CN113049517B - Temperature programming-infrared spectrum combined device and application thereof in catalyst preparation - Google Patents
Temperature programming-infrared spectrum combined device and application thereof in catalyst preparation Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 238000001514 detection method Methods 0.000 claims abstract description 41
- 238000011946 reduction process Methods 0.000 claims abstract description 20
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- QDAYJHVWIRGGJM-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QDAYJHVWIRGGJM-UHFFFAOYSA-B 0.000 description 2
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
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- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
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- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
Abstract
The invention relates to a program heating and infrared combined device and application thereof in catalyst preparation. The temperature programmed reaction system consists of a heating furnace, a reaction tube, more than two gas circuit modules with flow control and a temperature programmed control module. The Fourier transform infrared system consists of a gas sample cell and an infrared detector. The gas exiting the temperature programmed reaction tube can be directed to the detection system or vented to the atmosphere through a bypass. The gas entering the detection system can directly enter a gas sample cell of the Fourier transform infrared spectrometer or enter the gas sample cell of the Fourier transform infrared spectrometer after being detected by a thermal conductivity cell detector through a shunting/non-shunting gas path. The program heating and infrared combined device is used for researching the reduction process of the catalyst and is beneficial to comprehensively knowing the reduction process and the reaction mechanism.
Description
Technical Field
The invention belongs to the technical field of instruments and meters, and particularly relates to a thermal analyzer for characterization of a solid material, particularly a solid catalyst, and application thereof in research of a preparation process of the solid catalyst.
Background
The temperature programmed analysis technique is a technique for studying the law of a solid material or a solid material previously treated by a specific method according to the change of gas composition in a certain temperature programmed process in a specific gas flowing atmosphere and taking the change as a function of temperature or time. It is an automatic dynamic tracking measurement, so compared with static method it has the advantages of continuous, quick and simple, etc. and can be extensively used in various discipline fields of inorganic chemistry, organic chemistry, high-molecular chemistry, biochemistry, metallurgy, petrochemistry, mineralogy and geology, etc. The temperature programming analysis technology is an important research means in the field of catalysis, and is comprehensively applied to more than ten aspects including catalyst activity evaluation, catalyst preparation condition selection, catalyst composition determination, determination of the valence state of a metal active component, interaction between the metal active component and a carrier, active component dispersion threshold and metal dispersion degree determination, coordination state and distribution of active metal ions, solid catalyst surface acid-base determination, catalyst aging and inactivation mechanism, carbon deposition behavior of the catalyst, adsorption and surface reaction mechanism, catalyst regeneration and condition selection thereof, heterogeneous catalytic reaction kinetics and the like.
The temperature programming technique specifically includes Temperature Programming Desorption (TPD), temperature Programming Reduction (TPR), temperature programming oxidation, temperature programming vulcanization, temperature programming surface reaction, and the like. The TPD technology can be used for representing the action strength of the active components or carriers on the surface of the catalyst and the gas probe molecules. Such as under an inert atmosphere (e.g., N) 2 Or Ar atmosphere) with basic NH 3 As probe molecules, the obtained spectrogram reflects NH at different temperatures 3 Desorption conditions. NH (NH) 3 The higher the desorption temperature, the higher NH 3 The stronger the action with the surface active component or the carrier of the catalyst, the stronger the acidity of the catalyst is reflected indirectly; NH 3 The larger the desorption peak area is, the more desorbed NH is represented 3 The larger the amount of (A), the larger the number of acid sites is reflected indirectly. If NH is basic 3 Molecular exchange to acidic CO 2 The probe molecule can be used for characterizing the alkalinity of the catalyst. TPR technique is to reduce the concentration of H 2 Mixed with inert gas (e.g. H) 2 /Ar or H 2 /N 2 Mixed gas) is passed through the metal oxide at a flow rate while the temperature is raised at a programmed rate. At a specific temperatureAt the temperature, the specific oxidizing species are reduced, hydrogen is consumed, and a recorder records the change of the gas flow composition to obtain a TPR spectrogram. Each TPR peak in the spectrogram generally represents a reducible species in the catalyst, and the temperature corresponding to the maximum value of the TPR peak is called peak temperature and reflects the difficulty degree of reduction of an oxidized species on the catalyst; the size of the area contained under the peak profile is proportional to the amount of this oxide. The TPR technology can obtain the information of metal valence state change, intermetallic interaction, interaction between metal oxide and a carrier, activation energy of oxide reduction reaction and the like. In addition, many catalysts are typically operated over H 2 The oxide precursor is reduced under the atmosphere for preparation, and a plurality of important information of the catalyst preparation process can be obtained through the TPR technology.
The temperature programming device generally comprises two parts, namely a reaction system and an analysis and detection system (figure 1). The core of the reaction system comprises a heating furnace and a quartz reaction tube which can control a temperature rise program, and an execution component of the analysis and detection system is a thermal conductivity cell detector (TCD). Temperature-programmed devices generally require more than two gases, divided into purge gas and adsorption (reaction) gas. Ar or N is selected as the purge gas 2 The inert gas, the adsorption (reaction) gas typically being a probe molecule or a reactive gas (e.g. H) 2 、O 2 Or H 2 S, etc.) and an inert gas. When TCD is used as a detector, gas needs to enter the TCD as a reference after flow control, and then enters the TCD again after reaction, so that the comparison of the heat conductivity coefficients is realized, and the change of the gas composition is measured and recorded.
It should be noted that TCD can only detect changes in the composition of a gas and cannot perform qualitative and quantitative analysis of the components in the gas. This has limited the study of temperature programmed processes with complex gas compositions. For example, the metal-rich transition metal phosphide has metal characteristics, and shows good application prospects in important reactions catalyzed by metals, such as hydrorefining, selective hydrogenation, hydrodeoxygenation, electrolytic water hydrogen evolution and the like. Common transition metal phosphides can be mainly classified into group VIII transition metal phosphides (nickel phosphide, cobalt phosphide, palladium phosphide, etc.) and group VI transition metal phosphides (molybdenum phosphide, tungsten phosphide, etc.)) And (4) two types. Temperature-programmed reduction of these transition metal phosphate precursors in the corresponding oxidation states is the most common method for preparing phosphide catalysts (catal.lett., 2012, 142. The phosphate precursor not only consumes H in the reduction process 2 May release multiple gas components, such as H 2 O、H 2 P and phosphorus-containing components (e.g. PH) 3 ) Etc., cause a change in TCD signal, but the gas composition cannot be analyzed only by TCD, and thus the reduction process of the transition metal phosphate precursor cannot be studied in depth. In addition to the use of a TCD detector, mass spectrometry can also be used as a detector for temperature programmed analysis. The reduction process of transition metal phosphates was studied by Oyama et al (j.catal., 2004,221, 263-273) using a temperature programmed mass spectrometry technique, and H was found in the reduced gas 2 O、PH 3 And P, and the like. Mass spectrometry, however, can only monitor known specific components and cannot fully analyze gas composition. For example, in the preparation of transition metal phosphides 2 P requires an excess of phosphorus, while MoP and WP of subgroup VI can be prepared by reducing phosphate precursors with stoichiometric phosphorus/metal ratios. These scientific problems are difficult to recognize by the choice of detectors such as TCD and mass spectrometry.
The current in-situ infrared technology focuses on measuring the change of the solid surface of the catalyst and ignores the qualitative analysis of the gas generated in the preparation process of the catalyst. In addition, patent CN1464299A discloses a method for measuring hydrogen production reaction process and product of methanol on catalyst, which uses traditional in-situ reaction infrared spectroscopy technology, and uses an in-situ reaction cell to realize in-situ reaction and perform infrared spectroscopy analysis on the reaction product. The patent technology cannot give characteristic reaction on the surface of the solid catalyst and physical and chemical changes of reactants in the reaction process, and the patent focuses on the reaction process on the surface of the catalyst, so that qualitative research on the preparation process of the catalyst cannot be realized.
Disclosure of Invention
The invention aims to provide a temperature-programmed analysis device which can comprehensively analyze the composition of effluent gas in the temperature-programmed process and the application of the composition in the research of the preparation process of a catalyst.
In order to achieve the purpose, the invention provides a device for combining a temperature programming device with a thermal conductivity cell detector and a Fourier transform infrared spectrometer, which is technically characterized in that: the device consists of a temperature programmed reaction system and a detection system. The detection system is composed of a Fourier transform infrared gas sample cell and a detector, and a thermal conductivity cell detector (figure 2) can also be additionally arranged.
The Fourier transform infrared spectrum is widely applied to chemical composition analysis of a complex system, is one of common means for identifying compounds and determining molecular structures of substances, can simultaneously respond to various functional groups, and provides possibility for analyzing gas composition of the complex system. The structure of the unknown substance can be estimated according to the position and the shape of an absorption peak in the infrared spectrum, and the content of each component in the mixture can be determined according to the intensity of the characteristic absorption peak. Especially for some samples that are difficult to separate. The advantage of using infrared absorption spectroscopy to analyze chemical components is that it is fast, highly sensitive, uses a small sample volume, etc., while allowing analysis of samples in various states, such as gases, solids, liquids, etc.
The invention connects the temperature programming device with the thermal conductivity cell detector and the infrared spectrometer in series or in parallel, utilizes the infrared spectrometer to efficiently detect the gas product in the catalyst forming process in real time, and integrates the information of the temperature programming device, the thermal conductivity cell detector and the Fourier transform infrared spectrum, thereby obtaining the important information of the catalyst preparation process.
(1) And (4) carrying out temperature programming on the reaction system. The system comprises a heating furnace, a quartz reaction tube, more than two gas circuit modules with flow control and a program temperature rise control module.
(2) And (4) a detection system. The gas exiting the quartz reaction tube can either enter the detection system directly or be vented to the atmosphere through a bypass. The gas entering the detection system can directly enter a gas sample cell of the Fourier transform infrared spectrometer and then is exhausted, or the gas enters a gas sample cell of the Fourier transform infrared spectrometer through a shunt/non-shunt gas path after being detected by a thermal conductivity cell detector and then is exhausted, or one path of the gas is exhausted after being detected by the thermal conductivity cell detector through the shunt/non-shunt gas path and then is exhausted, and the other path of the gas enters the gas sample cell of the Fourier transform infrared spectrometer and then is exhausted.
The above-mentioned apparatus is used for catalyst preparation process research, and preferably adopts tubular furnace and quartz U-shaped tube reactor.
And (3) carrying out real-time qualitative analysis on the multi-component gas in the catalyst preparation process by using a Fourier transform infrared spectrometer. High sensitivity photoconductive detectors are preferred, while temperature-controlled gas sample cells need to be provided to prevent condensation of water vapor and other gases entering the gas detection cell. The Fourier transform infrared spectrometer also needs to be equipped with continuous infrared spectrum acquisition and recording software for continuously acquiring and recording infrared signals and temperature or time signals of a gas sample entering a gas detection cell and generating a corresponding spectrogram.
And a pipeline with a temperature control heat insulation layer is adopted for connection between the outlet of the temperature programming device and the inlet of the thermal conductivity cell detector, or between the outlet of the temperature programming device and the inlet of the thermal conductivity cell detector and between the outlet of the thermal conductivity cell detector and the inlet of the gas detection cell of the Fourier transform infrared spectrometer, or between the outlet of the temperature programming device and the inlet of the thermal conductivity cell detector and between the outlet of the temperature programming device and the inlet of the gas detection cell of the Fourier transform infrared spectrometer.
The outlet of the temperature programming device is also required to be provided with a pipeline for leading the air to the atmosphere. The device is used for discharging gas in the drying treatment or pretreatment process of a catalyst precursor or discharging gas in the cooling process of an instrument after the test is finished so as to avoid polluting a thermal conductivity cell detector and an infrared spectrometer gas detection cell.
The reaction system device, the thermal conductivity cell detector and the Fourier transform infrared detection system can have three connection modes: (1) use of infrared system alone: the outlet of the temperature programming device is connected with the inlet of the gas sample cell of the Fourier transform infrared spectrometer through a pipeline with a temperature control insulating layer. (2) connecting in series: the outlet of the temperature programming device is connected with the inlet of the thermal conductivity cell detector through a pipeline with a temperature control heat insulation layer, and the gas entering the thermal conductivity cell detector can adopt a shunting or non-shunting mode; the outlet of the thermal conductivity cell detector is connected with the inlet of the gas sample cell of the Fourier transform infrared spectrometer through a pipeline with a temperature control insulating layer. (3) connecting in parallel: the outlet of the temperature programming device is connected with the inlet of the thermal conductivity cell detector through a pipeline with a temperature control insulating layer, and the gas entering the thermal conductivity cell detector can adopt a shunting or non-shunting mode; the outlet of the temperature programming device is connected with the inlet of the gas sample cell of the Fourier transform infrared spectrometer through a pipeline with a temperature control insulating layer.
The instrument is used for researching the preparation process of the catalyst, firstly, inert gas is used for sweeping the solid catalyst precursor for 0.5-5 h at the temperature of 100-250 ℃, the sweeping flow is 20-200 mL/min, and the sweeping tail gas is exhausted to the atmosphere through a bypass. And then, switching the mixed reducing gas, purging the catalyst precursor at a flow rate of 20-200 mL/min, introducing the purged tail gas into a detection system, purging the detection system for 10-120 min, and collecting an infrared spectrum background spectrogram. The ramp-up and/or ramp-down sequence is initiated while the detection system registers a signal change. Finally, the temperature change (time-temperature spectrogram), the signal change (time or temperature-electric spectrogram) of the thermal conductivity cell and the signal change (time or temperature-infrared spectrogram) of the Fourier infrared spectrometer in the reduction process of the catalyst precursor are organically combined to know the preparation process and the reaction mechanism of the catalyst.
The invention has the advantages and beneficial effects that:
1. the invention focuses on the real-time qualitative analysis of the gas generated in the catalyst preparation process, combines the characteristic reaction of the solid surface of the catalyst and the physical and chemical changes, comprehensively obtains the science of the catalyst preparation process, and discloses the catalyst preparation mechanism.
2. The invention can monitor the change of gas composition along with time or temperature in the process of temperature programming in real time, comprehensively analyze the obtained information, can obtain important information of the process of temperature programming treatment of the catalyst, and is an effective means for researching the preparation process of the complex catalyst.
Drawings
FIG. 1 is a diagram of a conventional prior art temperature programming apparatus;
FIG. 2a is a schematic diagram of an infrared system used alone;
FIG. 2b is a schematic diagram of a temperature programmed-infrared tandem application;
FIG. 2c is a schematic diagram of a temperature programmed-infrared parallel use;
FIG. 3 shows Ni prepared in example 2 2 An XRD spectrum of P;
FIG. 4 shows Ni prepared in example 2 2 A programmed heating reduction-infrared spectrogram of the phosphate precursor of P;
FIG. 5 is an XRD spectrum of MoP prepared in example 3;
FIG. 6 is a temperature programmed reduction-IR spectrum of a phosphate precursor of MoP prepared in example 3;
FIG. 7 is an XRD spectrum of WP prepared in example 4;
FIG. 8 is a temperature programmed reduction-IR spectrum of the phosphate precursor of WP prepared in example 4.
Detailed Description
The temperature programming-infrared combined device and the application thereof in the preparation process of the transition metal phosphide research are explained in detail in the following by combining with the attached drawings.
Example 1
(1) Use of infrared system alone: the temperature programming-infrared combined device comprises a temperature programming reaction system and a detection system (figure 2 a). The temperature-programmed reaction system comprises: the gas circuit comprises more than two gas circuits, wherein each gas circuit is provided with a pressure reducing valve 1, a pressure gauge 2, a stop valve 3 and a mass flowmeter 4 and adopts a parallel connection mode; the outlet of the mass flowmeter is connected with the inlet of a reaction tube 5, the reaction tube is heated by a heating furnace 6, the outlet of the reaction tube is divided into two paths, one path is communicated with the atmosphere, and the other path is communicated with a detection system; the gas path entering the detection system is connected with the inlet of a gas sample cell 8 of an infrared spectrometer 7, and the gas flows out from the outlet of the gas sample cell to the atmosphere after being detected and recorded by infrared spectroscopy.
(2) Temperature programming-infrared spectrometer series connection: including a temperature programmed reaction system and a detection system (fig. 2 b). The temperature-programmed reaction system comprises: the gas circuit comprises more than two gas circuits, wherein each gas circuit is provided with a pressure reducing valve 1, a pressure gauge 2, a stop valve 3 and a mass flowmeter 4 and adopts a parallel connection mode; the outlet of the mass flowmeter is connected with the inlet of a reference gas path of a thermal conductivity cell detector 5, the outlet of the reference gas path is connected with the inlet of a reaction tube 6, the reaction tube is heated by a heating furnace 7, the outlet of the reaction tube is divided into two paths, one path is led to the atmosphere, and the other path enters a detection system; the gas entering the detection system enters a detection gas path of the thermal conductivity cell detector in a shunting or non-shunting mode, enters an inlet of a gas sample cell 9 of an infrared spectrometer 8 from an outlet after detection, and is led to the atmosphere from the outlet after detection of the infrared spectrometer.
(3) Temperature programming-parallel connection of infrared spectrometers: including a temperature programmed reaction system and a detection system (fig. 2 c). The temperature-programmed reaction system comprises: the gas circuit comprises more than two gas circuits, wherein each gas circuit is provided with a pressure reducing valve 1, a pressure gauge 2, a stop valve 3 and a mass flow meter 4 and adopts a parallel connection mode; gaseous direct 5 reference gas circuits that get into the thermal conductivity cell of mass flow meter export detect, flow by the export after the thermal conductivity cell detects, get into 6 entrys of reaction tube, the reaction tube passes through heating furnace 7 heating, flows by the reaction tube export behind the reaction tube, divide into three routes: one path is communicated with the atmosphere, the other path enters a detection gas path of the thermal conductivity cell detector in a shunting or non-shunting mode, and is communicated with the atmosphere through an outlet after detection, and the other path enters an inlet of a gas sample cell 9 of the infrared spectrometer 8 and flows out through the outlet to be communicated with the atmosphere after infrared spectrum detection.
Example 2
Preparation of Ni 2 Phosphate precursor of P catalyst
6.6g of nickel nitrate (Ni (NO) 3 ) 2 ·6H 2 O) was dissolved in 15mL of deionized water, and 3g of diammonium hydrogen phosphate ((NH) 4 ) 2 HPO 4 ) Dissolving in 10mL of deionized water, dropwise adding the diammonium phosphate aqueous solution into a nickel nitrate aqueous solution (200 rpm) which is continuously stirred at room temperature, and continuously stirring for 30min after the dropwise addition is finished. The mixture was placed on an electric furnace, heated while evaporating water with a glass rod under stirring, and after a large amount of water had been evaporated, transferred to a forced air drying oven to dry at 120 ℃ for 12 hours. Grinding and crushing the dried sample, transferring the sample into a muffle furnace, and roasting for 3 hours at 500 ℃ in air atmosphere to obtain Ni 2 Phosphate precursor of P catalyst.
Research on preparation of Ni from nickel phosphate precursor by using temperature programmed reduction-infrared combined device 2 P catalyst process
Taking Ni of 20-40 meshes 2 Phosphate precursor of P catalyst 15mg was chargedAnd (3) respectively loading 1g of roasted (550 ℃, air atmosphere and 3 h) 20-40-mesh quartz sand into two sides of the quartz U-shaped tube, connecting the gas pipeline 1 with nitrogen, and connecting the gas pipeline 2 with high-purity hydrogen. Firstly, opening a nitrogen gas path of gas 1, reducing pressure, controlling the flow rate to be 100mL/min, introducing a quartz U-shaped tube, and controlling the sample treatment temperature to be 200 ℃ by using a programmed heating furnace for treatment for 2 hours. The gas is exhausted to the atmosphere through a bypass in the sample processing process. And (3) starting an infrared spectrometer in advance to preheat for 6 hours, and controlling the temperature of the heat-insulating layer and the set temperature of the gas sample cell to be 200 ℃. And closing a nitrogen gas path of the gas 1, opening a hydrogen gas path of the gas 2, introducing reducing gas hydrogen into the quartz U-shaped tube, controlling the flow to be 100mL/min, directly introducing the gas from the outlet of the reaction tube into the inlet of a gas sample cell of the infrared spectrometer, purging for 1h, and finishing infrared spectrum background collection in the last 5 min. Running a temperature programming program (from 200 ℃ to 850 ℃ at the speed of 5 ℃/min) and starting infrared spectrum continuous spectrogram acquisition, and recording Ni in real time by a computer monitoring system in the whole process 2 And in the P precursor reduction process, a temperature-programmed heating furnace and infrared spectrum signals are controlled, and the signals are finally integrated.
FIG. 3 shows Ni prepared 2 XRD spectrogram of P catalyst, and result shows that Ni is successfully prepared 2 And (4) P phase. FIG. 4 illustrates Ni production from a phosphate precursor of nickel 2 TPR-IR spectrum of P catalyst process, as the reduction temperature is increased from 200 deg.C to 850 deg.C, the result is mainly detected as H 2 O、PH 3 And pentavalent phosphorus species (including P) 2 O 5 ·xH 2 O, phosphoric acid, phosphate, and mixtures thereof). When Ni is present 2 The pH is detected in the infrared spectrogram of the effluent gas when the reduction temperature of the phosphate precursor of the P catalyst is very low (200 ℃), namely 3 And pentavalent phosphorus species, indicating pH 3 Is not a product of direct hydrogenation reduction of pentavalent phosphates, since even zero-valent phosphorus is hydrogenated to produce a pH 3 More severe conditions are also required. Therefore, during the reduction process of the nickel phosphate precursor, the nickel phosphate precursor may be firstly reduced into phosphite or hypophosphite, and simultaneously partial phosphite or hypophosphite undergoes disproportionation reaction to generate PH 3 (ii) a And the pentavalent phosphorus species during the reduction process may bepH of formation 3 Quilt H 2 The product of the oxidation of O. When the reduction temperature is higher than 510 ℃, the pH value 3 And the peak intensity characteristic of the pentavalent phosphorus species increases significantly with increasing temperature, indicating the formation of Ni 2 The generation of these volatile phosphorus species is significantly promoted after P.
Example 3
Preparation of phosphate precursor of MoP catalyst
4g of ammonium molybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O) was dissolved in 15mL of deionized water, and 3g of ammonium monohydrogen phosphate ((NH) 4 ) 2 HPO 4 ) Dissolving in 10mL of deionized water, dropwise adding the diammonium phosphate aqueous solution into the ammonium molybdate aqueous solution which is continuously stirred at room temperature (200 rpm), and continuously stirring for 30min after the dropwise addition is finished. The mixture is placed on an electric furnace to be heated, a glass rod is used for stirring and evaporating water, and when a large amount of water is evaporated, the mixture is transferred to a forced air drying oven to be dried for 12 hours at 120 ℃. And grinding and crushing the dried sample, and then transferring the sample into a muffle furnace to roast for 3 hours at 500 ℃ in an air atmosphere to obtain a phosphate precursor of the MoP catalyst.
Research on process of preparing MoP catalyst from molybdenum phosphate precursor by using temperature programming reduction-infrared combined device
15mg of phosphate precursor of the 20-40-mesh MoP catalyst is filled into a quartz U-shaped tube, 1g of 20-40-mesh quartz sand after roasting (550 ℃, air atmosphere and 3 h) is respectively filled into two sides of the quartz U-shaped tube, the quartz U-shaped tube is connected, the gas pipeline 1 is connected with nitrogen, and the gas pipeline 2 is connected with high-purity hydrogen. Firstly, opening a nitrogen gas path of gas 1, reducing pressure, controlling the flow rate to be 100mL/min, introducing a quartz U-shaped tube, and controlling the sample treatment temperature to be 200 ℃ by using a programmed heating furnace for treatment for 2 hours. The gas is exhausted to the atmosphere through a bypass during the sample processing. And (3) starting an infrared spectrometer in advance to preheat for 6 hours, and controlling the temperature of the heat-insulating layer and the set temperature of the gas sample cell to be 200 ℃. And closing a nitrogen gas path of the gas 1, opening a hydrogen gas path of the gas 2, introducing reducing gas hydrogen into the quartz U-shaped tube, controlling the flow to be 100mL/min, directly introducing the gas from the outlet of the reaction tube into the inlet of a gas sample cell of the infrared spectrometer, purging for 1h, and finishing infrared spectrum background collection in the last 5 min. Running a temperature programming program (from 200 ℃ to 850 ℃ at the speed of 5 ℃/min), starting infrared spectrum continuous spectrogram acquisition, recording a temperature programming heating furnace and infrared spectrum signals in the reduction process of the MoP precursor in real time and in the whole process by a computer monitoring system, and finally integrating the signals.
Fig. 5 shows the XRD pattern of the prepared MoP catalyst, indicating successful preparation of the MoP phase. FIG. 6 shows a TPR-IR spectrum of a MoP catalyst prepared from a molybdenum phosphate precursor, wherein H is mainly detected as the reduction temperature is increased from 200 ℃ to 850 DEG C 2 O、PH 3 And pentavalent phosphorus species (including P) 2 O 5 ·xH 2 O, phosphoric acid, phosphate, and mixtures thereof). And Ni 2 The reduction process of the phosphate precursor of the P catalyst is similar, and when the reduction temperature of the phosphate precursor of the MoP catalyst is very low (200 ℃), the PH is detected in the infrared spectrogram of the effluent gas 3 And pentavalent phosphorus species, again indicating pH 3 Instead of being the product of direct hydrogenation reduction of pentavalent phosphates, phosphates may first be reduced to phosphites or hypophosphites, with some of the phosphites or hypophosphites undergoing disproportionation to produce pH 3 While the pentavalent phosphorus species may be the generated pH during the reduction process 3 Quilt H 2 The product of the oxidation of O. Characteristic peak of pentavalent phosphorus species (1270 cm) when reduction temperature is above 530 deg.C -1 ) The intensity did not increase significantly indicating that the resulting MoP did not promote the formation of volatile phosphorus species.
Example 4
Preparation of phosphate precursor of WP catalyst
5.6g of ammonium metatungstate ((NH) 4 ) 6 W 7 O 40 ·xH 2 O) was dissolved in 15mL of deionized water, and 3g of diammonium hydrogen phosphate ((NH) 4 ) 2 HPO 4 ) Dissolving in 10mL of deionized water, dropwise adding a diammonium phosphate aqueous solution into a continuously stirred (200 rpm) ammonium metatungstate aqueous solution at room temperature, and continuously stirring for 30min after dropwise adding. Heating the mixture on an electric furnace while stirring with a glass rod to evaporate water, transferring to a forced air drying oven to dry at 120 deg.C for 12 deg.C when a large amount of water is evaporatedh. And grinding and crushing the dried sample, and then transferring the sample into a muffle furnace to be roasted for 3 hours at 500 ℃ in an air atmosphere to obtain a phosphate precursor of the WP catalyst.
Research on process of preparing WP catalyst from tungsten phosphate precursor by using temperature programming reduction-infrared combined device
15mg of phosphate precursor of the WP catalyst with the size of 20-40 meshes is taken and filled into a quartz U-shaped tube, 1g of quartz sand with the size of 20-40 meshes after roasting (550 ℃, air atmosphere and 3 hours) is respectively filled into two sides of the quartz U-shaped tube, the quartz U-shaped tube is connected, a gas pipeline 1 is connected with nitrogen, and a gas pipeline 2 is connected with high-purity hydrogen. Firstly, opening a nitrogen gas path of gas 1, reducing pressure, controlling the flow rate to be 100mL/min, introducing a quartz U-shaped tube, and controlling the sample treatment temperature to be 200 ℃ by using a programmed heating furnace for treatment for 2 hours. The gas is exhausted to the atmosphere through a bypass during the sample processing. And (3) starting an infrared spectrometer in advance to preheat for 6 hours, and controlling the temperature of the heat-insulating layer and the set temperature of the gas sample cell to be 200 ℃. And closing a nitrogen gas path of the gas 1, opening a hydrogen gas path of the gas 2, introducing reducing gas hydrogen into the quartz U-shaped tube, controlling the flow to be 100mL/min, directly introducing the gas from the outlet of the reaction tube into the inlet of a gas sample cell of the infrared spectrometer, purging for 1h, and finishing infrared spectrum background acquisition in the last 5 min. And (3) running a program temperature-rising program (rising from 200 ℃ to 850 ℃ at the speed of 5 ℃/min), starting infrared spectrum continuous spectrogram acquisition, recording a program temperature-controlled heating furnace and infrared spectrum signals in the WP precursor reduction process in real time in the whole process by a computer monitoring system, and finally integrating the signals.
Figure 7 shows the XRD spectrum of the WP catalyst prepared, indicating successful preparation of the WP phase. FIG. 8 is a TPR-IR spectrum of a WP catalyst prepared from a phosphate precursor of tungsten with a primary detection of H as the reduction temperature increased from 200 ℃ to 850 DEG C 2 O、PH 3 And pentavalent phosphorus species (including P) 2 O 5 ·xH 2 O, phosphoric acid, phosphate, and mixtures thereof). And Ni 2 The reduction process of the phosphate precursor of the P and MoP catalysts is similar, and the PH is detected in the infrared spectrogram of the effluent gas when the reduction temperature of the phosphate precursor of the WP catalyst is very low (200 ℃), and 3 and pentavalent phosphorus species, indicating pH 3 Instead of being the product of direct hydrogenation reduction of pentavalent phosphates, phosphates may first be reduced to phosphites or hypophosphites, with some of the phosphites or hypophosphites undergoing disproportionation to produce pH 3 While the pentavalent phosphorus species may be the generated pH during the reduction process 3 Quilt H 2 O is a product of oxidation. Characteristic peak of pentavalent phosphorus species (1270 cm) when reduction temperature is higher than 530 deg.C -1 ) There is no significant increase in intensity, indicating that the WP produced does not promote the production of volatile phosphorus species.
Comparative Ni 2 Phosphate precursor reduction process for P, moP and WP catalysts, ni 2 The phosphate precursor reduction process of the P catalyst is greatly different from that of MoP and WP, and when the reduction temperature is higher than 510 ℃, the PH is higher 3 And the characteristic peak intensity of the pentavalent phosphorus species increased significantly and reached a maximum when the temperature was above 620 ℃ and remained stable. This is mainly due to the formation of Ni 2 P catalyzes the disproportionation of phosphite or hypophosphite to generate PH 3 Simultaneously catalyzing the pH 3 Quilt H 2 Oxidation of O generates pentavalent phosphorus species. And disproportionation reaction and pH of generated MoP and WP on phosphite or hypophosphite 3 Quilt H 2 The oxidation reaction of O has no catalytic effect. It is the reason above that leads to the production of Ni 2 P requires an excess of phosphorus, whereas only stoichiometric phosphorus is required for the preparation of MoP and WP.
The invention has been clearly disclosed by the above description. It will be apparent, however, to one skilled in the art that many modifications and improvements can be made to the invention. Therefore, any modification and improvement made to the present invention should be within the scope of the present invention as long as it does not depart from the spirit of the present invention. The scope of the invention is set forth in the appended claims.
Claims (4)
1. An application method of a program heating and infrared combined device in the reduction process of a solid catalyst is characterized in that:
the program heating and infrared combined device comprises a program heating reaction system, a thermal conductivity cell detector and a Fourier transform infrared detection system, wherein the program heating reaction system comprises a heating furnace, a reaction tube, more than two gas circuit modules with flow control and a program heating control module; the gas pipeline entering the detection system is connected to a detection gas circuit of a thermal conductivity cell detector in a shunting or non-shunting mode, an outlet pipeline of the detection gas circuit is connected to an inlet of a gas sample cell of the Fourier transform infrared detection system, and the gas sample cell flows out from an outlet to the atmosphere after infrared spectrum detection;
or the outlet of the reaction tube is divided into three paths: one path is communicated with the atmosphere, the other path is connected to a detection gas path of a thermal conductivity cell detector in a shunting or non-shunting mode, and is communicated with the atmosphere through an outlet after being detected, and the other path is connected to a gas sample cell inlet of a Fourier transform infrared detection system, and is communicated with the atmosphere through an outlet after being detected by an infrared spectrum;
the application method comprises the following steps: the solid catalyst precursor is filled into a reaction tube, firstly, inert gas is used for purging the solid catalyst precursor for 0.5-5 h at the temperature of 100-250 ℃, the purging flow is 20-200 mL/min, and the purging tail gas is exhausted to the atmosphere through a bypass; then, switching the mixed reducing gas, purging the catalyst precursor with a purging flow of 20-200 mL/min, introducing the purged tail gas into a detection system, purging for 10-120 min, and collecting an infrared spectrum background spectrogram; starting to execute a temperature rise and/or temperature fall program, and simultaneously detecting the change of a system record signal; and finally, organically combining a time-temperature spectrogram reflecting temperature change in the reduction process of the catalyst precursor, a time or temperature-electric signal spectrogram reflecting signal change of the thermal conductivity cell and a time or temperature-infrared spectrogram reflecting signal change of the Fourier infrared spectrometer, and further deducing the reduction process and the reaction mechanism of the catalyst.
2. The application method according to claim 1, characterized in that: the temperature or time is used as a standard for unifying the temperature programming reaction system, the thermal conductivity cell signal change and the infrared spectrum, the characteristic reaction of the reaction system and the physical and chemical change of the reaction species are determined according to the thermal conductivity cell signal change, then the gas product is qualitatively analyzed according to the infrared spectrum signal at the corresponding temperature, and the qualitative gas product and the physical and chemical change of the characteristic reaction and the reaction species are cooperatively analyzed to obtain the catalyst preparation mechanism.
3. The method of application according to claim 1, characterized in that: the inert gas is N 2 Ar or He as a purge gas, wherein the reducing gas is H with the concentration of 0.1-100% 2 And inert gas, and the reduction temperature is less than or equal to 1200 ℃.
4. The method of application according to claim 1, characterized in that: the precursor of the solid catalyst is a precursor of transition metal phosphate.
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