CN117443431A - Supported deoxidizing catalyst and preparation method and application thereof - Google Patents
Supported deoxidizing catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002808 molecular sieve Substances 0.000 claims abstract description 92
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 92
- 238000000034 method Methods 0.000 claims abstract description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000001301 oxygen Substances 0.000 claims abstract description 42
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 42
- 239000007789 gas Substances 0.000 claims abstract description 40
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 32
- 239000010703 silicon Substances 0.000 claims abstract description 32
- 239000004480 active ingredient Substances 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005470 impregnation Methods 0.000 claims abstract description 24
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229940045985 antineoplastic platinum compound Drugs 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 4
- 150000002941 palladium compounds Chemical class 0.000 claims abstract description 4
- 150000003058 platinum compounds Chemical class 0.000 claims abstract description 4
- 150000003304 ruthenium compounds Chemical class 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 25
- 238000002425 crystallisation Methods 0.000 claims description 20
- 230000008025 crystallization Effects 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 14
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical group [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000006392 deoxygenation reaction Methods 0.000 claims description 12
- 239000000741 silica gel Substances 0.000 claims description 9
- 229910002027 silica gel Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 19
- 229910001220 stainless steel Inorganic materials 0.000 description 16
- 239000010935 stainless steel Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000011343 solid material Substances 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0325—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/104—Oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of oxygen-containing organic gas deoxidization catalysts, and discloses a supported deoxidization catalyst, and a preparation method and application thereof. The preparation method of the supported deoxidizing catalyst comprises the following steps: 1) A silicon source calculated as silicon dioxide, a template agent, molecular sieve seeds calculated as silicon dioxide, alkali and water are mixed according to the following ratio of 1:0.01-0.5:0.01-0.2:0-0.5: mixing at a molar ratio of 1-10; 2) Crystallizing the mixed product; 3) Performing first roasting on the crystallized product to obtain a molecular sieve carrier; 4) And 3) loading active ingredient precursors on the molecular sieve carrier obtained in the step 3) or a carrier containing the molecular sieve carrier by using an impregnation method, and then carrying out second roasting, wherein the active ingredient precursors are one or more of platinum compounds, palladium compounds and ruthenium compounds. The supported deoxidizing catalyst has the advantages of higher dispersity of active species, long reaction service life and good deoxidizing effect.
Description
Technical Field
The invention relates to the field of oxygen-containing organic gas deoxidization catalysts, in particular to a supported deoxidization catalyst, and a preparation method and application thereof.
Background
Chemical production devices often face scenes such as high temperature and high pressure, explosive mixtures, a plurality of dangerous materials and the like, so that the chemical safety production has a plurality of potential safety hazards. Among them, the presence of oxygen-containing organic gases is a common safety hazard. When the oxygen content is in the explosion range or the oxygen content is continuously and cumulatively increased, gas-phase explosion accidents occur, and the production and the life of people are influenced.
There are various methods for achieving deoxygenation of oxygen-containing organic gases. Such as adsorption, cryogenic, catalytic, etc. The method for deoxidizing the oxygen in the organic gas by the catalytic oxidation method has the characteristics of simple operation, low price, wide adaptability and the like, and becomes a deoxidizing method with wide application prospect. In the method, the development of the deoxidizing catalyst is a core work and is also a common concern of more scientific researchers worldwide.
Waiting bud et al (industrial catalysis, 2020,28,11) discloses a micro chlorine resistant deoxidizing catalyst in hydrogen, which uses titanium dioxide as a carrier, noble metal Pt as an active component, and adds a corresponding amount of auxiliary agent, so that deoxidizing can be realized in a hydrogen atmosphere containing a micro amount of oxygen, and the deoxidizing catalyst has a certain chlorine resistant performance. Wang Haiyang et al (Natural gas chemical, C1 chemical and chemical, 2021, 46, 28-33) developed a coalbed methane deoxygenation catalyst by a self-sacrifice template method, which was applied to coalbed methane deoxygenation reactions, the developed catalyst used copper oxide as an active component, wherein the amount of copper oxide was adjusted by the amount of copper-containing precursor, and the prepared catalyst was characterized by various characterization means, and a higher deoxygenation rate was achieved at 400-500 ℃ in methane (20%) and nitrogen (rest) mixtures containing 3% oxygen. CN101664679a discloses a coalbed methane deoxidizing catalyst, which uses noble metal as an active component, alkali metal, alkaline earth metal and a combination thereof as an auxiliary agent, and the above materials are carried on an inert carrier in the form of a coating to prepare the catalyst.
The currently reported catalysts can often achieve better reaction performance at the initial stage of the reaction or can maintain long-period catalytic reaction activity in a system with low oxygen content. However, in a high oxygen-containing system, the materials often face the defects of poor dispersity of active components, poor reaction stability, coking deactivation and the like, and how to prepare the deoxidized catalyst with long period and high stability with high efficiency and low cost is still a challenge.
Disclosure of Invention
The invention aims to provide a supported deoxidizing catalyst for oxygen-containing organic gas and chemical tail gas and a preparation method thereof.
In order to achieve the above object, the present invention provides, in one aspect, a method for preparing a supported deoxidizing catalyst, characterized in that the method comprises the steps of,
1) A silicon source calculated as silicon dioxide, a template agent, molecular sieve seeds calculated as silicon dioxide, alkali and water are mixed according to the following ratio of 1:0.01-0.5:0.01-0.2:0-0.5: mixing at a molar ratio of 1-10;
2) Crystallizing the mixed product;
3) Performing first roasting on the crystallized product obtained in the step 2) to obtain a molecular sieve carrier;
4) Loading active ingredient precursors on the molecular sieve carrier obtained in the step 3) or the carrier containing the molecular sieve carrier by using an impregnation method, and then carrying out second roasting,
the active ingredient precursor is selected from one or more of platinum compounds, palladium compounds and ruthenium compounds.
Preferably, the silicon source, template, molecular sieve seed, base and water are combined in a ratio of 1:0.02-0.3:0.03-0.18:0-0.25: 1-8.
Preferably, the silicon source is one or more of white carbon black, silica gel and attapulgite.
Preferably, the template is tetrapropylammonium hydroxide.
Preferably, the base is sodium hydroxide and/or potassium hydroxide.
Preferably, the molecular sieve seed is a silicalite-1 molecular sieve.
Preferably, the crystallization conditions include: the temperature is 100-230 ℃ and the time is 10-300 minutes.
Preferably, the method further comprises: and (3) before the step (3), carrying out solid-liquid separation, washing and drying on the crystallized product obtained in the step (2).
Preferably, the conditions of the first firing include: the temperature is 500-600 ℃, and the roasting time is 2-10 hours.
Preferably, the conditions of the second firing include: the temperature is 350-450 ℃, and the roasting time is 1-5 hours.
Preferably, the impregnation method is an isovolumetric impregnation.
Preferably, the mass ratio of the active ingredient precursor to the molecular sieve carrier is 0.001 to 0.03 based on the mass of the active ingredient element: 1.
preferably, the active ingredient precursor is one or more of chloroplatinic acid, palladium nitrate, palladium chloride and ruthenium chloride.
In a second aspect of the present invention, there is provided a supported deoxidizing catalyst prepared by the method for preparing a supported deoxidizing catalyst of the first aspect of the present invention.
In a third aspect, the invention provides the use of the supported deoxygenation catalyst of the second aspect of the invention in deoxygenation of oxygen-containing organic gases and chemical tail gases.
Through the technical scheme, the catalyst carrier prepared by the preparation method is the Silicalite-1 molecular sieve with a hierarchical pore structure, and the Silicalite-1 molecular sieve with high crystallinity can be prepared in a short time by regulating the synthesis ratio. In addition, in the preparation of the carrier, the subsequent processes of acid and alkali treatment and the like are avoided, and the high crystallinity of the material is ensured. Furthermore, the introduction of the active sites is performed using an impregnation method, the rich pore structure of the Silicalite-1 molecular sieve promotes the dispersion during the introduction of the active sites, and also provides a plurality of sites for the active sites, which makes it possible to prepare a catalyst having a high metal dispersion degree, and provides a possibility for the exposure of more active sites. Besides the micropore structure, the catalyst has a mesoporous structure to a certain extent, so that materials involved in the deoxidation reaction have higher diffusion rate, coking carbon deposition in the reaction process can be reduced, and the service life of the catalyst is prolonged.
Drawings
Figure 1 is an XRD spectrum of the molecular sieve obtained in example 1.
FIG. 2 is a transmission electron micrograph of the molecular sieve obtained in example 1.
FIG. 3 is a scanning electron microscope image of the molecular sieve obtained in example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided a method for producing a supported deoxidizing catalyst, characterized in that the method comprises the steps of,
1) A silicon source calculated as silicon dioxide, a template agent, molecular sieve seeds calculated as silicon dioxide, alkali and water are mixed according to the following ratio of 1:0.01-0.5:0.01-0.2:0-0.5: mixing at a molar ratio of 1-10;
2) Crystallizing the mixed product;
3) Performing first roasting on the crystallized product obtained in the step 2) to obtain a molecular sieve carrier;
4) Loading active ingredient precursors on the molecular sieve carrier obtained in the step 3) or the carrier containing the molecular sieve carrier by using an impregnation method, and then carrying out second roasting,
the active ingredient precursor is selected from one or more of platinum compounds, palladium compounds and ruthenium compounds.
According to the present invention, by using the template agent of the present invention described below and adding an appropriate amount of molecular sieve seed crystals to provide crystal nuclei, crystallization time can be significantly shortened by controlling the composition of the synthetic gel within the scope of the present invention during synthesis.
In the invention, in the formula, water is used in a very small amount, so that the discharge of waste water can be remarkably reduced.
According to the present invention, in order to further shorten the crystallization time, improve the yield of molecular sieve products, and improve the deoxidizing performance of the catalyst, preferably, a silicon source calculated as silica, a template agent, molecular sieve seeds calculated as silica, alkali, and water are mixed according to a ratio of 1:0.02-0.3:0.03-0.18:0.01-0.3: mixing the components according to the molar ratio of 1-8; more preferably, the silicon source, template, molecular sieve seed, base and water are combined in a ratio of 1:0.05-0.25:0.05-0.15:0.05-0.2: 1-5.
According to the invention, preferably, the silicon source is one or more of white carbon black, silica gel and attapulgite; more preferably, the silicon source is white carbon black or silica gel.
Preferably, according to the present invention, the template is tetrapropylammonium hydroxide. The template agent is tetrapropylammonium hydroxide, and a proper amount of molecular sieve crystal seeds are added to provide crystal nuclei, so that the crystallization time can be obviously shortened and the deoxidization performance of the catalyst can be improved by controlling the composition of the synthesized gel in the range of the invention in the synthesis process.
According to the present invention, the base may be various inorganic bases commonly used in the art, preferably, the base is sodium hydroxide and/or potassium hydroxide.
Preferably, according to the present invention, the molecular sieve seed is a silicalite-1 molecular sieve.
In the preparation process of the molecular sieve, two stages of an induction period and a crystallization period are required. The induction period does not form molecular sieve crystals with a specific topology, but may produce precursors with a certain cyclic structure. These precursors are of vital importance for the synthesis of the final porous material. In the invention, a certain amount of molecular sieve seed crystal is added, and the seed crystal can generate more ready-made precursor in the dissolving process, so that the forming process of the precursor can be directly eliminated, the crystallization time of the whole molecular sieve material is further shortened, and the deoxidizing performance of the catalyst is improved.
The crystallization conditions according to the present invention may be various conditions commonly used in the art. Preferably, the crystallization conditions include: the temperature is 100-230 ℃ and the time is 10-300 minutes; more preferably, the crystallization conditions include: the temperature is 180-220 ℃ and the time is 10-180 minutes; further preferably, the crystallization conditions include: the temperature is 180 to 200℃for 10 to 120 minutes, more preferably 10 to 60 minutes, still more preferably 10 to 30 minutes, still more preferably 10 to 20 minutes, still more preferably 10 to 15 minutes.
In order to further increase the purity of the molecular sieve product according to the present invention, the process preferably further comprises: and (3) before the step (3), carrying out solid-liquid separation, washing and drying on the crystallized product obtained in the step (2).
The solid-liquid separation is not particularly limited, and methods for separating solids from liquids, which are generally used in the art, can be employed, and for example, filtration, centrifugation, and the like can be employed.
The washing liquid is not particularly limited, and for example, deionized water may be used for washing.
The above drying may be carried out, for example, at 90 to 120℃for 1 to 5 hours.
According to the present invention, in step 3), the conditions for the first firing include: the temperature is 500-600 ℃, and the roasting time is 2-10 hours; preferably, the conditions of the first firing include: the temperature is 500-550 ℃, and the roasting time is 2-6 hours.
According to the present invention, preferably, the active ingredient precursor is one or more of chloroplatinic acid, palladium nitrate, palladium chloride and ruthenium chloride.
According to the present invention, preferably, in step 4), the mass ratio of the active ingredient precursor to the molecular sieve carrier is 0.001 to 0.03 in terms of the single mass of the active ingredient: 1, a step of; more preferably, the mass ratio of the active ingredient precursor to the molecular sieve carrier is 0.003 to 0.02 based on the mass of the active ingredient element: 1, a step of; further preferably, the mass ratio of the active ingredient precursor to the molecular sieve carrier is 0.005 to 0.01 in terms of the single mass of the active ingredient: 1.
according to the invention, in step 4), the impregnation is carried out using an active ingredient precursor solution. The solvent in the active ingredient precursor solution may be, for example, water as long as it can dissolve the active ingredient precursor well. Further, the content of the active ingredient precursor in the active ingredient precursor solution is preferably 0.5 to 50% by weight, more preferably 0.1 to 10% by weight.
The impregnation is preferably an isovolumetric impregnation.
According to the present invention, the conditions of the impregnation are not particularly limited as long as the active ingredient precursor can be sufficiently adhered, and preferably the conditions of the impregnation include standing at 20 to 40 c (room temperature) for 1 to 5 hours, preferably 2 to 3 hours.
According to the invention, preferably, the method further comprises: and drying the impregnated carrier after the impregnation. The drying conditions are not particularly limited, and may be, for example, drying at 100 to 180℃for 1 to 10 hours.
According to the present invention, the conditions for the second firing include: the temperature is 350-450 ℃, and the roasting time is 1-5 hours; preferably, the conditions of the second firing include: the temperature is 400-450 ℃, and the roasting time is 2-4 hours.
According to a second aspect of the present invention, there is provided a supported deoxygenation catalyst prepared by the method of preparing a supported deoxygenation catalyst of the first aspect of the present invention.
According to a third aspect of the present invention there is provided the use of the supported deoxygenation catalyst of the second aspect of the present invention in deoxygenation of oxygen-containing organic gases and chemical tail gases.
The present invention will be described in detail by way of examples, but the present invention is not limited to the following examples.
In the examples and comparative examples of the present invention, the room temperature was about 25 ℃.
In the following examples and comparative examples, each of the medicines is commercially available unless otherwise specified.
Example 1
After 10g of white carbon black (silicon source) and 10g of tetrapropylammonium hydroxide (40 wt% aqueous solution) are uniformly mixed, silicalite-1 molecular sieve seed crystal and 1.0g of sodium hydroxide are added and uniformly stirred (the mole ratio of silicon source to template agent to molecular sieve seed crystal to alkali to water is 1:0.12:0.05:0.15:2 based on silicon dioxide), the mixture is transferred to a stainless steel reaction kettle or a stainless steel tube with a polytetrafluoroethylene lining, and crystallized for 10min at 200 ℃. And after crystallization, washing the obtained product with deionized water and centrifugally separating, removing water, and drying at 100 ℃. Then roasting at 550 ℃ for 5 hours, and XRD results show that the all-silicon silicalite-1 molecular sieve is prepared.
The method comprises the steps of impregnating a chloroplatinic acid aqueous solution into a baked silicalite-1 molecular sieve (Pt is calculated according to the mass ratio of a simple substance) to a molecular sieve carrier to be 0.005:1) by using an isovolumetric impregnation method, standing for 2 hours at room temperature, drying at 150 ℃ for 5 hours to remove water, and roasting the obtained solid material at 400 ℃ for 3 hours to obtain the supported deoxidizing catalyst.
In a propylene feed gas having an oxygen content of 3% by volume, a pressure of 0.3MPa, a temperature of 250℃and a volume space velocity of 3000h -1 Under the condition of carrying out deoxidation reaction of oxygen-containing organic gas, detecting that the oxygen content of outlet gas is less than 0.1 volume percent.
Example 2
After 10g of white carbon black (silicon source) and 10g of tetrapropylammonium hydroxide (20 wt% aqueous solution) are uniformly mixed, silicalite-1 molecular sieve seed crystal and 1.0g of sodium hydroxide are added and uniformly stirred (the mole ratio of silicon source, template agent, molecular sieve seed crystal, alkali and water is 1:0.06:0.05:0.15:2.7, respectively) calculated by silicon dioxide, and then the mixture is transferred into a stainless steel reaction kettle or a stainless steel tube with a polytetrafluoroethylene lining, and crystallized for 10 minutes at 200 ℃. And after crystallization, washing the obtained product with deionized water and centrifugally separating, removing water, and drying at 100 ℃. Then roasting at 550 ℃ for 5 hours, and XRD results show that the all-silicon silicalite-1 molecular sieve is prepared.
The method comprises the steps of impregnating a chloroplatinic acid aqueous solution into a baked silicalite-1 molecular sieve (Pt is calculated according to the mass ratio of a simple substance) to a molecular sieve carrier to be 0.01:1) by using an isovolumetric impregnation method, standing for 2 hours at room temperature, drying at 150 ℃ for 5 hours to remove water, and roasting the obtained solid material at 600 ℃ for 3 hours to obtain the supported deoxidizing catalyst.
In a propylene feed gas with an oxygen content of 5% by volume, a pressure of 0.4MPa, a temperature of 230℃and a volume space velocity of 5000h -1 Under the condition of carrying out deoxidation reaction of oxygen-containing organic gas, detecting that the oxygen content of outlet gas is less than 0.2 volume percent.
Example 3
After 15g of fine silica gel (silicon source) and 15g of tetrapropylammonium hydroxide (30 wt% aqueous solution) were uniformly mixed, silicalite-1 molecular sieve and 0.6g of sodium hydroxide were added and uniformly stirred (the mole ratio of silicon source, template agent, molecular sieve seed crystal, alkali and water calculated as silica is 1:0.09:0.07:0.06:2.3), and the mixture was left standing at room temperature for 10 hours, transferred to a stainless steel reaction kettle or stainless steel reactor equipped with polytetrafluoroethylene lining, and crystallized at 180 ℃ for 60 minutes. And after crystallization, washing the obtained product with deionized water and centrifugally separating, removing water, and drying at 100 ℃. Then roasting for 3 hours at 550 ℃, and XRD results show that the silicalite-1 molecular sieve is prepared.
The method comprises the steps of impregnating a baked silicalite-1 molecular sieve (Pd (based on the mass of a single substance) with a molecular sieve carrier in a mass ratio of 0.008:1) by using an isovolumetric impregnation method, standing for 2 hours at room temperature, drying at 150 ℃ for 5 hours to remove water, and roasting the obtained solid material at 500 ℃ for 3 hours to obtain the supported deoxidizing catalyst.
In chloropropene feed gas with 3 volume percent of oxygen, the pressure is 0.3MPa, the temperature is 250 ℃ and the volume space velocity is 5000h -1 Under the condition of carrying out deoxidation reaction of oxygen-containing organic gas, detecting that the oxygen content of outlet gas is less than 0.1 volume percent.
Example 4
After 15g of fine silica gel (silicon source) and 15g of tetrapropylammonium hydroxide (40 wt% aqueous solution) were uniformly mixed, silicalite-1 molecular sieve and 0.6g of sodium hydroxide were added and uniformly stirred (the mole ratio of silicon source, template agent, molecular sieve seed crystal, alkali and water calculated as silica is 1:0.12:0.07:0.06:2), and the mixture was left standing at room temperature for 10 hours, transferred to a stainless steel reaction kettle or stainless steel reactor equipped with a polytetrafluoroethylene liner, and crystallized at 180 ℃ for 60 minutes. And after crystallization, washing the obtained product with deionized water and centrifugally separating, removing water, and drying at 100 ℃. Then roasting for 3 hours at 550 ℃, and XRD results show that the silicalite-1 molecular sieve is prepared.
The method comprises the steps of impregnating a baked silicalite-1 molecular sieve (Pd (based on the mass of a single substance) with a molecular sieve carrier in a mass ratio of 0.01:1) by using an isovolumetric impregnation method, standing for 2 hours at room temperature, drying at 150 ℃ for 5 hours to remove water, and roasting the obtained solid material at 400 ℃ for 3 hours to obtain the supported deoxidizing catalyst.
In chloropropene feed gas with 3 volume percent of oxygen, the pressure is 0.3MPa, the temperature is 250 ℃ and the volume space velocity is 5000h -1 Under the condition of carrying out deoxidation reaction of oxygen-containing organic gas, detecting that the oxygen content of outlet gas is less than 0.15 volume percent.
Example 5
After mixing 15g of fine silica gel (silicon source) with 30g of tetrapropylammonium hydroxide (25 wt% aqueous solution) uniformly, adding silicalite-1 molecular sieve seed crystal and 2.0g of potassium hydroxide and stirring uniformly (silicon source calculated as silicon dioxide, template agent calculated as silicon dioxide)The mole ratio of the molecular sieve seed crystal, the alkali and the water is 1:0.15:0.03:0.2: 5) Transferring into stainless steel tube, and crystallizing at 200deg.C for 20min. And after crystallization, washing the obtained product with deionized water and centrifugally separating, removing water, and drying at 100 ℃ overnight. Then roasting at 550 ℃ for 5 hours to obtain the molecular sieve, and obtaining the molecular sieve through XRD and N 2 Adsorption results show that the all-silicon silicalite-1 molecular sieve with an open structure is prepared.
Impregnating a ruthenium chloride aqueous solution into a baked silicalite-1 molecular sieve (Ru (based on the mass of the single substance) and a molecular sieve carrier in a mass ratio of 0.01:1) by using an isovolumetric impregnation method, standing for 2 hours at room temperature, drying at 150 ℃ for 5 hours to remove water, and roasting the obtained solid material at 400 ℃ for 3 hours to obtain the supported deoxidizing catalyst.
In chloropropene feed gas with 3 volume percent of oxygen, the pressure is 0.3MPa, the temperature is 260 ℃ and the volume space velocity is 3000h -1 Under the condition of carrying out deoxidation reaction of oxygen-containing organic gas, detecting that the oxygen content of outlet gas is less than 0.2 volume percent.
Example 6
10g of fine silica gel (silicon source), 15g of tetrapropylammonium hydroxide (40 wt% aqueous solution), silicalite-1 molecular sieve seed crystal and 1.0g of sodium hydroxide were uniformly mixed in a mortar (molar ratio of silicon source, template agent, molecular sieve seed crystal, alkali and water calculated as silica: 1:0.18:0.15:0.15:3) and then transferred to a stainless steel tube, and crystallized at 200℃for 60 minutes. And after crystallization, washing the obtained product with deionized water and centrifugally separating, removing water, and drying at 100 ℃ overnight. Then roasting at 550 ℃ for 8 hours to obtain the molecular sieve, and obtaining the molecular sieve through XRD and N 2 Adsorption results show that the all-silicon silicalite-1 molecular sieve with an open structure is prepared.
The method comprises the steps of impregnating a baked silicalite-1 molecular sieve (Pd (based on the mass of a single substance) with a molecular sieve carrier in a mass ratio of 0.001:1) by using an isovolumetric impregnation method, standing for 2 hours at room temperature, drying at 150 ℃ for 5 hours to remove water, and roasting the obtained solid material at 550 ℃ for 3 hours to obtain the supported deoxidizing catalyst.
In chloropropene feed gas with 3 volume percent of oxygen, the pressure is 0.3MPa, the temperature is 260 ℃ and the volume space velocity is 3000h -1 Under the condition of carrying out deoxidation reaction of oxygen-containing organic gas, detecting that the oxygen content of outlet gas is less than 0.2 volume percent.
Example 7
After 15g of fine silica gel (silicon source) and 8g of tetrapropylammonium hydroxide (40 wt% aqueous solution) were uniformly mixed, silicalite-1 molecular sieve seed crystal was added and stirred uniformly (the molar ratio of silicon source, template agent, molecular sieve seed crystal and water calculated as silicon dioxide is 1:0.06:0.13:1.07), transferred to a stainless steel reaction kettle or stainless steel tube equipped with polytetrafluoroethylene lining, and crystallized at 200 ℃ for 15min. And after crystallization, washing the obtained product with deionized water and centrifugally separating, removing water, and drying at 100 ℃. Then roasting at 550 ℃ for 5 hours to obtain the molecular sieve, and obtaining the molecular sieve through XRD and N 2 Adsorption results show that the all-silicon silicalite-1 molecular sieve with an open structure is prepared.
The method comprises the steps of impregnating a palladium chloride aqueous solution with a certain concentration into a roasted silicalite-1 molecular sieve (Pd (based on the mass of the single substance) and a molecular sieve carrier in a mass ratio of 0.01:1) by using an isovolumetric impregnation method, standing for 2 hours at room temperature, drying at 150 ℃ for 5 hours to remove water, and roasting the obtained solid material at 550 ℃ for 3 hours to obtain the supported deoxidizing catalyst.
In a propylene raw material gas with 5 volume percent of oxygen, the pressure is 0.4MPa, the temperature is 250 ℃ and the volume airspeed is 3000-5000h -1 Under the condition of carrying out deoxidation reaction of oxygen-containing organic gas, detecting that the oxygen content of outlet gas is less than 0.1 volume percent.
Comparative example 1
After 10g of white carbon black and 1.0g of tetrapropylammonium hydroxide (40 wt% aqueous solution) are uniformly mixed, 1.0g of sodium hydroxide is added and uniformly stirred, and the mixture is transferred into a stainless steel reaction kettle or a stainless steel tube with a polytetrafluoroethylene lining and crystallized for 10min at 200 ℃. And after crystallization, washing the obtained product with deionized water and centrifugally separating, removing water, and drying at 100 ℃. Then calcined at 550 c for 5 hours, the XRD result showed that all-silicon silicalite-1 molecular sieve having an open structure could not be obtained.
The method comprises the steps of impregnating a chloroplatinic acid aqueous solution into a baked silicalite-1 molecular sieve (Pt is calculated according to the mass ratio of a simple substance) to a molecular sieve carrier to be 0.005:1) by using an isovolumetric impregnation method, standing for 2 hours at room temperature, drying at 150 ℃ for 5 hours to remove water, and roasting the obtained solid material at 400 ℃ for 3 hours to obtain the supported deoxidizing catalyst.
In a propylene feed gas having an oxygen content of 3% by volume, a pressure of 0.3MPa, a temperature of 250℃and a volume space velocity of 3000h -1 Under the condition of carrying out deoxidation reaction of oxygen-containing organic gas, detecting that the oxygen content of outlet gas is more than 0.2 volume percent.
Comparative example 2
After 10g of white carbon black and 1.0g of tetrapropylammonium hydroxide (40 wt% aqueous solution) are uniformly mixed, 15g of sodium hydroxide is added and uniformly stirred, and the mixture is transferred into a stainless steel reaction kettle or a stainless steel tube with a polytetrafluoroethylene lining, and crystallized for 10min at 200 ℃. And after crystallization, washing the obtained product with deionized water and centrifugally separating, removing water, and drying at 100 ℃. Then calcined at 550 c for 5 hours, the XRD results showed that no all-silica silicalite-1 molecular sieve could be obtained.
The method comprises the steps of impregnating a chloroplatinic acid aqueous solution into a baked silicalite-1 molecular sieve (Pt is calculated according to the mass ratio of a simple substance) to a molecular sieve carrier to be 0.005:1) by using an isovolumetric impregnation method, standing for 2 hours at room temperature, drying at 150 ℃ for 5 hours to remove water, and roasting the obtained solid material at 400 ℃ for 3 hours to obtain the supported deoxidizing catalyst.
In a propylene feed gas having an oxygen content of 3% by volume, a pressure of 0.3MPa, a temperature of 250℃and a volume space velocity of 3000h -1 Under the condition of carrying out deoxidation reaction of oxygen-containing organic gas, detecting that the oxygen content of outlet gas is more than 0.3 volume percent.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (15)
1. A preparation method of a supported deoxidizing catalyst is characterized by comprising the following steps,
1) A silicon source calculated as silicon dioxide, a template agent, molecular sieve seeds calculated as silicon dioxide, alkali and water are mixed according to the following ratio of 1:0.01-0.5:0.01-0.2:0-0.5: mixing at a molar ratio of 1-10;
2) Crystallizing the mixed product;
3) Performing first roasting on the crystallized product obtained in the step 2) to obtain a molecular sieve carrier;
4) Loading active ingredient precursors on the molecular sieve carrier obtained in the step 3) or the carrier containing the molecular sieve carrier by using an impregnation method, and then carrying out second roasting,
the active ingredient precursor is selected from one or more of platinum compounds, palladium compounds and ruthenium compounds.
2. The method of claim 1, wherein the silicon source, template, molecular sieve seed, base and water are combined in a ratio of 1:0.02-0.3:0.03-0.18:0-0.25: 1-8.
3. The method of claim 1, wherein the silicon source is one or more of white carbon black, silica gel, and attapulgite.
4. A method according to any one of claims 1 to 3, wherein the templating agent is tetrapropylammonium hydroxide.
5. A process according to any one of claims 1 to 3, wherein the base is sodium hydroxide and/or potassium hydroxide.
6. A process according to any one of claims 1 to 3 wherein the molecular sieve seed is a silicalite-1 molecular sieve.
7. A method according to any one of claims 1-3, wherein the crystallization conditions include: the temperature is 100-230 ℃ and the time is 10-300 minutes.
8. A method according to any one of claims 1-3, wherein the method further comprises: and (3) before the step (3), carrying out solid-liquid separation, washing and drying on the crystallized product obtained in the step (2).
9. A method according to any one of claims 1-3, wherein the conditions of the first firing include: the temperature is 500-600 ℃, and the roasting time is 2-10 hours.
10. A method according to any one of claims 1-3, wherein the conditions of the second firing include: the temperature is 350-450 ℃, and the roasting time is 1-5 hours.
11. A method according to any one of claims 1-3, wherein the impregnation method is an isovolumetric impregnation.
12. A method according to any one of claims 1 to 3, wherein the mass ratio of the active ingredient precursor to the molecular sieve support is 0.001 to 0.03, based on the mass of the active ingredient element: 1.
13. a method according to any one of claims 1 to 3, wherein the active ingredient precursor is one or more of chloroplatinic acid, palladium nitrate, palladium chloride and ruthenium chloride.
14. A supported deoxidizing catalyst prepared by the method of any one of claims 1 to 10.
15. Use of the supported deoxygenation catalyst of claim 13 in deoxygenation of oxygen-containing organic gases and chemical tail gases.
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