Adsorbent, preparation method and application

Abstract

The invention belongs to the technical field of gas adsorption determination of samples, and particularly relates to an adsorbent, a preparation method and application. The invention provides an adsorbent. The adsorbent comprises a carrier and an active component, the carrier is silicon dioxide or aluminum oxide, and the active components comprise benzene sulfinate and transition metal low-valence oxide. On the second aspect, the invention provides a preparation method of the adsorbent provided by the invention, and the preparation method comprises the following steps: calcining the carrier, dispersing in water, adding benzene sulfinate and transition metal low-valence oxide into water, stirring, reacting under an inert condition, filtering, and drying under the inert condition to obtain the adsorbent. The adsorbent provided by the invention adsorbs acetaldehyde at a certain temperature, does not act on ethanol, and can completely desorb acetaldehyde at a higher temperature, so that the adsorbent can be used for obtaining the content change of the product acetaldehyde in an ethanol surface dehydrogenation reaction in a temperature programming process.

Description

Technical Field

[0001] The invention relates to the technical field of gas adsorption determination of samples, and in particular to an adsorbent, a preparation method and an application thereof. Background Art

[0002] In petrochemical industry, catalysts are widely used in chemical production processes. Among them, amination and hydrogenation catalysts can produce amines by amination and hydrogenation of alcohols, which can become important chemical raw materials. Alcohol amination reaction is a multiphase catalytic process with a relatively complex reaction mechanism and a large number of reaction intermediates. Therefore, studying the alcohol amination reaction process and reaction mechanism plays an important role in the development and improvement of catalysts.

[0003] According to the literature and previous experiments, an important step in the amination reaction of alcohol is the surface dehydrogenation of alcohol, that is, the dehydrogenation of alcohol to form aldehyde. For the amination reaction of ethanol, it is the dehydrogenation of ethanol to form acetaldehyde. Therefore, detecting the real-time changes of ethanol and acetaldehyde under programmed temperature conditions is an important data for studying ethanol amination catalysts.

[0004] The commonly used instrument for detecting changes in vapor content is gas chromatography, where ethanol and acetaldehyde are separated by a chromatographic column, and then qualitative and quantitative analysis is performed by different retention times. However, this method cannot detect changes in the content of ethanol and acetaldehyde under programmed temperature conditions in real time. Another commonly used detector is a mass spectrometer, but since the molecular ion peak and main fragment peak of acetaldehyde are interfered by the ethanol fragment peak, the mass spectrometer cannot clearly determine changes in the content of acetaldehyde.

[0005] Before using mass spectrometry to detect changes in the content of reactant ethanol and product acetaldehyde, an adsorbent can be added. At a certain temperature, the adsorbent can adsorb acetaldehyde and has no effect on ethanol. At a higher temperature, acetaldehyde can be completely desorbed. By controlling the temperature, the adsorption and desorption of acetaldehyde can be controlled. By repeating the experiment, the real-time changes and content of acetaldehyde with temperature can be obtained.

[0006] Since both ethanol and acetaldehyde are organic substances, their properties are similar. Although the boiling points of acetaldehyde and ethanol differ by nearly 60 degrees, the volatility of both is very good. It is difficult to directly separate ethanol and acetaldehyde. At present, the prior art generally separates them through a multi-stage separation tower, or adds a substance to react with the acetaldehyde or ethanol therein, distills out another substance, and then adds other substances to the substance after the reaction to restore the original state, and then distills it out. The adsorbent of acetaldehyde in the prior art is mainly activated carbon, but the adsorption of activated carbon belongs to physical adsorption, which also has an adsorption effect on ethanol, which is not conducive to removing acetaldehyde gas from ethanol vapor. Application No. CN200810013160.4 "Adsorbent and preparation method for removing acetaldehyde gas from carbon dioxide" discloses an adsorbent and preparation method for effectively removing acetaldehyde gas from carbon dioxide, and the adsorbent is characterized by a modified X-type or Y-type molecular sieve. Application No. CN201510965438.8 "Device for removing formaldehyde and acetaldehyde from high-purity reagent acetonitrile" discloses an acetonitrile aldehyde impurity adsorbent and adsorption device, and application No. CN201811025236.5 "Device for removing acetaldehyde impurities from acetic acid" discloses a device for removing acetaldehyde impurities from acetic acid. Both of these devices adsorb acetaldehyde.

[0007] According to the existing technology, it is impossible to detect the changes in the content of ethanol and acetaldehyde under programmed temperature conditions in real time. Therefore, developing a new adsorbent and applying it to the determination technology of ethanol surface dehydrogenation reaction during programmed temperature can better study the changes in the content of reactants and products in the alcohol surface dehydrogenation reaction. Summary of the invention

[0008] In order to solve the above problems in the prior art, the present invention provides an adsorbent, a preparation method and an application thereof.

[0009] In a first aspect, the present invention provides an adsorbent, comprising a carrier and an active component; the carrier comprises silicon dioxide or aluminum oxide, and the active component comprises benzenesulfinate and a low-valent oxide of a transition metal.

[0010] For transition metal low-valent oxides, such as transition metal Fe, the transition metal low-valent oxide referred to in the present invention is ferrous oxide (ferrous iron), not ferric oxide (ferric iron).

[0011] As a specific embodiment of the present invention, based on the total mass of the adsorbent, the adsorbent includes: 40wt% to 90wt% of a carrier, 5wt% to 30wt% of benzenesulfinate, and 5wt% to 30wt% of a transition metal low-valent oxide.

[0012] Preferably, based on the total mass of the adsorbent, the adsorbent comprises: 60-80 wt% of a carrier, 10-20 wt% of benzenesulfinate, and 10-20 wt% of a transition metal low-valent oxide.

[0013] As a specific embodiment of the present invention, the benzene sulfinate includes sodium benzene sulfinate or potassium benzene sulfinate.

[0014] As a specific embodiment of the present invention, the low-valent oxide of the filtration metal is selected from at least one of ferrous oxide, cuprous oxide and manganese oxide.

[0015] As a specific embodiment of the present invention, the BET specific surface area of ​​the adsorbent is 15 to 30 m 2 / g, the pore volume of the single point method is 0.04~0.1cm 3 / g.

[0016] In a second aspect, the present invention provides a method for preparing the adsorbent provided in the first aspect of the present invention, comprising: calcining a carrier and dispersing it in water to obtain a dispersion, adding an active component to the dispersion to obtain a mixed solution, stirring the mixed solution and reacting it under inert conditions, filtering it, and drying it under inert conditions to obtain the adsorbent.

[0017] As a specific embodiment of the present invention, the calcination conditions include: temperature of 1000-1200° C. and time of 6-48 hours.

[0018] Preferably, the calcination conditions include: temperature of 1100-1200° C. and time of 12-36 hours.

[0019] As a specific embodiment of the present invention, the reaction conditions include: temperature of 10 to 50° C. and time of 0.5 to 4 h.

[0020] Preferably, the reaction conditions include: temperature of 20-40° C. and time of 1-2 h.

[0021] As a specific embodiment of the present invention, the drying conditions include: a temperature of 80 to 120° C. and a time of 0.5 to 4 hours.

[0022] Preferably, the drying conditions include: a temperature of 90 to 110° C. and a time of 1 to 2 hours.

[0023] In a third aspect, the present invention provides an application of the adsorbent provided in the first aspect of the present invention and the adsorbent prepared by the preparation method provided in the second aspect of the present invention in adsorbing a mixed gas of ethanol and acetaldehyde; the application refers to obtaining a change in the acetaldehyde content in the product when ethanol undergoes a surface dehydrogenation reaction to generate acetaldehyde under programmed temperature conditions, by utilizing the different adsorption capacities of the adsorbent for ethanol and acetaldehyde at different temperatures;

[0024] The application process includes: placing a catalyst in a fixed bed reactor, placing an adsorbent in a sample tube, connecting the outlet of the fixed bed reactor with the inlet of the sample tube, connecting the outlet of the sample tube with a mass spectrometer, introducing a gas containing ethanol into the fixed bed reactor, and causing a surface dehydrogenation reaction of ethanol in the fixed bed reactor to generate acetaldehyde under the action of the catalyst; the gas discharged from the fixed bed reactor enters the sample tube, and enters the mass spectrometer after being adsorbed by the adsorbent in the sample tube, and the mass spectrometer tests the content of ethanol and acetaldehyde in the gas; and the change in the content of acetaldehyde in the product when ethanol undergoes a surface dehydrogenation reaction in the presence of the catalyst is obtained by using different degrees of adsorption of ethanol and formaldehyde by the adsorbent at different temperatures.

[0025] The programmed temperature rise process is to increase the temperature according to the steps set by the program, such as increasing the temperature from room temperature to 500°C at a heating rate of 10°C / min.

[0026] Preferably, the temperature of the surface dehydrogenation reaction of ethanol in the fixed bed reactor is 50-250°C, the reaction pressure is normal pressure, the heating rate of the reactor is 1-90°C / min, the temperature of the sample tube is 0-120°C, and the pressure of the sample tube is normal pressure.

[0027] Compared with the prior art, the present invention has achieved the following beneficial effects.

[0028] The present invention provides an adsorbent, which has simple components, is easy to obtain, and has low cost; the preparation process is simple, the raw materials are easily available, and the production cost is low. The adsorbent adsorbs acetaldehyde at a certain temperature and has no effect on ethanol. At a higher temperature, acetaldehyde can be completely desorbed, and can be used to monitor the change in the acetaldehyde content of the product in the surface dehydrogenation reaction of ethanol in real time during the programmed temperature increase process.

[0029] The active component benzenesulfinate mainly plays the role of adsorbing acetaldehyde. The sulfur on benzenesulfinate attacks the carbonyl on acetaldehyde with nucleophilicity to generate benzenesulfonate, which can adsorb formaldehyde. When the content of benzenesulfinate is too low, the adsorption capacity of acetaldehyde will be weakened at 30-70°C. When the content of benzenesulfinate is too high, the adsorption capacity of acetaldehyde will be strong at 70-100°C. Both are not conducive to the adsorption and desorption of acetaldehyde by regulating the temperature, and cannot be used to determine the change of acetaldehyde content in the product of ethanol surface dehydrogenation reaction during the programmed temperature rise process.

[0030] Benzenesulfinate is easily oxidized, which causes it to lose the ability to adsorb acetaldehyde. Transition metal low-valent oxides can be oxidized into transition metal high-valent oxides. Therefore, the presence of transition metal low-valent oxides can relatively keep benzenesulfinate from being oxidized and maintain the adsorbent performance of benzenesulfinate. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1This is the mass spectrum of the sample tube at 30° C. in Application Example 1 of the present invention;

[0032] Figure 2 This is the mass spectrum of the sample tube at 70° C. in Application Example 1 of the present invention;

[0033] Figure 3 This is a graph showing the change in acetaldehyde content of the product with temperature in Application Example 1 of the present invention. DETAILED DESCRIPTION

[0034] The test method used in the present invention is as follows:

[0035] 1. Test of adsorbent performance:

[0036] Adsorbent was added to the sample tube, and then gases with volume fractions of 0.50% ethanol, 0.50% acetaldehyde and 99.0% helium were passed into the sample tube at a flow rate of 50 mL / min. The temperatures of the sample tube were set to 0°C, 30°C, 50°C, 70°C, and 100°C, respectively. After stabilization for 1 min, the contents of ethanol and acetaldehyde in the gas discharged from the sample tube were detected by gas chromatograph.

[0037] 2. Specific surface area and pore volume determination:

[0038] Weigh a certain mass of sample and put it into the sample tube, put the sample tube into the instrument and degas. Then put the sample tube into the analysis station for analysis and conduct a full analysis of the nitrogen adsorption and desorption isotherm. The specific surface area of ​​the catalyst is calculated by the BET method, and the pore volume of the catalyst is calculated by the single point method (taking p / p0=0.995).

[0039] 3. Programmed temperature surface dehydrogenation reaction:

[0040] Weigh a certain mass of catalyst and put it into the reactor, introduce H2 into the reactor, raise the reactor to a certain temperature at 10℃ / min under H2 purge, maintain it for a certain time, and then lower it to a certain temperature, connect the reactor with the adsorbent sample tube, and connect the adsorbent sample tube with the mass spectrometer. Set the temperature of the adsorbent sample tube T1, introduce helium gas containing ethanol into the reactor, and after the baseline is stable, raise the reactor to a certain temperature at 10℃ / min, and use the mass spectrometer to detect the changes of the signals of ethanol (m / z=31) and acetaldehyde (m / z=44) over time. Change the temperature of the adsorbent sample tube T2, and keep other conditions the same, and use the mass spectrometer to record the changes of the signals of ethanol (m / z=31) and acetaldehyde (m / z=44) over time.

[0041] 4. Determination method of the content of each component of the obtained adsorbent:

[0042] The sample is placed in a tablet press for tableting, and the tableted sample is placed in an X-ray fluorescence spectrometer. A Rh target high-power X-ray tube is used, and the tube voltage and tube current are set. The non-oxygen element content in the carrier, the sulfur content in the benzenesulfinate, and the transition metal element content in the transition metal low-valent oxide are respectively determined, and then the contents of the carrier, benzenesulfinate, and transition metal low-valent oxide are calculated according to the chemical formula.

[0043] The present invention will be further described below in conjunction with specific embodiments, but they do not constitute any limitation to the present invention.

[0044] Embodiment 1:

[0045] The preparation method comprises the following steps.

[0046] a. Weigh 7g of silicon dioxide and place it in a muffle furnace, heat it to 1200℃ and calcine it for 24h. Then take it out after cooling down, and record it as solid A;

[0047] b. Soak solid A in 50 ml of water, add 1.5 g of sodium benzenesulfinate and 1.5 g of ferrous oxide in sequence, mix and stir evenly, and record it as solution B;

[0048] c. Transfer solution B to a reactor and seal it, introduce nitrogen to replace the remaining air in the reactor, and react at 30°C for 2h to obtain a mixed solution C;

[0049] d. Centrifuge the mixed solution C to obtain solid D;

[0050] e. The solid D was dried at 100° C. under a nitrogen atmosphere for 2 h to obtain the finished adsorbent 1.

[0051] The content of each component, specific surface area and pore volume of the adsorbent are shown in Table 1. The test results of the adsorbent adsorbing ethanol and acetaldehyde are shown in Table 2. It can be seen from Table 2 that the adsorbent can almost completely adsorb acetaldehyde and a small amount of ethanol at 0°C. At 70 and 100°C, acetaldehyde and ethanol are almost not adsorbed. At 30-50°C, ethanol is almost not adsorbed, and different amounts of acetaldehyde can be adsorbed.

[0052] Embodiment 2:

[0053] The preparation method comprises the following steps.

[0054] a. Weigh 7g of alumina and place it in a muffle furnace, heat it to 1160℃ and calcine it for 36h. Then take it out after cooling down, and record it as solid A.

[0055] b. Soak solid A in 50 ml of water, add 1.5 g of potassium benzenesulfinate and 1.5 g of cuprous oxide in sequence, mix and stir evenly, and record it as solution B;

[0056] c. Transfer solution B to a reactor, seal it, introduce nitrogen to replace the remaining air in the reactor, and react at 35°C for 1.5h to obtain a mixed solution C;

[0057] d. Centrifuge the mixed solution C to obtain solid D;

[0058] e. Solid D was dried at 110° C. in a nitrogen atmosphere for 2 h to obtain a finished adsorbent 2.

[0059] The content of each component, specific surface area and pore volume of the adsorbent are shown in Table 1. The test results of the adsorbent adsorbing ethanol and acetaldehyde are shown in Table 2. It can be seen from Table 2 that the adsorbent can almost completely adsorb acetaldehyde and a small amount of ethanol at 0°C. At 70 and 100°C, acetaldehyde and ethanol are almost not adsorbed. At 30-50°C, ethanol is almost not adsorbed, and different amounts of acetaldehyde can be adsorbed.

[0060] Embodiment 3:

[0061] The preparation method comprises the following steps.

[0062] a. Weigh 8.5g of silicon dioxide and place it in a muffle furnace, heat it to 1200℃ and calcine it for 24h. Then take it out after cooling down, and record it as solid A;

[0063] b. Soak solid A in 50 ml of water, add 0.75 g of sodium benzenesulfinate and 0.75 g of ferrous oxide in sequence, mix and stir evenly, and record it as solution B;

[0064] c. Transfer solution B to a reactor and seal it, introduce nitrogen to replace the remaining air in the reactor, and react at 30°C for 2h to obtain a mixed solution C;

[0065] d. Centrifuge the mixed solution C to obtain solid D;

[0066] e. The solid D was dried at 100° C. under a nitrogen atmosphere for 2 h to obtain the finished adsorbent 3.

[0067] The content of each component, specific surface area and pore volume of the adsorbent are shown in Table 1. The test results of the adsorbent adsorbing ethanol and acetaldehyde are shown in Table 2. It can be seen from Table 2 that the adsorbent can almost completely adsorb acetaldehyde and a small amount of ethanol at 0°C. At 70 and 100°C, acetaldehyde and ethanol are almost not adsorbed. At 30-50°C, ethanol is almost not adsorbed, and different amounts of acetaldehyde can be adsorbed.

[0068] Embodiment 4:

[0069] The adsorbent was prepared in the manner of Example 1, except that: c) the reaction was carried out at 40° C. for 1 h to obtain adsorbent 4.

[0070] The content of each component, specific surface area and pore volume of the adsorbent are shown in Table 1. The test results of the adsorbent adsorbing ethanol and acetaldehyde are shown in Table 2. It can be seen from Table 2 that the adsorbent can almost completely adsorb acetaldehyde and a small amount of ethanol at 0°C. At 70 and 100°C, acetaldehyde and ethanol are almost not adsorbed. At 30-50°C, ethanol is almost not adsorbed, and different amounts of acetaldehyde can be adsorbed.

[0071] Embodiment 5:

[0072] The adsorbent was prepared in the manner of Example 1, except that e) the adsorbent was dried at 110° C. under a nitrogen atmosphere for 1.5 h to obtain adsorbent 5.

[0073] The content of each component, specific surface area and pore volume of the adsorbent are shown in Table 1. The test results of the adsorbent adsorbing ethanol and acetaldehyde are shown in Table 2. It can be seen from Table 2 that the adsorbent can almost completely adsorb acetaldehyde and a small amount of ethanol at 0°C. At 70 and 100°C, acetaldehyde and ethanol are almost not adsorbed. At 30-50°C, ethanol is almost not adsorbed, and different amounts of acetaldehyde can be adsorbed.

[0074] Embodiment 6:

[0075] The preparation method comprises the following steps.

[0076] a. Weigh 7g of silicon dioxide and place it in a muffle furnace, heat it to 1200℃ and calcine it for 24h. Then take it out after cooling down, and record it as solid A;

[0077] b. Soak solid A in 50 ml of water, add 1.5 g of sodium benzenesulfinate and 1.5 g of manganese oxide in turn, mix and stir evenly, and record it as solution B;

[0078] c. Transfer solution B to a reactor and seal it, introduce nitrogen to replace the remaining air in the reactor, and react at 30°C for 2h to obtain a mixed solution C;

[0079] d. Centrifuge the mixed solution C to obtain solid D;

[0080] e. The solid D was dried at 100° C. under a nitrogen atmosphere for 2 h to obtain the finished adsorbent 1.

[0081] The content of each component, specific surface area and pore volume of the adsorbent are shown in Table 1. The test results of the adsorbent adsorbing ethanol and acetaldehyde are shown in Table 2. It can be seen from Table 2 that the adsorbent can almost completely adsorb acetaldehyde and a small amount of ethanol at 0°C. At 70 and 100°C, acetaldehyde and ethanol are almost not adsorbed. At 30-50°C, ethanol is almost not adsorbed, and different amounts of acetaldehyde can be adsorbed.

[0082] Comparative Example 1:

[0083] The preparation method comprises the following steps.

[0084] a. Weigh 8.5g of silicon dioxide and place it in a muffle furnace, heat it to 1200℃ and calcine it for 24h. Then take it out after cooling down, and record it as solid A;

[0085] b. Soak solid A in 50 ml of water, add 1.5 g of sodium benzenesulfinate, mix and stir evenly, and record it as solution B;

[0086] c. Transfer solution B to a reactor and seal it, introduce nitrogen to replace the remaining air in the reactor, and react at 30°C for 2h to obtain a mixed solution C;

[0087] d. Centrifuge the mixed solution C to obtain solid D;

[0088] e. The solid D was dried at 100° C. in a nitrogen atmosphere for 2 h to obtain a finished contrast agent 1.

[0089] The content of each component, specific surface area and pore volume of the adsorbent are shown in Table 1. The test results of the adsorbent adsorbing ethanol and acetaldehyde are shown in Table 2. It can be seen from Table 2 that the adsorbent adsorbs a small amount of ethanol and a large amount of acetaldehyde at 0°C, and almost no adsorption of acetaldehyde and ethanol occurs at 70 and 100°C. At 30-50°C, it can adsorb different amounts of ethanol and acetaldehyde.

[0090] Comparative Example 2:

[0091] The preparation method comprises the following steps.

[0092] a. Weigh 7g of silicon dioxide and place it in a muffle furnace, heat it to 1200℃ and calcine it for 24h. Then take it out after cooling down, and record it as solid A;

[0093] b. Soak solid A in 50 ml of water, add 1.5 g of ferrous oxide, mix and stir evenly, and record it as solution B;

[0094] c. Transfer solution B to a reactor and seal it, introduce nitrogen to replace the remaining air in the reactor, and react at 30°C for 2h to obtain a mixed solution C;

[0095] d. Centrifuge the mixed solution C to obtain solid D;

[0096] e. Solid D was dried at 100° C. in a nitrogen atmosphere for 2 h to obtain contrast agent 2.

[0097] The results of the content of each component, specific surface area and pore volume of the adsorbent are shown in Table 1. The adsorbent's ability to adsorb ethanol and acetaldehyde is shown in Table 2. It can be seen from Table 2 that the adsorbent adsorbs a small amount of ethanol and a large amount of acetaldehyde at 0°C, and almost no acetaldehyde and ethanol are adsorbed at 70 and 100°C. At 30-50°C, it can adsorb different amounts of ethanol and acetaldehyde.

[0098] Comparative Example 3:

[0099] a. Weigh 7g of silicon dioxide and place it in a muffle furnace, heat it to 1200℃ and calcine it for 24h. Then take it out after cooling down, and record it as solid A;

[0100] b. Soak solid A in 50 ml of water, recorded as solution B;

[0101] c. Transfer solution B to a reactor and seal it, introduce nitrogen to replace the remaining air in the reactor, and react at 30°C for 2h to obtain a mixed solution C;

[0102] d. Centrifuge the mixed solution C to obtain solid D;

[0103] e. Solid D was dried at 100° C. under a nitrogen atmosphere for 2 h to obtain contrast agent 3.

[0104] The results of the content of each component, specific surface area and pore volume of the adsorbent are shown in Table 1. The adsorbent's ability to adsorb ethanol and acetaldehyde is shown in Table 2. It can be seen from Table 2 that the adsorbent adsorbs a small amount of ethanol and acetaldehyde at 0°C, and almost no acetaldehyde and ethanol are adsorbed at 70 and 100°C. At 30-50°C, it can adsorb different amounts of ethanol and acetaldehyde.

[0105] Comparative Example 4:

[0106] The adsorbent was prepared in the manner of Example 1, except that the contents of sodium benzenesulfinate and silicon dioxide were different, and the content of sodium benzenesulfinate was less than 5 wt % of the mass of the catalyst, to obtain comparative agent 4.

[0107] The results of the content of each component, specific surface area and pore volume of the adsorbent are shown in Table 1. The adsorbent's ability to adsorb ethanol and acetaldehyde is shown in Table 2. As can be seen from Table 2, the adsorbent adsorbs a small amount of ethanol and a large amount of acetaldehyde at 0°C, acetaldehyde and ethanol are almost not adsorbed at 70 and 100°C, and can adsorb different amounts of ethanol and acetaldehyde at 30-50°C.

[0108] Comparative Example 5:

[0109] The adsorbent was prepared in the manner of Example 1. The difference from Example 1 was that the contents of sodium benzenesulfinate and silicon dioxide were different. The content of sodium benzenesulfinate was higher than 30 wt % of the mass of the catalyst. Comparative agent 5 was obtained.

[0110] The results of the content of each component, specific surface area and pore volume of the adsorbent are shown in Table 1. The adsorbent's ability to adsorb ethanol and acetaldehyde is shown in Table 2. As can be seen from Table 2, the adsorbent can almost completely adsorb acetaldehyde and a small amount of ethanol at 0°C. At 30-70°C, ethanol is almost not adsorbed, and different amounts of acetaldehyde can be adsorbed. At 100°C, ethanol is almost not adsorbed, and acetaldehyde is slightly adsorbed.

[0111] Comparative Example 6:

[0112] The Y-type molecular sieve was used as the adsorbent to obtain the comparative agent 6, and the test results of the comparative agent 6 for adsorbing ethanol and acetaldehyde are shown in Table 2. It can be seen that at 30-70°C, the adsorption amounts of acetaldehyde and ethanol are not much different.

[0113] Comparative Example 7:

[0114] Activated carbon was used as the adsorbent to obtain comparative agent 7, and the test results of comparative agent 7 for adsorbing ethanol and acetaldehyde are shown in Table 2. It can be seen that at 30-70°C, the adsorption amounts of acetaldehyde and ethanol are not much different.

[0115] Application Example 1

[0116] The adsorbent used is the finished adsorbent prepared according to Example 1. The application method comprises the following steps.

[0117] 1. Weigh 0.1g of catalyst and put it into the reactor. The catalyst is a metal cobalt catalyst supported on an alumina carrier, in which the mass content of the alumina carrier is 80% and the mass content of the metal cobalt is 20%.

[0118] 2. Place 10 g of adsorbent 1 in the adsorbent sample tube.

[0119] 3. Introduce H2 gas into the reactor. While purging with H2 gas, raise the temperature of the reactor to 500°C at 10°C / min, maintain for 1 hour, and then cool to room temperature to reduce the catalyst. Connect the reactor, adsorbent sample tube, and mass spectrometer, and control the temperature of the adsorbent sample tube to 30°C. Then, introduce a mixed gas of 8% ethanol vapor and 92% helium by volume into the reactor. After the baseline is stable, raise the temperature of the reactor to 250°C at 10°C / min. Use a mass spectrometer to detect the changes in the signals of ethanol (m / z=31) and acetaldehyde (m / z=44) over time. The results are as follows: Figure 1 shown.

[0120] 4. Repeat steps 1, 2, and 3, except that the temperature of the adsorbent sample tube in step 3 is set to 70°C. Use a mass spectrometer to detect the changes in the signals of ethanol (m / z=31) and acetaldehyde (m / z=44) over time. The results are as follows: Figure 2 shown.

[0121] 5. Use Figure 2 The signal of acetaldehyde (m / z = 44) was subtracted Figure 1 The signal of acetaldehyde (m / z=44) was obtained Figure 3 , that is, the acetaldehyde content of the product in the dehydrogenation reaction of ethanol on the catalyst surface changes with temperature during the programmed temperature increase process.

[0122] Test Example 1

[0123] Test method 4 (X-ray fluorescence spectrometry) was used to determine the content of each component in the adsorbent obtained in Examples 1-6 and Comparative Examples 1-5, and test method 2 was used to test the specific surface area and pore volume of the adsorbent obtained in Examples 1-6 and Comparative Examples 1-5.

[0124] The results are shown in Table 1.

[0125] Table 1 Adsorbent characteristic test results

[0126]

[0127]

[0128] Test Example 2

[0129] The adsorption capacity of ethanol and acetaldehyde of the adsorbents obtained in Examples 1-6 and Comparative Examples 1-7 was measured according to Test Method 1 (test of adsorbent performance).

[0130] The results are shown in Table 2.

[0131] Table 2 Adsorbent adsorption test results

[0132]

[0133]

[0134] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. An adsorbent, characterized in that: The invention comprises a carrier and an active component; the carrier comprises silicon dioxide or aluminum oxide, and the active component comprises benzene sulfinate and a transition metal low-valent oxide.

2. The adsorbent according to claim 1, characterized in that Based on the total mass of the adsorbent, the adsorbent comprises: 40 wt% to 90 wt% of a carrier, 5 wt% to 30 wt% of a benzene sulfinate, and 5 wt% to 30 wt% of a transition metal low-valent oxide; Preferably, based on the total mass of the adsorbent, the adsorbent comprises: 60 wt% to 80 wt% of a carrier, 10 wt% to 20 wt% of benzene sulfinate, and 10 wt% to 20 wt% of a transition metal low-valent oxide.

3. The adsorbent according to claim 2, characterized in that The benzenesulfinate includes sodium benzenesulfinate or potassium benzenesulfinate; And / or, the transition metal low-valent oxide is at least one selected from ferrous oxide, cuprous oxide, and manganese oxide.

4. The adsorbent according to any one of claims 1 to 3, characterized in that The BET specific surface area of ​​the adsorbent is 15 to 30 m 2 / g, the pore volume of the single point method is 0.04~0.1cm 3 / g.

5. A method for preparing the adsorbent according to any one of claims 1 to 4, characterized in that: include: The carrier is calcined and then dispersed in water, active components are added to the water to obtain a mixed solution, the mixed solution is stirred and reacted under inert conditions, filtered, and dried under inert conditions to obtain an adsorbent.

6. The preparation method according to claim 5, characterized in that: The calcination conditions include: a temperature of 1000-1200° C. and a time of 6-48 hours; preferably, the calcination conditions include: a temperature of 1100-1200° C. and a time of 12-36 hours.

7. The preparation method according to claim 5 or 6, characterized in that: The reaction conditions include: temperature of 10-50°C, time of 0.5-4h; preferably, the reaction conditions include: temperature of 20-40°C, time of 1-2h.

8. The preparation method according to claim 7, characterized in that: The drying conditions include: a temperature of 80 to 120° C. and a time of 0.5 to 4 hours; preferably, the drying conditions include: a temperature of 90 to 110° C. and a time of 1 to 2 hours.

9. Use of the adsorbent according to any one of claims 1 to 4 or the adsorbent prepared by the preparation method according to any one of claims 5 to 8 in adsorbing a mixed gas of ethanol and acetaldehyde; the use refers to obtaining the change of acetaldehyde content in the product when ethanol undergoes surface dehydrogenation reaction to generate acetaldehyde under programmed temperature conditions by utilizing the different adsorption capacities of the adsorbent for ethanol and acetaldehyde at different temperatures; The application process includes: The catalyst is placed in a fixed bed reactor, the adsorbent is placed in a sample tube, the outlet of the fixed bed reactor is connected to the inlet of the sample tube, the outlet of the sample tube is connected to a mass spectrometer, a gas containing ethanol is introduced into the fixed bed reactor, and ethanol undergoes a surface dehydrogenation reaction in the fixed bed reactor under the action of the catalyst to generate acetaldehyde; the gas discharged from the fixed bed reactor enters the sample tube, and after being adsorbed by the adsorbent in the sample tube, enters the mass spectrometer, and the mass spectrometer tests the content of ethanol and acetaldehyde in the gas; the adsorption degree of ethanol and formaldehyde by the adsorbent is different at different temperatures, so as to obtain the change of acetaldehyde content in the product when ethanol undergoes a surface dehydrogenation reaction in the presence of the catalyst.

10. The use according to claim 9, characterized in that: The temperature at which the surface dehydrogenation reaction of ethanol occurs in the fixed bed reactor is 50-250°C, and the temperature of the sample tube is 0-120°C.

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