CN106166500A - A kind of preparation method of the catalyst of catalytic decomposition methanthiol - Google Patents
A kind of preparation method of the catalyst of catalytic decomposition methanthiol Download PDFInfo
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- CN106166500A CN106166500A CN201610527512.2A CN201610527512A CN106166500A CN 106166500 A CN106166500 A CN 106166500A CN 201610527512 A CN201610527512 A CN 201610527512A CN 106166500 A CN106166500 A CN 106166500A
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- Prior art keywords
- methanthiol
- catalyst
- catalytic decomposition
- source
- rare earth
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000003421 catalytic decomposition reaction Methods 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 56
- 239000010703 silicon Substances 0.000 claims abstract description 56
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 38
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 35
- 239000003513 alkali Substances 0.000 claims abstract description 29
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 3
- 241000209094 Oryza Species 0.000 claims description 32
- 235000007164 Oryza sativa Nutrition 0.000 claims description 32
- 235000009566 rice Nutrition 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 20
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000010903 husk Substances 0.000 claims description 9
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 claims description 4
- 229910020489 SiO3 Inorganic materials 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 2
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 2
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 2
- MOXJKKOSZCHGEU-UHFFFAOYSA-M hydrogen sulfate;tetrapropylazanium Chemical compound OS([O-])(=O)=O.CCC[N+](CCC)(CCC)CCC MOXJKKOSZCHGEU-UHFFFAOYSA-M 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 19
- 238000001816 cooling Methods 0.000 description 10
- 229910052911 sodium silicate Inorganic materials 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910003243 Na2SiO3·9H2O Inorganic materials 0.000 description 8
- 239000005543 nano-size silicon particle Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 229950000845 politef Drugs 0.000 description 6
- -1 wherein Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000002336 sorption--desorption measurement Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 description 2
- 229910002617 Gd(NO3)3·6H2O Inorganic materials 0.000 description 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 2
- 229910002852 Sm(NO3)3·6H2O Inorganic materials 0.000 description 2
- 239000002154 agricultural waste Substances 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- PYNUOAIJIQGACY-UHFFFAOYSA-N propylazanium;chloride Chemical compound Cl.CCCN PYNUOAIJIQGACY-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical class [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 210000004884 grey matter Anatomy 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910006287 γ-MnO2 Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses the preparation method of the catalyst of a kind of catalytic decomposition methanthiol, comprise the following steps: silicon source, alkali source, template, mineralizer and rare earth metal source are carried out mixed grinding, it is allowed to mix homogeneously, the pastel obtained is sealed, through crystallization, product through filtering, wash, drying, high-temperature roasting, obtain the catalyst of catalytic decomposition methanthiol containing rare earth element；The present invention uses cheap silicon source to be raw material, solves the expensive problem in silicon source during conventional synthesis；On the other hand utilizing solid phase uninanned platform method, can realize easy Fast back-projection algorithm and go out catalyst, step simple and fast, energy consumption is low, and avoids the use of the solvent secondary pollution to environment in building-up process, and whole building-up process is cheap, quick, environmental protection.
Description
Technical field
The present invention relates to the preparation method of the catalyst of a kind of catalytic decomposition methanthiol, belong to catalyst preparation technology neck
Territory.
Background technology
Methanthiol is a kind of acid foul gas, is widely used in synthetic material, pesticide, medicine and other fields, but it is deposited
Endanger at inflammable, explosive, high toxicity etc..As a kind of organic sulfur contaminant, methanthiol is prevalent in natural gas and most stone
In oil product (such as liquefied petroleum gas), in liquefied petroleum gas as a example by the quantitative analysis of mercaptans content, methanthiol reaches closely
60%.Therefore, methanthiol causes certain threat to atmosphere quality.Realize the efficient-decomposition of methanthiol, for protection people
Physically and mentally healthy and realize China's sulfur emission reduction targets and have great importance.
At present, catalytic decomposition is a kind of efficient, methanthiol removal methods of low energy consumption.Conventional catalyst decomposes methanthiol
Catalyst mainly has V2O5、γ-MnO2, the metal-oxide such as ZnO and metal and composite oxide supported sulfonated phthalocyanine cobalt thereof
(CoPcS) catalysis material such as, but utilize above-mentioned catalyst to decompose methanthiol and can produce dimethyl sulfide and Methyl disulfide
The organic sulfur contaminant that ether etc. are new.Edouard Huguet et al. finds, HZSM-5 molecular sieve catalyst can realize methanthiol
100% converts, but catalyst life is short, easy in inactivation；Research worker finds that rare earth modified HZSM-5 activity is high, and good stability can be big
Reduce mercaptan catalyst degradation temperature greatly, and the life-span is far above unmodified HZSM-5 molecular sieve catalyst.But tradition is dilute
The synthetic method (hydrothermal synthesis method, Microwave Radiation Synthesis Method, infusion process, ion exchange etc.) of soil modified HZSM-5 all exists not
With problem, as complicated in building-up process, pollute environment, high in cost of production problem, the simplest and the most direct, environmental protection, cheap synthesis technique road
Line is one of emphasis of current research worker breakthrough.
Rice husk is agricultural wastes, and the place of production is extensive, cheap, and it is fired in the grey matter powder after ash silicone content relatively
Height, rice hull ash is mainly composed of amorphous Si O after testing2, content is generally 80-95%, and impurity component has Na2O、CaO、MgO、
Fe2O3、Al2O3With C etc., can be used for preparing the chemical products such as white carbon, carborundum, waterglass, aeroge, but this series products pair
Purity requirement is higher, other inorganic constituentss in rice husk, seriously constrains the industrialization process of rice hull ash class HIGH-PURITY SILICON product.And
Utilize rice hull ash synthesizing high-silicon zeolite product, the highest to the purity requirement of silicon source, and added value is high, so being that rice hull ash is the most sharp
A good prospect.
Summary of the invention
It is an object of the invention to provide the preparation method of the catalyst of a kind of catalytic decomposition methanthiol, specifically include following step
Rapid:
(1) it is silicon in molar ratio: alkali source: template: the ratio of mineralizer=1 0.4-0.5 0.08-0.1 0.7-0.9, respectively
Weigh silicon source, alkali source, template, mineralizer, account for contained by silicon source, alkali source, template, mineralizer according still further to rare earth metal
SiO2Gross mass and the ratio interpolation rare earth metal of the X% of the rare earth metal quality sum added, weigh corresponding rare earth source,
It is mixed together grinding 5-20min with silicon source, alkali source, template, mineralizer, is allowed to mix homogeneously, obtains pastel, its middle rare earth
It is as follows that the mass percent of metal calculates formula:
(2) pastel step (1) obtained seals, and after 160-180 DEG C of reaction 8-24h, is cooled to room temperature；
(3) product that step (2) obtains is washed with deionized to neutrality filtration, and filter cake is at 50-100 DEG C of dry 5-24h；
(4) the product Temperature fall after 450-550 DEG C of roasting 4-10h step (3) obtained, obtains urging containing rare earth element
Change the catalyst decomposing methanthiol.
Preferably, described silicon source is the rice hull ash that rice husk obtains after 550 DEG C of calcining 4-6h under aerobic conditions, wherein dioxy
SiClx content is 80-95%, or nano silicon.
Preferably, described alkali source is the Na containing water of crystallization2SiO3。
Preferably, described template is 4-propyl bromide, 4-propyl ammonium chloride, tetrapropyl ammonium iodide or tetrapropyl sulphuric acid
Hydrogen ammonium.
Preferably, described mineralizer is ammonium chloride or ammonium fluoride.
Preferably, described rare earth source is the one in Lanthanum (III) nitrate, samaric nitrate, cerous nitrate, europium nitrate, Gadolinium trinitrate, Erbium trinitrate.
The invention have the benefit that
(1) use the rice hull ash that agricultural wastes rice husk obtains after high-temperature roasting as silicon source, rationally recycle agricultural useless
Gurry, saves catalyst synthesis cost, reduces environmental pollution simultaneously.
(2) solid phase synthesis catalyst, greatly reduces synthesis step, can realize easy Fast back-projection algorithm and go out catalytic decomposition methanthiol
Catalyst, shorten generated time, thus improve combined coefficient, the most cost-effective.
(3) solvent-free addition, makes building-up process more environmental protection.
Accompanying drawing explanation
Fig. 1 is the XRD figure picture of the catalyst of the catalytic decomposition methanthiol that the embodiment of the present invention 1 prepares；
Fig. 2 is the isothermal adsorption desorption curve chart of the catalyst of the catalytic decomposition methanthiol that the embodiment of the present invention 1 prepares；
Fig. 3 is the XRD figure picture of the catalyst of the catalytic decomposition methanthiol that the embodiment of the present invention 2 prepares；
Fig. 4 is the XRD figure picture of the catalyst of the catalytic decomposition methanthiol that the embodiment of the present invention 3 prepares；
Fig. 5 is the XRD figure picture of the catalyst of the catalytic decomposition methanthiol that the embodiment of the present invention 4 prepares；
Fig. 6 is the XRD figure picture of the catalyst of the catalytic decomposition methanthiol that the embodiment of the present invention 5 prepares；
Fig. 7 is the XRD figure picture of the catalyst of the catalytic decomposition methanthiol that the embodiment of the present invention 6 prepares.
Detailed description of the invention
The present invention is described further with specific embodiment below in conjunction with the accompanying drawings, but protection scope of the present invention is not
It is limited to described content.
Embodiment 1
The preparation method of the catalyst RE/HZSM-5 of catalytic decomposition methanthiol described in the present embodiment, specifically includes following steps:
(1) in logical oxygen Muffle furnace, rice husk is calcined 4h in 550 DEG C, obtains the rice hull ash that dioxide-containing silica is 80%, grind
Standby as silicon source afterwards, wherein calcination procedure Elevated Temperature Conditions is: with 10 DEG C/min temperature programming to after 400 DEG C, continue with 2 DEG C/min
Continue and be warming up to 550 DEG C, after keeping 4h, be naturally cooling to room temperature；
(2) in molar ratio for silicon: alkali source: template: the ratio of mineralizer=1 0.46 0.09 0.8 weighs raw material, according still further to
Rare earth metal accounts for SiO contained by silicon source, alkali source, template, mineralizer2Gross mass and the rare earth metal quality sum added
5% ratio add rare earth metal, wherein, silicon source is the rice hull ash that step (1) obtains, and alkali source is Na2SiO3·9H2O, template
Agent is 4-propyl bromide, and mineralizer is ammonium chloride, and rare earth source is Eu (NO3)3·6H2O, the actual amount of silicon is in rice hull ash
Silicon and Na2SiO3·9H2Silicon sum in O, weigh respectively 0.41g rice hull ash, 0.43g ammonium chloride, 0.24g 4-propyl bromide,
1.315g Na2SiO3·9H2O、0.093g Eu(NO3)3·6H2O, is placed in mortar together, through the grinding of 20min, is allowed to
Mix homogeneously；
(3) mixing pastel step (2) obtained moves in the reactor that 100mL politef is liner and seals, 180 DEG C
After reaction 21h, it is cooled to room temperature；
(4) product that step (3) obtains is washed with deionized to neutrality filtration, and then filter cake is incubated 12h, product at 70 DEG C
It is dried completely；
(5) product after step (4) being dried, at 550 DEG C of roasting 4h, furnace cooling, obtains the catalyst of catalytic decomposition methanthiol
Eu/HZSM-5。
The catalyst Eu/HZSM-5 of the catalytic decomposition methanthiol obtained by embodiment 1, through X-ray diffraction analysis, such as Fig. 1
Shown in, 2 θ=7.8 ° in figure, 8.8 °, 23.2 °, 23.8 °, 24.3 ° there is obvious MFI characteristic peak, it is known that the material prepared
Structure is the MFI topological structure that HZSM-5 has；Characterize through nitrogen adsorption-desorption, as in figure 2 it is shown, and calculate the average hole of its BET
Footpath is 0.80nm, and specific surface area is 163m2/g；The experiment of resulting materials catalytic decomposition methanthiol, when reaction temperature is 550 DEG C
Time, the conversion ratio of methanthiol reaches 92%, shows that prepared material has the performance of the catalytic decomposition methanthiol of excellence.
Embodiment 2
The preparation method of the catalyst RE/HZSM-5 of catalytic decomposition methanthiol described in the present embodiment, specifically includes following steps:
(1) in molar ratio for silicon: alkali source: template: the ratio of mineralizer=1 0.5 0.08 0.9 weighs raw material, according still further to
Rare earth metal accounts for SiO contained by silicon source, alkali source, template, mineralizer2Gross mass and the rare earth metal quality sum added
1% ratio add rare earth metal, wherein, silicon source is nano silicon, and alkali source is Na2SiO3·5H2O, template is four
Propyl ammonium chloride, mineralizer is ammonium fluoride, and rare earth metal source is Gd (NO3)3·6H2O, the actual amount of silicon is nano silicon
In silicon and Na2SiO3·5H2Silicon sum in O, weighs 0.31g nano silicon, 0.33g ammonium fluoride, 0.18g tetra-respectively
Propyl ammonium chloride, 1.06g Na2SiO3·5H2O、0.018g Gd(NO3)3·6H2O, is placed in mortar, together through 5min's
Grind, be allowed to mix homogeneously；
(2) mixing pastel step (1) obtained moves in the reactor that 50mL politef is liner and seals, 160 DEG C
After reaction 12h, it is cooled to room temperature；
(3) product that step (2) obtains is washed with deionized to neutrality filtration, and then filter cake is incubated 24h, product at 80 DEG C
It is dried completely；
(3) product after step (3) being dried, at 450 DEG C of roasting 10h, furnace cooling, obtains the catalysis of catalytic decomposition methanthiol
Agent Gd/HZSM-5.
The catalyst Gd/HZSM-5 of the catalytic decomposition methanthiol obtained by embodiment 2, through X-ray diffraction analysis, such as Fig. 3
Shown in, 2 θ=7.8 ° in figure, 8.8 °, 23.2 °, 23.8 °, 24.3 ° there is obvious MFI characteristic peak, it is known that the material prepared
Structure is the MFI topological structure that HZSM-5 has；Characterize through nitrogen adsorption-desorption, and calculate its BET average pore size and be
0.91nm, specific surface area is 172m2/g；The experiment of resulting materials catalytic decomposition methanthiol, when reaction temperature is 600 DEG C, first
The conversion ratio of mercaptan reaches 94%, shows that prepared material has the performance of the catalytic decomposition methanthiol of excellence.
Embodiment 3
The preparation method of the catalyst RE/HZSM-5 of catalytic decomposition methanthiol described in the present embodiment, specifically includes following steps:
(1) in logical oxygen Muffle furnace, rice husk is calcined 6h in 550 DEG C, obtains the rice hull ash that dioxide-containing silica is 91%, grind
Standby as silicon source afterwards, wherein calcination procedure Elevated Temperature Conditions is: with 5 DEG C/min temperature programming to after 400 DEG C, continue with 2 DEG C/min
Continue and be warming up to 550 DEG C, after keeping 6h, be naturally cooling to room temperature；
(2) in molar ratio for silicon: alkali source: template: the ratio of mineralizer=1 0.4 0.1 0.9 weighs raw material, according still further to dilute
Earth metal accounts for SiO contained by silicon source, alkali source, template, mineralizer2Gross mass and the rare earth metal quality sum added
The ratio of 3% adds rare earth metal, and wherein, silicon source is the rice hull ash that step (1) obtains, and alkali source is Na2SiO3·9H2O, template
For 4-propyl ammonium chloride, mineralizer is ammonium chloride, and rare earth metal source is Er (NO3)3·5H2O, the actual amount of silicon is in rice hull ash
Silicon and Na2SiO3·9H2Silicon sum in O, weighs 0.4g rice hull ash, 0.48g ammonium chloride, 0.22g tetrapropyl chlorination respectively
Ammonium, 1.14g Na2SiO3·9H2O、0.049g Er(NO3)3·5H2O, is placed in mortar together, through the grinding of 15min, makes
Mix homogeneously；
(3) pastel step (2) obtained moves in the reactor that 100mL politef is liner and seals, 170 DEG C of reactions
After 18h, it is cooled to room temperature；
(4) product that step (3) obtains is washed with deionized to neutrality filtration, and then filter cake is incubated 5h, product at 100 DEG C
It is dried completely；
(5) product after step (4) being dried, at 500 DEG C of roasting 7h, furnace cooling, obtains the catalyst of catalytic decomposition methanthiol
Er/HZSM-5。
The catalyst Er/HZSM-5 of the catalytic decomposition methanthiol obtained by embodiment 3, through X-ray diffraction analysis, such as Fig. 4
Shown in, 2 θ=7.8 ° in figure, 8.8 °, 23.2 °, 23.8 °, 24.3 ° there is obvious MFI characteristic peak, it is known that the material prepared
Structure is the MFI topological structure that HZSM-5 has；The experiment of resulting materials catalytic decomposition methanthiol, when reaction temperature is 550 DEG C
Time, the conversion ratio of methanthiol reaches 90%, shows that prepared material has the performance of the catalytic decomposition methanthiol of excellence.
Embodiment 4
The preparation method of the catalyst RE/HZSM-5 of catalytic decomposition methanthiol described in the present embodiment, specifically includes following steps:
(1) in logical oxygen Muffle furnace, rice husk is calcined 5h in 550 DEG C, obtains the rice hull ash that dioxide-containing silica is 95%, grind
Standby as silicon source afterwards, wherein calcination procedure Elevated Temperature Conditions is: with 5 DEG C/min temperature programming to after 400 DEG C, continue with 4 DEG C/min
Continue and be warming up to 550 DEG C, after keeping 5h, be naturally cooling to room temperature；
(2) in molar ratio for silicon: alkali source: template: the ratio of mineralizer=1 0.5 0.1 0.7 weighs raw material, according still further to dilute
Earth metal accounts for SiO contained by silicon source, alkali source, template, mineralizer2Gross mass and the rare earth metal quality sum added
The ratio of 2% adds rare earth metal, and wherein, silicon source is the rice hull ash that step (1) obtains, and alkali source is Na2SiO3·9H2O, template
For tetrapropyl ammonium hydrogen sulfate, mineralizer is ammonium fluoride, and rare earth source is Sm (NO3)3·6H2O, the actual amount of silicon is in rice hull ash
Silicon and Na2SiO3·9H2Silicon sum in O, weighs 0.32g rice hull ash, 0.26g ammonium fluoride, 0.28g tetrapropyl hydrogen sulfate respectively
Ammonium, 1.42g Na2SiO3·9H2O、0.036g Sm(NO3)3·6H2O, is placed in mortar together, through the grinding of 15min, makes
Mix homogeneously；
(3) mixing pastel step (2) obtained moves in the reactor that 100mL politef is liner and seals, 160 DEG C
After reaction 24h, it is cooled to room temperature；
(4) product that step (3) obtains is washed with deionized to neutrality filtration, and then filter cake is incubated 15h, product at 50 DEG C
It is dried completely；
(5) product after step (4) being dried, at 480 DEG C of roasting 10h, furnace cooling, obtains the catalysis of catalytic decomposition methanthiol
Agent Sm/HZSM-5.
The catalyst Sm/HZSM-5 of the catalytic decomposition methanthiol obtained by embodiment 4, through X-ray diffraction analysis, such as Fig. 5
Shown in, 2 θ=7.8 ° in figure, 8.8 °, 23.2 °, 23.8 °, 24.3 ° there is obvious MFI characteristic peak, it is known that the material prepared
Structure is the MFI topological structure that HZSM-5 has；Characterize through nitrogen adsorption-desorption, and calculate its BET average pore size and be
0.84nm, specific surface area is 159m2/g；The experiment of resulting materials catalytic decomposition methanthiol, when reaction temperature is 570 DEG C, first
The conversion ratio of mercaptan reaches 98%, shows that prepared material has the performance of the catalytic decomposition methanthiol of excellence.
Embodiment 5
The preparation method of the catalyst RE/HZSM-5 of catalytic decomposition methanthiol described in the present embodiment, specifically includes following steps:
(1) in molar ratio for silicon: alkali source: template: the ratio of mineralizer=1 0.46 0.09 0.8 weighs raw material, according still further to
Rare earth metal accounts for SiO contained by silicon source, alkali source, template, mineralizer2Gross mass and the rare earth metal quality sum added
5% ratio add rare earth metal, wherein, silicon source is nano silicon, and alkali source is Na2SiO3·9H2O, template is four
Propyl group ammonium bromide, mineralizer is ammonium chloride, and rare earth source is La (NO3)3·6H2O, the actual amount of silicon is in nano silicon
Silicon and Na2SiO3·9H2Silicon sum in O, weighs 0.32g nano silicon, 0.42g ammonium chloride, 0.24g tetrapropyl respectively
Ammonium bromide, 1.31g Na2SiO3·9H2O、0.10g La(NO3)3·6H2O, is placed in mortar together, through the grinding of 10min,
It is allowed to mix homogeneously；
(2) pastel step (1) obtained moves in the reactor that 50mL politef is liner and seals, 180 DEG C of reactions
After 24h, it is cooled to room temperature；
(3) product that step (2) obtains is washed with deionized to neutrality filtration, and then filter cake is incubated 10h at 100 DEG C, produces
Thing is dried completely；
(4) product after step (3) being dried, at 550 DEG C of roasting 5h, furnace cooling, obtains the catalyst of catalytic decomposition methanthiol
La/HZSM-5。
The catalyst La/HZSM-5 of the catalytic decomposition methanthiol obtained by embodiment 5, through X-ray diffraction analysis, such as Fig. 6
Shown in, 2 θ=7.8 ° in figure, 8.8 °, 23.2 °, 23.8 °, 24.3 ° there is obvious MFI characteristic peak, it is known that the material prepared
Structure is the MFI topological structure that HZSM-5 has；The experiment of resulting materials catalytic decomposition methanthiol, when reaction temperature is 580 DEG C
Time, the conversion ratio of methanthiol reaches 99%, shows that prepared material has the performance of the catalytic decomposition methanthiol of excellence.
Embodiment 6
The preparation method of the catalyst RE/HZSM-5 of catalytic decomposition methanthiol described in the present embodiment, specifically includes following steps:
(1) in logical oxygen Muffle furnace, rice husk is calcined 4h in 550 DEG C, obtains the rice hull ash that dioxide-containing silica is 85%, grind
Standby as silicon source afterwards, wherein calcination procedure Elevated Temperature Conditions is: with 5 DEG C/min temperature programming to after 400 DEG C, continue with 4 DEG C/min
Continue and be warming up to 550 DEG C, after keeping 4h, be naturally cooling to room temperature；
(2) in molar ratio for silicon: alkali source: template: the ratio of mineralizer=1 0.4 0.08 0.7 weighs raw material, according still further to
Rare earth metal accounts for SiO contained by silicon source, alkali source, template, mineralizer2Gross mass and the rare earth metal quality sum added
4% ratio add rare earth metal, wherein, silicon source is the rice hull ash that step (1) obtains, and alkali source is Na2SiO3·5H2O, template
Agent is tetrapropyl ammonium iodide, and mineralizer is ammonium fluoride, and rare earth source is Ce (NO3)3·6H2O, the actual amount of silicon is in rice hull ash
Silicon and Na2SiO3·5H2Silicon sum in O, weigh respectively 0.42g rice hull ash, 0.26g ammonium fluoride, 0.25g tetrapropyl ammonium iodide,
0.85g Na2SiO3·5H2O、0.077g Ce(NO3)3·6H2O, is placed in mortar together, through the grinding of 12min, is allowed to mixed
Close uniformly；
(3) pastel step (2) obtained moves in the reactor that 50mL politef is liner and seals, 170 DEG C of reactions
After 8h, it is cooled to room temperature；
(4) product that step (3) obtains is washed with deionized to neutrality filtration, and then filter cake is incubated 20h, product at 50 DEG C
It is dried completely；
(5) solid product after step (4) being dried, at 520 DEG C of roasting 6h, furnace cooling, obtains urging of catalytic decomposition methanthiol
Agent Ce/HZSM-5.
The catalyst Ce/HZSM-5 of the catalytic decomposition methanthiol obtained by embodiment 6, through X-ray diffraction analysis, such as Fig. 7
Shown in, 2 θ=7.8 ° in figure, 8.8 °, 23.2 °, 23.8 °, 24.3 ° there is obvious MFI characteristic peak, it is known that the material prepared
Structure is the MFI topological structure that HZSM-5 has；Characterize through nitrogen adsorption-desorption, and calculate its BET average pore size and be
0.78nm, specific surface area is 152m2/g；The experiment of resulting materials catalytic decomposition methanthiol, when reaction temperature is 600 DEG C, first
The conversion ratio of mercaptan reaches 100%, shows that prepared material has the performance of the catalytic decomposition methanthiol of excellence.
Claims (6)
1. the preparation method of the catalyst of a catalytic decomposition methanthiol, it is characterised in that specifically include following steps:
(1) it is silicon in molar ratio: alkali source: template: the ratio of mineralizer=1 0.4-0.5 0.08-0.1 0.7-0.9, respectively
Weigh silicon source, alkali source, template, mineralizer, account for contained by silicon source, alkali source, template, mineralizer according still further to rare earth metal
SiO2Gross mass and the ratio interpolation rare earth metal of the 1-5% of the rare earth metal quality sum added, weigh rare earth source, with silicon
Source, alkali source, template, mineralizer are mixed together grinding 5-20min, are allowed to mix homogeneously, obtain pastel；
(2) pastel step (1) obtained seals, and after 160-180 DEG C of reaction 8-24h, is cooled to room temperature；
(3) product that step (2) obtains is washed with deionized to neutrality filtration, and filter cake is at 50-100 DEG C of dry 5-24h；
(4) the product Temperature fall after 450-550 DEG C of roasting 4-10h step (3) obtained, obtains urging containing rare earth element
Change the catalyst decomposing methanthiol.
The preparation method of the catalyst of catalytic decomposition methanthiol the most according to claim 1, it is characterised in that described silicon source is
The rice hull ash that rice husk obtains after 550 DEG C of calcining 4-6h under aerobic conditions, wherein dioxide-containing silica is 80-95%, or nanometer two
Silicon oxide.
The preparation method of the catalyst of catalytic decomposition methanthiol the most according to claim 1, it is characterised in that described alkali source is
Na containing water of crystallization2SiO3。
The preparation method of the catalyst of catalytic decomposition methanthiol the most according to claim 1, it is characterised in that described template
For 4-propyl bromide, 4-propyl ammonium chloride, tetrapropyl ammonium iodide or tetrapropyl ammonium hydrogen sulfate.
The preparation method of the catalyst of catalytic decomposition methanthiol the most according to claim 1, it is characterised in that described mineralizer
For ammonium chloride or ammonium fluoride.
The preparation method of the catalyst of catalytic decomposition methanthiol the most according to claim 1, it is characterised in that described rare earth source
For the one in Lanthanum (III) nitrate, samaric nitrate, cerous nitrate, europium nitrate, Gadolinium trinitrate, Erbium trinitrate.
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| CN114602451A (en) * | 2022-02-28 | 2022-06-10 | 昆明理工大学 | Preparation method, product and application of mutually-embedded nano composite rare earth metal oxide cluster catalyst |
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