CN112916039B - Gaseous hydrocarbon catalytic oxidation deoxidation Pt/Beta catalyst and preparation and application thereof - Google Patents
Gaseous hydrocarbon catalytic oxidation deoxidation Pt/Beta catalyst and preparation and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
Abstract
The invention relates to a gaseous hydrocarbon catalytic oxidation deoxidation Pt/Beta catalyst and a preparation and application method thereof. According to the catalyst provided by the invention, platinum is doped in the framework structure of the Beta molecular sieve crystal in a single atom form, and the catalyst has the advantages of high reaction activity, good stability, repeated use and the like in the catalytic oxidation and deoxidation reaction process of gaseous hydrocarbons. The preparation method of the catalyst provided by the invention has the advantages of simple steps, good controllability and low-cost preparation. The application method can efficiently realize the deoxidation and inerting of the gas in the top space of the oil tank, and is a novel and efficient oil tank inerting technical approach.
Description
Technical Field
The invention relates to a gaseous hydrocarbon catalytic oxidation deoxidation catalyst and a preparation and application method thereof, belonging to the technical field of catalytic inerting of aircraft fuel tanks.
Background
In the flying process of the airplane, fuel oil is gradually consumed, external air enters the oil tank, and the space above the liquid level in the oil tank is filled with fuel oil saturated steam mainly containing light hydrocarbon to form an inflammable and explosive gas mixture. When the oil tank encounters danger factors such as shrapnel breakdown, sparks, lightning, local heating and the like, the kerosene and steam mixture can explode and seriously threaten the safety of the airplane. In 1996, TWA800 caused the aircraft to explode due to the fire on the center tank, resulting in the loss of life of all 230 full aircraft. The statistical results of 3726 civil aircraft accidents all over the world from 1966 to 2009 by the technical team of cabin safety research show that 370 accidents are related to fuel tank combustion and explosion. In view of this, inerting the gas in the headspace of the tank to reduce the oxygen content below the limits of combustion and explosion is an inevitable requirement for ensuring aircraft safety.
There are many technical approaches for inerting the fuel tank, for example, means such as carrying halon 1301 or filling the fuel tank with liquid nitrogen as an inerting gas, filling an explosion suppression foam in the fuel tank, arranging an explosion suppression metal barrier, performing onboard pressure swing adsorption or cryogenic air separation to produce nitrogen, etc., however, these methods have the disadvantages of heavy weight, high cost, complex maintenance procedure, etc. At present, an On-Board Inert Gas Generator System (OBIGGS) technology for online preparing nitrogen-rich Gas by using a hollow fiber membrane is basically mature, has the advantages of small volume, light weight and the like, and becomes a widely used aircraft fuel tank inerting technology. However, the technology still has many problems, such as large aircraft compensation loss, high pressure required by a separation membrane inlet, which results in that a plurality of types cannot be used (such as helicopters), small membrane fiber channels and permeation pore diameters are gradually blocked, ozone in an air source causes severe attenuation of membrane performance, light hydrocarbon leakage pollution is caused when a nitrogen-rich gas replaces an oil tank, and the like.
In view of the above problems, white-peterson air force base, honeywell and pyre have jointly developed "Green inerting technology" (GOBIGGS) from 2006. The process is to introduce light hydrocarbon mixed gas and supplementary air in the gas phase space of the upper part of the oil tank into a catalytic oxidation reactor for catalytic oxidation, convert oxygen into carbon dioxide and water vapor to remove oxygen, and the reacted gas is sent into the oil tank to reduce the oxygen content of the oil tank and realize inerting of the oil tank through cyclic replacement. This technique has obvious advantages: the volume is small and the weight is light; air is not required to be introduced from an engine, compensation loss is small, and the method can be applied to occasions without proper air sources (such as a helicopter); the starting speed is high, the inerting efficiency is high, and the replacement speed is high; does not discharge kerosene steam, is green and environment-friendly, and greatly reduces the loss of light components of the kerosene compared with a nitrogen replacement mode.
In the green inerting technology (GOBIGGS), the catalytic oxidation catalyst is the core of its technology. The type and formulation of the catalyst used in this technique has not been reported in the open literature. The basic catalyst formulation was explored at Zhejiang university, but there was littleThe use of Pt/M-ZSM-5 as an aircraft fuel tank inerting catalyst has been disclosed only in 1 patent (CN 201711079914.1). The catalyst is prepared by using Pt (NH)3)4Cl2The mesoporous ZSM-5 molecular sieve is impregnated by the solution, and the impregnation treatment is disclosed in the literature (spring rain, Pt-loaded Volatile Organic Compounds (VOCs) catalytic elimination of zeolite molecular sieves, Ph. university of Zhejiang, 2015.). The catalyst is designed for catalyzing and eliminating VOCs, platinum is in a nano-scale or even micro-scale particle state, the atomic utilization rate is poor, and the catalyst is mainly used for eliminating organic matters, so that the adsorption and conversion performance of the organic matters are mainly emphasized. The inerting process of the oil tank faces to the catalytic oxidation and deoxidation of light hydrocarbon, and aims to remove oxygen, so that the catalyst is required to have strong oxygen adsorption and conversion capacity. The adsorption and activation of oxygen require higher dispersion degree of active metal, and the distribution state of the active metal is preferably realized at the monatomic level, which cannot be realized by catalyst preparation methods such as a common impregnation method, a deposition and precipitation method and the like.
In order to solve the technical problems, the invention provides that platinum is embedded into a framework structure of the Beta type molecular sieve crystal in an in-situ synthesis mode, so that the platinum element realizes monoatomic level distribution, and the activation and full reaction of oxygen are realized. This structure has a strong metal-support interaction, which allows the monoatomic state of the noble metal to be maintained. The Beta type molecular sieve has three-dimensional crossed straight channel micropores, and the diameter of the micropores is larger than that of ZSM-5, so that the diffusion and the reaction of light hydrocarbon raw materials at low temperature are facilitated, the low-temperature activity is improved, and coking and carbon generation are not easy to occur. Therefore, the catalyst provided by the patent has good reaction activity and stability, and is expected to meet the technical requirement of fuel tank inerting application.
Disclosure of Invention
The invention aims to provide a gaseous hydrocarbon catalytic oxidation deoxidation catalyst and preparation and application methods thereof. By utilizing the catalyst and the application method provided by the invention, light hydrocarbon in the space above the aircraft oil tank can be subjected to catalytic oxidation reaction, oxygen in the gas in the oil tank is rapidly removed to the safe explosion-proof level below 9 mol%, the low oxygen content level below 3 mol% can be realized, and the safety of the oil tank is improved. The preparation method of the catalyst provided by the invention is simple and reliable, and low-cost production of the catalyst is expected to be realized. The invention can provide a catalyst preparation and application scheme for the fuel tank inerting technology of a new generation of airplane.
In order to achieve the purpose, the technical scheme of the invention is as follows:
one aspect of the present invention provides a catalytic oxidation and deoxygenation catalyst for gaseous hydrocarbons:
the catalyst is Pt/Beta; beta is a Beta type molecular sieve; pt is platinum, the platinum is doped in a framework structure of the Beta molecular sieve crystal in a monatomic form, and the existing state of the platinum is one or two of an ionic state or an oxide; in the catalyst, the mass content of platinum is 0.1-1.5%; the silicon-aluminum atomic ratio of the Beta-type molecular sieve, i.e., Si/Al, is 15-40.
In another aspect, the invention provides a method for preparing a gaseous hydrocarbon catalytic oxidation deoxygenation catalyst, which comprises the following steps:
the preparation of the catalyst comprises the following steps:
the Pt/Beta molecular sieve is prepared by adopting a direct synthesis mode. The aluminum source and the silicon source are necessary synthetic raw materials, the aluminum source is one or more than two of sodium metaaluminate, aluminum nitrate, aluminum isopropoxide and aluminum sol, and the silicon source is one or more than two of silica sol, sodium silicate, water glass, tetraethyl silicate, silica aerogel and white carbon black.
1) Preparing crystallized colloid:
tetraethylammonium hydroxide, namely TEAOH is used as a template agent; mixing an aluminum source, sodium hydroxide, TEAOH, tetraammineplatinum hydroxide and deionized water according to the proportion of n Na2O:Al2O3:t TEAOH:y Pt:l H2Mixing O in proportion, and stirring for 10-30 min until all O is dissolved, wherein n is 1-5, t is 2-6, y is 0.01-0.2, and l is 50-200;
adding silicon source or silicon source and proper amount of deionized water into the solution to form composition of xNa2O:Al2O3:s SiO2:t TEAOH:y Pt:h H2And (3) fully stirring the colloidal mixture of O for 30-60 minutes, and transferring the mixture into a closed reaction kettle. Wherein x is 1-5, s is 30-80, t is 2-6, y is 0.01-0.2, and h is 70-200.
2) Crystallizing a molecular sieve:
and (3) placing the closed synthesis kettle filled with the crystallized colloid into an oven, heating the closed synthesis kettle from room temperature to 120-fold-class 160 ℃ at the speed of 1-5 ℃/min, crystallizing for 12-96 hours under autogenous pressure, cooling the closed synthesis kettle from the crystallization temperature to room temperature at the speed of 120-fold-class 200 ℃/min, performing solid-liquid separation in a centrifugal separation mode, fully washing a solid product by using deionized water until the pH value is less than 9, and drying the obtained solid product for 6-24 hours at the temperature of 100-fold-class 130 ℃ to obtain the Pt/Na-Beta molecular sieve raw powder.
3) After-treatment of the molecular sieve:
transferring the Pt/Na-Beta molecular sieve raw powder into a muffle furnace, and heating the Pt/Na-Beta-cal molecular sieve raw powder from room temperature to 500-700 ℃ at the speed of 2-5 ℃/min in an air environment to obtain the calcined Pt/Na-Beta-cal molecular sieve. Mixing Pt/Na-Beta-cal molecular sieve with 0.6-1.2mol/L NH4NO3And (3) mixing the solutions according to a solid-to-liquid ratio of 1g (10-20) mL, heating to 70-90 ℃ under the stirring condition, continuously stirring at the temperature, keeping for 0.5-5 hours, cooling, performing centrifugal separation, and fully washing a solid product with deionized water. Drying the product at 100-120 deg.C for 6-12 h to obtain ammonium-exchange-treated Pt/NH4-Beta molecular sieves. Mixing Pt/NH4Putting the Beta molecular sieve into a muffle furnace, raising the temperature to 450-600 ℃ at the temperature rise speed of 1-5 ℃/min, and roasting at constant temperature in the air atmosphere for 2-5 hours to obtain the Pt/Beta molecular sieve.
4) Catalyst forming and activating:
tabletting, molding, crushing and screening the Pt/Beta molecular sieve powder to prepare a particle catalyst with 20-40 meshes; or, the catalyst is molded by extruding; or mixing the molecular sieve with polyethylene glycol, alumina sol and deionized water, ball-milling to obtain slurry, coating the slurry on a honeycomb ceramic carrier with 100-2000 pores, and roasting at 400-600 ℃ to obtain the honeycomb monolithic catalyst.
The calcined formed catalyst can be directly placed into a reactor for use, and the catalyst can also be activated before reaction so as to improve the initial activity of the catalyst. The process of the activation treatment is as follows: putting the formed catalyst into a proper reactor, introducing hydrogen or a mixed gas of hydrogen and inert gas, wherein the inert gas is one or more than two of nitrogen, helium and argon, the molar concentration of the hydrogen in the mixed gas is 5-99%, heating from room temperature to 550 ℃ at the heating rate of 1-10 ℃/min, stopping heating after activating for 1-3 hours, and naturally cooling to room temperature in the activating atmosphere to obtain the activated catalyst.
The third aspect of the invention provides an application method of the gaseous hydrocarbon catalytic oxidation deoxidation catalyst, which comprises the following steps:
the prepared Pt/Beta catalyst is used for catalytic oxidation and deoxidation reaction of gaseous hydrocarbons. The gaseous hydrocarbon is a gas phase substance in a space above the liquid level in a container for storing kerosene, and comprises air and volatile gaseous hydrocarbon; the kerosene is one or more of RP-3 kerosene, rocket kerosene or high-density synthetic kerosene.
In the catalytic oxidation and deoxidation reaction process of gaseous hydrocarbons, the catalyst is used in the form of one of a fixed bed formed by filling granular catalyst obtained by tabletting or extruding into strips in a reactor, or a monolithic bed formed by placing honeycomb monolithic catalyst in a reactor. Typical reaction conditions are: the volume space velocity (GHSV) of the gaseous hydrocarbon raw material passing through the catalyst bed layer is 300-10000h-1(ii) a The reaction temperature is 150-350 ℃; the pressure of the reaction system is 0.1-2 MPa.
The active component of the gaseous hydrocarbon catalytic oxidation deoxidation catalyst provided by the invention is monatomic platinum embedded in a molecular sieve framework structure, and the catalyst has the advantages of high reaction activity, good stability, repeated use and the like in the process of the gaseous hydrocarbon catalytic oxidation deoxidation reaction. The preparation method of the catalyst provided by the invention has the advantages of good controllability, simple steps and easy realization, and is expected to realize low-cost synthesis preparation. The application method can efficiently realize the gas deoxidation inerting of the top space of the aircraft oil tank, and is a novel and efficient oil tank inerting technical approach.
The flow of the reaction evaluating apparatus for verifying the technical scheme of the present invention is shown in fig. 1. Inert purge gas or supplementary air is filled in the gas bottle, the gas is decompressed by a decompression valve, the flow of the gas is regulated by a flowmeter, and the gas enters a reactor. The upper part of the liquid level of the oil tank is in a gas stateThe hydrocarbon, the oxygen content in which is monitored by the oxygen sensor (c) in real time. The gaseous hydrocarbons are pumped out by an air pump, and enter the tubular reactor after the flow is regulated by a flow meter. The periphery of the reactor is provided with a heating furnace (R) for providing a proper reaction temperature environment for the reactor, and the catalyst bed (Nc) is positioned in a constant temperature section in the middle of the reactor. The reaction material is subjected to catalytic oxidation reaction on a catalyst, oxygen in the reaction material is consumed, products such as carbon dioxide, carbon monoxide and water are generated, and the reacted material passes through a condenser
Cooling and storing in a low-temperature liquid storage device
Is separated into a gas phase product and a liquid phase product, and the liquid phase product is mainly condensed water. The gas product passes through a dryer
Returning to the upper space of the oil tank, in the dryer
An oxygen sensor is arranged on the downstream pipeline
The oxygen content in the product after the reaction was monitored.
Drawings
FIG. 1 is a schematic flow diagram of an evaluation device for catalytic oxidation and deoxidation reactions of gaseous hydrocarbons;
air cylinder, pressure reducing valve, flowmeter, oil tank, oxygen sensor, air pump, flowmeter, reactor, catalyst bed and heating furnace,
a condenser, a condenser and a water-cooling device,
a low-temperature liquid storage device is arranged on the upper portion of the shell,
a drying device is arranged in the drying device,
an oxygen sensor.
Detailed Description
The present invention is further illustrated by the following examples, but the present invention is not limited to these examples.
Example 1:
preparing a catalyst:
1) preparing crystallized colloid:
adding 9g of sodium metaaluminate, 8g of sodium hydroxide, 65mL of TEAOH solution (concentration 25%), 0.75g of tetraammineplatinum hydroxide and 36g of deionized water into a 500mL plastic beaker, and mechanically stirring at 200rpm for 20 minutes to form a clear solution; taking 126g of white carbon black and 12g of deionized water, slowly adding the white carbon black and the deionized water into a beaker, and continuously mechanically stirring the mixture at the rotating speed of 200rpm for 30 minutes to form a molar composition of 3Na2O:Al2O3:42SiO2:2.2TEAOH:0.05Pt:110H2Homogeneous colloid of O.
2) Crystallizing a molecular sieve:
the molecular sieve crystallization colloid is placed in a stainless steel synthesis kettle, a kettle cover is sealed, the kettle cover is placed in a drying oven with a rotary support, a rotary motor is started, the synthesis kettle makes circular motion at the rotating speed of 60rpm, and the molecular sieve crystallization colloid is ensured to be heated uniformly. Heating to 145 ℃ at the heating rate of 2 ℃/min, crystallizing for 48 hours under autogenous pressure, quenching and cooling, performing solid-liquid separation in a centrifugal separation mode, fully washing a solid product by using deionized water until the pH value is less than 9, and drying the obtained solid product for 12 hours at the temperature of 110 ℃ to obtain the Pt/Na-Beta molecular sieve raw powder.
3) After-treatment of the molecular sieve:
taking 15g of Pt/Na-Beta molecular sieve raw powder, putting the raw powder into a 250mL beaker, and adding 180mL of 0.8mol/L NH4NO3Heating the solution to 75 deg.C under electromagnetic stirring at 100rpm, continuously stirring at the temperature for 2 hr, cooling, centrifuging, and separating the solid with deionized waterThe product was washed thoroughly. The product was dried at 120 ℃ for 10 hours to obtain ammonium-exchanged Pt/NH4-Beta molecular sieves.
Mixing Pt/NH4And putting the Beta molecular sieve into a muffle furnace, raising the temperature to 500 ℃ at a heating rate of 2 ℃/min, and roasting for 3 hours at a constant temperature in an air atmosphere to obtain the Pt/Beta molecular sieve. By XRD detection and analysis, main peaks are positioned at 8.0,21.4,22.3,26.8 and 29.2 degrees in an X-ray diffraction pattern of the crystal, which shows that the crystal form is a Beta type molecular sieve; no diffraction peak of Pt metal or its oxide appeared, indicating that Pt is highly dispersed in the molecular sieve. The EXAFS and spherical aberration correction-high resolution transmission electron microscope characterization results show that Pt is distributed in a single atom level. By XRF analysis, the mass content of Pt in the molecular sieve is 0.35%.
4) And (3) catalyst molding:
the Pt/Beta molecular sieve powder is pressed into tablets, crushed and sieved to prepare the particle catalyst with the particle size of 20-40 meshes, and the particle catalyst is marked as catalyst A.
Evaluation of catalytic oxidative deoxygenation reaction of gaseous hydrocarbons:
7.5g of the catalyst A was charged in the reactor of the apparatus shown in FIG. 1, and a 5L-sealed container in which 2L of RP-3 kerosene was placed was used as the oil tank, and the oxygen content in the gas phase was 20.5 mol% in the initial state. Under the condition of nitrogen purging of 0.3L/min, the temperature of the reactor is raised to 180 ℃ at the heating rate of 10 ℃/min, after the temperature fluctuation of the reactor is less than +/-2 ℃, the nitrogen purging is stopped, an air pump is started, the gaseous hydrocarbons above the liquid level in the oil tank are introduced into the reaction bed at the flow rate of 0.5L/min, and the conversion is carried out for 2000h-1The reaction pressure is 0.1MPa at normal pressure. The oxygen content measured in the tail gas after 2min of aeration was 1.9 mol%, and the deoxygenation conversion was 91%. And (3) continuously introducing the tail gas back to the oil tank, wherein the oxygen content in the space above the oil tank is reduced to below 9 mol% (reaching the explosion-proof oxygen content control limit of the existing oil tank) after 6.5min, and the oxygen content in the space above the oil tank is reduced to below 2.3 mol% after 20 min.
Example 2:
preparing a catalyst:
the catalyst preparation procedure of example 1 was repeated, 7.5g of the catalyst a was placed in the reactor of the apparatus shown in fig. 1, a mixed gas of hydrogen and nitrogen was introduced, the molar concentration of hydrogen in the mixed gas was 30%, the flow rate of gas introduction was 0.3L/min, the temperature was raised to 500 ℃ at a rate of 5 ℃/min, the heating was stopped for 1 hour of activation, and the temperature was naturally lowered to room temperature in a mixed atmosphere of hydrogen and nitrogen, to obtain an activated catalyst B.
Evaluation of catalytic oxidative deoxygenation reaction of gaseous hydrocarbons:
the reaction evaluation procedure of example 1 was repeated except that the catalyst loading process was omitted. The oxygen content measured in the tail gas after the gaseous hydrocarbon is introduced for 2min is 0.8 mol%, and the deoxygenation conversion rate is 96%. After 5.6min, the oxygen content in the space above the oil tank is reduced to below 9 mol%, and after 20min, the oxygen content in the space above the oil tank is reduced to below 1.6 mol%.
Example 3:
preparing a catalyst:
the catalyst preparation procedure of example 1 was repeated except that the molecular sieve powder of step 4) was extruded into a rod and calcined at 550 ℃ to a diameter
Catalyst C was recorded as a stripe having a length of 2.0. + -. 0.2 mm.
Evaluation of catalytic oxidative deoxygenation reaction of gaseous hydrocarbons:
the reaction evaluation procedure of example 1 was repeated by charging 10g of catalyst C into the reactor of the apparatus shown in FIG. 1. The oxygen content measured in the tail gas after the gaseous hydrocarbon is introduced for 2min is 2.1 mol%, and the deoxygenation conversion rate is 90%. After 6.9min, the oxygen content in the space above the oil tank is reduced to below 9 mol%, and after 20min, the oxygen content in the space above the oil tank is reduced to below 2.2 mol%.
Example 4:
preparing a catalyst:
the catalyst preparation procedure of example 1 was repeated except that the silicon source of the Pt/Na-Beta molecular sieve was changed to tetraethyl silicate (TEOS) and the synthetic colloidal molar composition was: 2.3Na2O:Al2O3:60TEOS:2.2TEAOH:0.05Pt:120H2And O, the crystallization temperature is 140 ℃, and the crystallization time is 36 h. The Pt/Beta catalyst is prepared by the method,wherein the mass content of Pt is 0.25%, tabletting, molding, and crushing into 20-40 mesh particles, which is marked as catalyst D.
Evaluation of catalytic oxidative deoxygenation reaction of gaseous hydrocarbons:
the reaction evaluation procedure of example 1 was repeated by charging 7.5g of catalyst D into the reactor of the apparatus shown in FIG. 1. The oxygen content measured in the tail gas 2.6 mol% after kerosene vapor was introduced for 2min, and the deoxygenation conversion was 87%. After 7.5min, the oxygen content in the space above the oil tank is reduced to below 9 mol%, and after 20min, the oxygen content in the space above the oil tank is reduced to below 2.6 mol%.
Example 5:
using the catalyst A prepared in example 1 and a catalyst loading of 15g, the reaction evaluation procedure in example 1 was repeated except that the flow rate of the introduced gaseous hydrocarbon was changed to 1.66L/min and the reduced reaction space velocity was 5000 hours-1The reaction temperature was changed to 215 ℃. Repeated investigation is carried out for many times, the upper space of the oil tank is aerated before each evaluation, and the initial oxygen content reaches 20.5 mol%. The evaluation time is 20min each time, the evaluation process is repeated 6 times, the catalyst is not regenerated in the middle, and the main reaction results are shown in table 1.
TABLE 1 Cyclic utilization Properties of the catalytic Oxidation deoxygenation catalyst for gaseous hydrocarbons
The experimental results of the above examples show that the gaseous hydrocarbon catalytic oxidation deoxidation catalyst provided by the invention has the advantages of high activity, high activation speed, no reduction before reaction, repeated use and the like in the deoxidation reaction process. The preparation method of the catalyst provided by the invention has the advantages of good controllability, simple steps and low cost. The application method can efficiently realize the inerting of the oil tank and does not generate harmful exhaust emission. The technical scheme is expected to provide a catalytic technical support for the green inerting technology of the aircraft fuel tank in China.
Claims (10)
1. A preparation method of a gaseous hydrocarbon catalytic oxidation deoxidation catalyst is characterized by comprising the following steps:
the catalyst is Pt/Beta; beta is a Beta type molecular sieve; pt is platinum, and the platinum is doped in the framework structure of the Beta molecular sieve crystal in a single atom form;
in the catalyst, the mass content of platinum is 0.1-1.5%; the silicon-aluminum atomic ratio of the Beta type molecular sieve, namely Si/Al, is 15-40;
the preparation method of the catalyst comprises the following steps:
1) preparing crystallized colloid:
tetraethylammonium hydroxide (TEAOH) is used as a template agent, and an aluminum source, sodium hydroxide, TEAOH, tetrammine platinum hydroxide and deionized water are mixed according to the proportionn Na2O: Al2O3: t TEAOH: y Pt: l H2Mixing the components in the proportion of O, fully stirring for 10-30 minutes until the components are completely dissolved,nis a mixture of a water-soluble polymer and a water-soluble polymer, wherein the water-soluble polymer is 1-5,tis the mixture of 2-6 percent of the raw materials,yis in the range of 0.01 to 0.2,lis 50 to 200;
adding silicon source or silicon source and deionized water into the above solution to obtain the compositionx Na2O: Al2O3: s SiO2: tTEAOH: y Pt: h H2Fully stirring the colloidal mixture of O for 30-60 minutes, and transferring the mixture into a closed reaction kettle; wherein the content of the first and second substances,xis a mixture of a water-soluble polymer and a water-soluble polymer, wherein the water-soluble polymer is 1-5,sis in the range of 30-80 percent,tis the mixture of 2-6 percent of the raw materials,yis in the range of 0.01 to 0.2,his 70 to 200;
2) crystallizing a molecular sieve:
the closed synthesis kettle filled with the crystallized colloid is placed in an oven, and the temperature is raised from room temperature to 120-160-oC, crystallizing for 12-96 hours under autogenous pressure, cooling the crystallization temperature to room temperature at the speed of 120-<9, the obtained solid substance is added at 100-oDrying for 6-24 hours under the condition of C to obtain Pt/Na-Beta molecular sieve raw powder;
3) after-treatment of the molecular sieve:
transferring the Pt/Na-Beta molecular sieve raw powder into a muffle furnace, and heating the Pt/Na-Beta molecular sieve raw powder from room temperature to 500-700 ℃ at the speed of 2-5 ℃/min in an air environmentoC, obtaining the roasted Pt/Na-Beta-cal molecular sieve;
mixing Pt/Na-Beta-cal molecular sieve with 0.6-1.2mol/L NH4NO3The solution is mixed according to the solid-to-liquid ratio of 1g (10-20) mL, and the temperature is raised to 70-90 ℃ under the stirring conditionoC, continuously stirring at the temperature, keeping for 0.5-5 hours, centrifugally separating, and fully washing a solid product by using deionized water; the product is prepared at 100-120-oDrying for 6-12 hours at C to obtain ammonium exchange treated Pt/NH4-a Beta molecular sieve; mixing Pt/NH4-Beta molecular sieves placed in muffle furnace, at 1-5oThe temperature rise rate of C/min is increased to 450-oAnd C, roasting for 2-5 hours at constant temperature in the air atmosphere to obtain the Pt/Beta molecular sieve.
2. The method of claim 1, wherein: the existing state of the platinum is one or two of an ionic state or an oxide.
3. The method of claim 1, wherein:
shaping a Pt/Beta molecular sieve catalyst:
tabletting, molding, crushing and screening the Pt/Beta molecular sieve powder to prepare a particle catalyst with 20-40 meshes; or, the catalyst is molded by extruding; or mixing the molecular sieve with polyethylene glycol, alumina sol and deionized water, ball-milling to obtain slurry, coating the slurry on a honeycomb ceramic carrier with 100-2000 pores, and roasting at 400-600 ℃ to obtain the honeycomb monolithic catalyst.
4. The method of claim 1, wherein:
activation of the catalyst before the reaction:
putting the catalyst into a reactor, introducing hydrogen or a mixed gas of hydrogen and inert gas, wherein the inert gas is one or more than two of nitrogen, helium and argon, and the molar concentration of the hydrogen in the mixed gas is 5-99 percent, calculated as 1-10 percentoThe temperature rise rate of C/min is increased from room temperature to 300-oC, activation ofAnd (3) stopping heating after 1-3 hours, and naturally cooling to normal temperature in an activating atmosphere to obtain the activated catalyst.
5. The method of claim 1, wherein: the aluminum source is one or more than two of sodium metaaluminate, aluminum nitrate, aluminum isopropoxide and aluminum sol, and the silicon source is one or more than two of silica sol, sodium silicate, water glass, tetraethyl silicate, silica aerogel and white carbon black.
6. A catalytic oxidation and deoxidation catalyst for gaseous hydrocarbons, obtainable by the process of any one of claims 1 to 5.
7. Use of a catalyst according to claim 6, wherein: the Pt/Beta catalyst is used in the catalytic oxidation deoxidation reaction of gaseous hydrocarbons.
8. Use according to claim 7, characterized in that: the gaseous hydrocarbon is a gas phase substance in a space above the liquid level in a container for storing kerosene, and comprises air and volatile gaseous hydrocarbon; the kerosene is one or more of RP-3 kerosene, rocket kerosene or high-density synthetic kerosene.
9. Use according to claim 7, characterized in that:
in the process of the catalytic oxidation and deoxidation reaction of the gaseous hydrocarbons, the catalyst is used in a form of filling granular catalyst obtained by tabletting or extruding into strips into a reactor to form a fixed bed, or placing honeycomb monolithic catalyst into the reactor to form one of monolithic beds.
10. Use according to claim 7, 8 or 9, characterized in that:
the volume space velocity (GHSV) of the gaseous hydrocarbon raw material passing through the catalyst bed layer is 300-10000h-1(ii) a The reaction temperature is 150-350-oC; the pressure of the reaction system is 0.1-2 MPa.
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