonium bromide, aluminum source of aluminum-source alumina and alkali source sodium hydroxide are added. Silicon source of SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by Na2Calculated by O, the molar ratio of each component is SiO2:Al2O3:Na2O is template agent 1:0.024:0.3: 0.2. Fully grinding the raw materials to obtain a mixture;
putting the mixture into a reaction kettle, crystallizing for 44 hours at 180 ℃, taking out a crystallized solid product, and drying to obtain a ZSM-5 molecular sieve material containing organosilane;
taking the ZSM-5 molecular sieve material containing the organic silane into a porcelain boat, and putting the porcelain boat into a muffle furnace, wherein the temperature control conditions are as follows: heating to 600 deg.C at a rate of 5 deg.C/min, and calcining at 600 deg.C under 30% oxygen for 10 hr to obtain zeolite molecular sieve with improved wettability.
Example 6
The method comprises the steps of taking organic silicon hydrolyzed by dimethyl dimethoxy silane and sodium silicate nonahydrate as silicon sources, adding a template agent of tetrapropyl ammonium hydroxide, aluminum source aluminum sulfate and alkali source sodium hydroxide, wherein the organic silicon source accounts for 35% of the total mass of silane. Silicon source of SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by Na2Calculated by O, the molar ratio of each component is SiO2:Al2O3:Na2O is 1:0.03:0.35:0.24 as a template. Fully grinding the raw materials to obtain a mixture;
putting the mixture into a reaction kettle, crystallizing for 40 hours at 180 ℃, taking out a crystallized solid product, and drying to obtain a ZSM-5 molecular sieve material containing organosilane;
taking the ZSM-5 molecular sieve material containing the organic silane into a porcelain boat, and putting the porcelain boat into a muffle furnace, wherein the temperature control conditions are as follows: heating to 650 deg.C at 6 deg.C/min, and calcining at 650 deg.C under 20% oxygen for 12h to obtain zeolite molecular sieve with improved wettability.
Referring to fig. 5 and 6, the obtained zeolite molecular sieve is a ZSM-5 molecular sieve, and the contact angle thereof is 24 °.
Example 7
Organic silicon hydrolyzed by n-dodecyl trimethoxy silane and sodium silicate nonahydrate are used as silicon sources, and then template agents of tetrapropyl ammonium bromide, aluminum source aluminum sulfate and alkali source sodium hydroxide are added. Silicon source of SiO2Aluminum meterDerived from Al2O3The alkali source is calculated by Na2Calculated by O, the molar ratio of each component is SiO2:Al2O3:Na2And O is a template agent which is 1:0.03:0.4:0.3, wherein the organic silicon source accounts for 40% of the total mass of the silane. Fully grinding the raw materials to obtain a mixture;
putting the mixture into a reaction kettle, crystallizing at 180 ℃ for 36 hours, taking out a crystallized solid product, and drying to obtain an organosilane-containing ZSM-5 molecular sieve material;
taking the ZSM-5 molecular sieve material containing the organic silane into a porcelain boat, and putting the porcelain boat into a muffle furnace, wherein the temperature control conditions are as follows: heating to the roasting temperature of 700 ℃ at the speed of 7 ℃/min, roasting for 5h at the temperature of 700 ℃ under the condition of 20 percent oxygen, and finally obtaining the zeolite molecular sieve with improved wettability.
Example 8
Organosilicon hydrolyzed by n-hexadecyl trimethoxy silane and sodium silicate nonahydrate are used as silicon sources, and then template agents of tetrapropyl ammonium hydroxide, aluminum source aluminum sulfate and alkali source sodium hydroxide are added. Silicon source of SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by Na2Calculated by O, the molar ratio of each component is SiO2:Al2O3:Na2And O is a template agent which is 1:0.03:0.45:0.3, wherein the organic silicon source accounts for 40% of the total mass of the silane. Fully grinding the raw materials to obtain a mixture;
putting the mixture into a reaction kettle, crystallizing at 180 ℃ for 36 hours, taking out a crystallized solid product, and drying to obtain an organosilane-containing ZSM-5 molecular sieve material;
taking the ZSM-5 molecular sieve material containing the organic silane into a porcelain boat, and putting the porcelain boat into a muffle furnace, wherein the temperature control conditions are as follows: heating to 750 deg.C at 8 deg.C/min, and calcining at 750 deg.C and 10% oxygen for 6 hr to obtain zeolite molecular sieve with improved wettability.
Referring to fig. 7 and 8, the obtained zeolite molecular sieve is a ZSM-5 molecular sieve having a contact angle of 12 °.
Example 9
Hydrolyzed with phenyltrimethoxysilaneOrganic silicon and solid silica gel are used as silicon sources, wherein the organic silicon source accounts for 20% of the total mass of the silane, and then template agents of tetrapropyl ammonium hydroxide, aluminum source aluminum sulfate and alkali source sodium hydroxide are added. Silicon source of SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by Na2Calculated by O, the molar ratio of each component is SiO2:Al2O3:Na2And O is a template agent which is 1:0.03:0.5:0.24, wherein the organic silicon source accounts for 20 percent of the total mass of the silane. Fully grinding the raw materials to obtain a mixture;
putting the mixture into a reaction kettle, crystallizing at 180 ℃ for 36 hours, taking out a crystallized solid product, and drying to obtain an organosilane-containing ZSM-5 molecular sieve material;
taking the ZSM-5 molecular sieve material containing the organic silane into a porcelain boat, and putting the porcelain boat into a muffle furnace, wherein the temperature control conditions are as follows: heating to 800 deg.C at a rate of 1 deg.C/min, and calcining at 800 deg.C under 10% oxygen for 24h to obtain zeolite molecular sieve with improved wettability.
Example 10
Organic silicon hydrolyzed by diphenyl dimethoxy silane and sodium silicate nonahydrate are used as silicon sources, and then template agents of tetrapropyl ammonium hydroxide, aluminum source aluminum sulfate and alkali source sodium hydroxide are added. Silicon source of SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by Na2Calculated by O, the molar ratio of each component is SiO2:Al2O3:Na2And O is a template agent which is 1:0.03:0.4:0.2, wherein the organic silicon source accounts for 10 percent of the total mass of the silane. Fully grinding the raw materials to obtain a mixture;
putting the mixture into a reaction kettle, crystallizing for 30 hours at 180 ℃, taking out a crystallized solid product, and drying to obtain a ZSM-5 molecular sieve material containing organosilane;
taking the ZSM-5 molecular sieve material containing the organic silane into a porcelain boat, and putting the porcelain boat into a muffle furnace, wherein the temperature control conditions are as follows: heating to 600 deg.C at a rate of 10 deg.C/min, and calcining at 600 deg.C in 1% oxygen for 20 hr to obtain zeolite molecular sieve with improved wettability.
Comparative example 1
The organic silicon hydrolyzed by dimethyl dimethoxy silane is used as a silicon source, and then template agent tetrapropyl ammonium hydroxide, aluminum source aluminum sulfate and alkali source sodium hydroxide are added. Silicon source of SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by Na2Calculated by O, the molar ratio of each component is SiO2:Al2O3:Na2O is 1:0.02:0.3:0.2 as a template. Fully grinding the raw materials to obtain a mixture;
putting the mixture into a reaction kettle, crystallizing at 180 ℃ for 36 hours, taking out a crystallized solid product, and drying to obtain a pure organosilane ZSM-5 molecular sieve material;
taking the ZSM-5 molecular sieve material of the pure organosilane into a porcelain boat, putting the porcelain boat into a muffle furnace, and controlling the temperature under the following conditions: heating to 550 deg.C at a rate of 5 deg.C/min, and calcining at 550 deg.C under 10% oxygen for 10 hr.
Comparative example 2
Sodium silicate nonahydrate is used as a silicon source, and then template agents of tetrapropyl ammonium hydroxide, aluminum source aluminum sulfate and alkali source sodium hydroxide are added. Silicon source of SiO2The aluminum source is calculated as Al2O3The alkali source is calculated by Na2Calculated by O, the molar ratio of each component is SiO2:Al2O3:Na2O is 1:0.02:0.3:0.2 as a template. Fully grinding the raw materials to obtain a mixture;
putting the mixture into a reaction kettle, crystallizing for 40 hours at 180 ℃, taking out a crystallized solid product, and drying to obtain a ZSM-5 molecular sieve material without organosilane;
taking the ZSM-5 molecular sieve material not containing the organosilane into a porcelain boat, and putting the porcelain boat into a muffle furnace, wherein the temperature control conditions are as follows: heating to 550 deg.C at a rate of 10 deg.C/min, and calcining at 550 deg.C under 10% oxygen for 10 hr.
Comparative example 3
The organic silicon hydrolyzed by dimethyl dimethoxy silane is used as a silicon source, and then template agent tetrapropyl ammonium hydroxide, aluminum source aluminum sulfate and alkali source sodium hydroxide are added. Silicon source of SiO2The aluminum source is counted as Al2O3The alkali source is calculated by Na2Calculated by O, the molar ratio of each component is SiO2:Al2O3:Na2O is 1:0.02:0.3:0.2 as a template. Fully grinding the raw materials to obtain a mixture;
putting the mixture into a reaction kettle, crystallizing at 180 ℃ for 36 hours, taking out a crystallized solid product, and drying to obtain a pure organosilane ZSM-5 molecular sieve material;
taking the ZSM-5 molecular sieve material of the pure organosilane into a porcelain boat, putting the porcelain boat into a muffle furnace, and controlling the temperature under the following conditions: heating to 550 deg.C at a rate of 5 deg.C/min, and vacuum-baking at 550 deg.C for 10 hr.
TABLE 1
As can be seen from the data in the above table, the silicon source is adjusted from a single type to be composed of inorganic silicon and organic silicon, and the baking conditions are limited, so that the template agent or the seed crystal is removed, and part of organic groups in the template agent or the seed crystal are selectively retained, the corresponding organic groups are retained while the template agent is baked, and the wettability of the molecular sieve is adjusted within a required range. The method realizes the preparation of the high-performance ZSM-5 zeolite by a green synthetic route, and has strong application value.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (13)
1. A synthetic method capable of improving wettability of a ZSM-5 zeolite molecular sieve is characterized by comprising the following steps:
s1, grinding and mixing the structure directing agent and the solid raw material to obtain a ground mixture;
s2, placing the ground mixture into a reaction kettle, and carrying out crystallization reaction for 24-44 hours at 160-190 ℃ to obtain a crystallized solid product;
s3, drying and roasting the crystallized solid product to obtain the required zeolite molecular sieve,
wherein the structure directing agent is selected from at least one of a templating agent and a seed; the solid raw materials are a silicon source, an alkali source and an aluminum source; the roasting conditions are as follows: the roasting atmosphere is at least one of oxygen and nitrogen, the temperature is raised to 400-800 ℃ at the speed of 1-10 ℃/min, and the roasting time is 1-24 h.
2. The synthesis method capable of improving the wettability of the ZSM-5 zeolite molecular sieve as claimed in claim 1, wherein the roasting atmosphere is composed of oxygen and nitrogen, wherein the volume content of the oxygen is 1-100%.
3. The method as claimed in claim 1, wherein the structure directing agent is a template and the silicon source is SiO in step S12The aluminum source is calculated as Al2O3The alkali source is calculated by Na2Calculated by O, the molar ratio of each component is SiO2:Al2O3:Na2O is 1: 0.004-0.03: 0.1-0.5: 0.1-0.3 of a template agent.
4. The synthesis method of claim 1, wherein in step S1, the structure directing agent is a seed crystal, and the seed crystal is added in an amount of 4-10% of the mass of the silicon source.
5. A synthesis method capable of improving the wettability of a ZSM-5 zeolite molecular sieve as claimed in claim 1, wherein the silicon source is composed of inorganic silicon and organic silicon prepared by hydrolysis of organic silane.
6. A synthesis method according to claim 5, capable of improving the wettability of ZSM-5 zeolite molecular sieve, wherein the organosilane is selected from one or more of dimethyldimethoxysilane, methyltrimethoxysilane, diethyldiethoxysilane, propyltriethoxysilane, n-dodecyltrimethoxysilane, n-hexadecyltrimethoxysilane, phenyltrimethoxysilane and diphenyldimethoxysilane.
7. A synthesis method capable of improving the wettability of a ZSM-5 zeolite molecular sieve according to claim 5, wherein the inorganic silicon is selected from one or more of sodium silicate nonahydrate, solid silica gel and white carbon black.
8. The synthesis method capable of improving the wettability of the ZSM-5 zeolite molecular sieve as claimed in claim 5, wherein the organic silicon accounts for 10-40% by mass of the silicon source, and the inorganic silicon accounts for 60-90% by mass of the silicon source.
9. The method as claimed in claim 1, wherein the aluminum source is selected from one or more of aluminum sulfate, sodium metaaluminate and nano alumina.
10. A synthesis method according to claim 1, capable of improving the wettability of the ZSM-5 zeolite molecular sieve, wherein the template agent is tetrapropylamine salt.
11. A synthesis method according to claim 10, capable of improving the wettability of the molecular sieve of ZSM-5 zeolite, wherein the tetrapropylamine salt is selected from one or more of tetrapropylammonium hydroxide, tetrapropylammonium bromide and tetrapropylammonium chloride.
12. A synthesis method according to claim 1, capable of improving the wettability of the molecular sieve of ZSM-5 zeolite, characterized in that the seeds are of ZSM-5 zeolite.
13. The synthesis method for improving the wettability of a ZSM-5 zeolite molecular sieve as recited in claim 1, wherein said alkali source is sodium hydroxide.
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| CN113184877A (en) * | 2021-05-10 | 2021-07-30 | 安阳工学院 | Hollow octahedral NaP molecular sieve and preparation method thereof |
| CN113683099A (en) * | 2021-08-31 | 2021-11-23 | 大连理工大学 | Method for synthesizing defect type zeolite molecular sieve rich in hydroxyl pits |
| CN114789063A (en) * | 2022-06-22 | 2022-07-26 | 浙江晟格生物科技有限公司 | Silicon-aluminum solid acid catalyst, preparation method and application |
| CN116477639A (en) * | 2023-03-16 | 2023-07-25 | 浙江工业大学 | Method for synthesizing ZSM-5 molecular sieve by using polymer assisted solvent-free method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113184877A (en) * | 2021-05-10 | 2021-07-30 | 安阳工学院 | Hollow octahedral NaP molecular sieve and preparation method thereof |
| CN113184877B (en) * | 2021-05-10 | 2023-06-09 | 安阳工学院 | Hollow octahedral NaP molecular sieve and preparation method thereof |
| CN113683099A (en) * | 2021-08-31 | 2021-11-23 | 大连理工大学 | Method for synthesizing defect type zeolite molecular sieve rich in hydroxyl pits |
| CN113683099B (en) * | 2021-08-31 | 2023-12-29 | 大连理工大学 | Method for synthesizing defective zeolite molecular sieve rich in hydroxy nest |
| CN114789063A (en) * | 2022-06-22 | 2022-07-26 | 浙江晟格生物科技有限公司 | Silicon-aluminum solid acid catalyst, preparation method and application |
| CN116477639A (en) * | 2023-03-16 | 2023-07-25 | 浙江工业大学 | Method for synthesizing ZSM-5 molecular sieve by using polymer assisted solvent-free method |
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