Oxygenate adsorbents in hydrogen and methods of making and removing oxygenates from industrial by-product hydrogen
By preparing an adsorbent containing molecular sieves, carbon powder, and hydroxypropyl cellulose to support active components of metal oxides, the problems of low adsorption capacity and difficult regeneration were solved, achieving efficient and economical removal of oxygen-containing compounds.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHINA UNIV OF PETROLEUM (BEIJING)
- Filing Date
- 2023-09-06
- Publication Date
- 2026-06-05
AI Technical Summary
Existing adsorption methods for removing oxygen-containing compounds from industrial by-product hydrogen suffer from problems such as low adsorption capacity of adsorbents and difficulty in regeneration, resulting in high operating costs and complex processes.
An adsorbent containing active metal oxide components is prepared by loading a carrier composed of molecular sieves, carbon powder, and hydroxypropyl cellulose, and is then formed, dried, and calcined. This adsorbent is used to adsorb oxygen-containing compounds at room temperature and pressure and is regenerated under a protective atmosphere.
It achieves highly selective and deep removal of oxygen-containing compounds from industrial by-product hydrogen, with high adsorption capacity and regenerable adsorbent, reducing operating costs and process complexity.
Abstract
Description
Technical Field
[0001] This invention belongs to the field of oxygen-containing compound removal technology in hydrogen gas, specifically relating to an adsorbent for oxygen-containing compounds in hydrogen gas, its preparation method, and a method for removing oxygen-containing compounds from industrial by-product hydrogen gas using the adsorbent. Background Technology
[0002] Hydrogen has a high calorific value, is widely available, and is clean with no carbon emissions. It reacts with oxygen to produce water, and water electrolysis can produce both hydrogen and oxygen. Therefore, hydrogen energy, as a highly efficient and clean secondary energy source, has significant advantages and is receiving increasing attention. However, industrial byproduct hydrogen typically contains trace amounts of oxygen-containing compounds such as methanol, methyl ethyl ketone, sec-butanol, furan, formic acid, and formaldehyde. The presence of these oxygen-containing compounds can adversely affect hydrogenation catalysts, fine chemical catalysts, and hydrogen fuel cell catalysts, as they preferentially adsorb onto the catalysts, affecting their lifespan and efficiency. Therefore, deep removal of oxygen-containing compounds is crucial for protecting the catalysts in downstream processes and ensuring the long-term stable operation of the equipment.
[0003] Methods for removing oxygen-containing compounds mainly include catalytic hydrogenation, water washing, and adsorption. Catalytic hydrogenation utilizes highly selective hydrogenation catalysts to remove oxygen-containing compounds by hydrogenating them into water under suitable process conditions. However, this technology suffers from complex processes and operating conditions, high hydrogen consumption, and difficulty in achieving deep removal of oxygen-containing compounds. Water washing removes oxygen-containing compounds by dissolving them in water. This method can remove oxygen-containing compounds at room temperature, but it suffers from poor removal precision and introduces water impurities into the hydrogen gas, requiring further dehydration and making the process complex. Adsorption is widely used for removing oxygen-containing compounds due to its simple process, easy operation, and low operating costs. Industrially, adsorbents such as activated alumina, silica gel, activated carbon, kaolin, or molecular sieves are generally used. These adsorbents are placed upstream of the reaction vessel containing the catalyst to remove oxygen-containing compound impurities from the raw materials, protecting the catalyst's lifespan and activity.
[0004] However, existing adsorption methods for removing oxygen-containing compounds from industrial by-product hydrogen generally have many problems, the most typical of which are low adsorption capacity of the adsorbent and difficulty in regenerating the adsorbent, which leads to high operating costs and complex processes.
[0005] Therefore, there is a current need to develop adsorbents that have high adsorption capacity for oxygen-containing compounds in industrial by-product hydrogen and are regenerable. Summary of the Invention
[0006] The purpose of this invention is to provide an adsorbent with high adsorption capacity and good regeneration performance for oxygen-containing compounds in industrial by-product hydrogen. This adsorbent exhibits good selectivity for oxygen-containing compounds, deep purification of oxygen-containing compounds, and a large adsorption capacity for oxygen-containing compounds during breakthrough. Another purpose of this invention is to provide a method for preparing the above-mentioned adsorbent and a method for removing oxygen-containing compounds from industrial by-product hydrogen using this hydrogen oxygen-containing compound adsorbent.
[0007] To achieve the above objectives, the present invention provides the following three technical solutions.
[0008] In a first aspect, the present invention provides an adsorbent for oxygen-containing compounds in hydrogen, wherein the adsorbent comprises a support and an active metal oxide component loaded on the support;
[0009] Based on the total mass of the raw material components of the adsorbent carrier as 100%, the raw material components of the adsorbent carrier include 20-80 wt% molecular sieve, 10-70 wt% binder, 2-10 wt% first auxiliary agent and 1-6 wt% second auxiliary agent.
[0010] The first additive is toner;
[0011] The second auxiliary agent is hydroxypropyl cellulose.
[0012] According to a preferred embodiment of the first aspect, the first additive includes at least one of coal-derived carbon powder, wood-based carbon powder, and coconut shell carbon powder.
[0013] According to a preferred embodiment of the first aspect, the molecular sieve includes at least one of 13X molecular sieve, NaY molecular sieve, ZSM-5 molecular sieve, composite molecular sieve of SBA-15 and ZSM-5, and composite molecular sieve of 13X and ZSM-5.
[0014] According to a preferred embodiment of the first aspect, the binder includes at least one of boehmite, diatomaceous earth, attapulgite, and activated alumina.
[0015] According to a preferred embodiment of the first aspect, the carrier of the adsorbent can be prepared by the following method: mixing molecular sieve, binder, first auxiliary agent, second auxiliary agent and water, forming a shape, and then drying and calcining under a protective atmosphere to obtain the carrier of the adsorbent.
[0016] Furthermore, the forming process is extrusion forming;
[0017] Furthermore, the outer diameter of the formed part is 1.5-3mm and the length is 3-5mm;
[0018] Furthermore, the drying temperature is 80-130°C;
[0019] Furthermore, the drying time is 4-12 hours;
[0020] Furthermore, the protective atmosphere is a nitrogen atmosphere;
[0021] Furthermore, the calcination temperature is 300-600℃;
[0022] Furthermore, the roasting time is 3-6 hours.
[0023] According to a preferred embodiment of the first aspect, the active metal oxide component includes at least one of sodium oxide, magnesium oxide, zinc oxide, copper oxide, and nickel oxide.
[0024] According to a preferred embodiment of the first aspect, the loading of the metal oxide active component is 1.0-6.0 wt%, based on 100% of the carrier mass of the adsorbent.
[0025] In a second aspect, the present invention provides a method for preparing the oxygen-containing compound adsorbent in hydrogen provided in the first aspect, wherein the preparation method includes:
[0026] 1) Molecular sieve, binder, first auxiliary agent, second auxiliary agent and water are mixed and shaped, and then dried and calcined under a protective atmosphere to obtain the carrier of adsorbent;
[0027] 2) The precursor salt of the active component of metal oxide is loaded onto the carrier of the adsorbent, and then dried and calcined under a protective atmosphere to obtain the oxygen-containing compound adsorbent in hydrogen.
[0028] According to a preferred embodiment of the second aspect, in step 1), the forming is extrusion forming.
[0029] According to a preferred embodiment of the second aspect, in step 1), the outer diameter of the formed part is 1.5-3 mm.
[0030] According to a preferred embodiment of the second aspect, in step 1), the drying temperature is 80-130°C.
[0031] According to a preferred embodiment of the second aspect, in step 1), the drying time is 4-12 hours.
[0032] According to a preferred embodiment of the second aspect, in step 1), the protective atmosphere is a nitrogen atmosphere.
[0033] According to a preferred embodiment of the second aspect, in step 1), the calcination temperature is 300-600°C.
[0034] According to the preferred embodiment of the second aspect, in step 1), the roasting time is 3-6 hours.
[0035] According to a preferred embodiment of the second aspect, in step 2), the drying temperature is 80-130°C.
[0036] According to a preferred embodiment of the second aspect, in step 2), the drying time is 4-12 hours.
[0037] According to a preferred embodiment of the second aspect, in step 2), the protective atmosphere is a nitrogen atmosphere.
[0038] According to a preferred embodiment of the second aspect, in step 2), the calcination temperature is 300-600°C.
[0039] According to the preferred embodiment of the second aspect, in step 2), the roasting time is 3-6 hours.
[0040] According to a preferred embodiment of the second aspect, in step 2), the loading of the precursor salt of the metal oxide active component onto the carrier of the adsorbent is achieved in the following manner:
[0041] The carrier of the adsorbent is impregnated with a precursor salt solution of the active metal oxide component;
[0042] Furthermore, the impregnation is an equal-volume impregnation;
[0043] Furthermore, the precursor salt solution of the metal oxide active component has a molar concentration of 0.2-1.5 mol / L, based on the volume of the solution.
[0044] Thirdly, the present invention provides a method for removing oxygen-containing compounds from industrial by-product hydrogen, wherein the method uses the oxygen-containing compound adsorbent provided in the first aspect to adsorb the oxygen-containing compounds in the industrial by-product hydrogen to be treated, thereby achieving the removal of oxygen-containing compounds from the industrial by-product hydrogen.
[0045] According to a preferred embodiment of the third aspect, the oxygen-containing compounds in the industrial by-product hydrogen include at least one of organic oxygen-containing compounds such as alcohols, ketones, acids, esters, aldehydes, and furans.
[0046] Furthermore, taking the mass of industrial by-product hydrogen as 100%, the mass percentage of oxygen-containing compounds in the industrial by-product hydrogen is 0.1-5%.
[0047] According to a preferred embodiment of the third aspect, the industrial by-product hydrogen includes at least one of sec-butanol dehydrogenation by-product hydrogen, butanediol dehydrogenation by-product hydrogen, and ethanol dehydrogenation by-product hydrogen.
[0048] According to a preferred embodiment of the third aspect, the adsorption of oxygen-containing compounds in industrial by-product hydrogen to be treated using the oxygen-containing compound adsorbent provided in the first aspect includes:
[0049] The industrial by-product hydrogen to be treated is passed into the oxygen-containing adsorbent in the hydrogen provided by the first aspect for adsorption.
[0050] Furthermore, the adsorption occurs at room temperature;
[0051] Furthermore, the adsorption occurs at atmospheric pressure;
[0052] Furthermore, the flow rate of the industrial by-product hydrogen to be treated is 200-600 mL / min (e.g., 400 mL / min).
[0053] According to a preferred embodiment of the third aspect, the method further includes regenerating the exhausted adsorbent in a protective atmosphere at 150-350°C (e.g., 200°C) and then reusing it to adsorb oxygen-containing compounds in industrial by-product hydrogen to be treated.
[0054] Furthermore, the protective atmosphere is a nitrogen atmosphere;
[0055] Furthermore, the regeneration time is 3-6 hours (e.g., 5 hours);
[0056] Furthermore, the failed adsorbent is a permeated adsorbent; wherein, the adsorbent permeates when the content of oxygen-containing compounds in the adsorbed product exceeds 1 ppm.
[0057] The oxygen-containing compound adsorbent provided by this invention is an adsorbent for removing oxygen-containing compounds. It is formed by loading a metal oxide active component onto a special carrier obtained by combining molecular sieves, carbon powder, hydroxypropyl cellulose, and a binder. It exhibits good selectivity for oxygen-containing compounds, high adsorption capacity, deep deoxygenation depth, and easy regeneration. Using the adsorbent provided by this invention to remove oxygen-containing compounds from industrial by-product hydrogen can achieve a deep removal of oxygen-containing compounds to below 1 ppm. Detailed Implementation
[0058] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.
[0059] Example 1
[0060] This embodiment provides an adsorbent for oxygen-containing compounds in hydrogen, which is prepared by the following method:
[0061] 9 kg of 13X molecular sieve, 15 kg of boehmite, 6 kg of coal-derived carbon powder and 0.2 kg of hydroxypropyl cellulose were mixed evenly, and then an appropriate amount of deionized water was added to extrude the mixture into strips to obtain a sample with a diameter of 1.5 mm and a length of 3 mm. The sample was dried at 120 °C for 12 h and calcined at 550 °C for 4 h under a nitrogen atmosphere to obtain the adsorbent carrier.
[0062] 5.0 g of sodium nitrate was dissolved in 80 g of deionized water and stirred thoroughly. The solution was then dispersed on 100 g of the prepared adsorbent support and impregnated at room temperature for 20 hours. The impregnated support was dried at 120 °C for 12 hours and calcined at 550 °C for 4 hours under a nitrogen atmosphere to obtain an adsorbent for oxygen-containing compounds in hydrogen. The prepared adsorbent, based on the mass of the adsorbent support (100%), had a Na₂O loading of 2.8 wt%.
[0063] This embodiment provides a method for removing oxygen-containing compounds from industrial by-product hydrogen gas, including:
[0064] 1) 30 mL of the adsorbent prepared in Example 1 was loaded into a fixed-bed reactor to contain 1000 mg / Nm³. 3 Hydrogen gas was used as the feed gas for methyl ethyl ketone (MEK). The feed gas was introduced into a fixed-bed reactor at a flow rate of 400 mL / min and adsorbed by contacting the adsorbent under room temperature and atmospheric pressure conditions. The content of MEK in the outlet gas was detected by gas chromatograph. When the content of MEK in the outlet gas exceeded 1 ppm, it was considered that the adsorbent had broken through, and the breakthrough adsorption capacity of MEK was calculated to be 12.7%.
[0065] 2) The permeated adsorbent sample was regenerated in a nitrogen atmosphere at 200°C for 5 hours to obtain a regenerated adsorbent. The regenerated adsorbent was then used as an adsorbent for the adsorption of the feed gas according to step 1). The permeation adsorption capacity of the regenerated adsorbent was measured to be 12.3%.
[0066] Example 2
[0067] This embodiment provides an adsorbent for oxygen-containing compounds in hydrogen, which is prepared by the following method:
[0068] Adsorbent preparation: 9 kg NaY molecular sieve, 15 kg diatomaceous earth, 6 kg coconut shell activated carbon and 0.2 kg hydroxypropyl cellulose were mixed evenly, and then an appropriate amount of deionized water was added to extrude the mixture into strips to obtain a sample with a diameter of 1.5 mm and a length of 3 mm. The sample was dried at 120 °C for 12 h and calcined at 550 °C for 4 h under a nitrogen atmosphere to obtain the adsorbent carrier.
[0069] 4.2 g of anhydrous cobalt nitrate was dissolved in 80 g of deionized water and stirred thoroughly until dissolved. The solution was then dispersed on 100 g of the prepared adsorbent support and impregnated at room temperature for 20 hours. The impregnated support was dried at 120 °C for 12 hours and calcined at 550 °C for 4 hours under a nitrogen atmosphere to obtain an adsorbent for oxygen-containing compounds in hydrogen. The prepared adsorbent, based on the mass of the adsorbent support (100%), had a CoO loading of 1.6 wt%.
[0070] This embodiment provides a method for removing oxygen-containing compounds from industrial by-product hydrogen gas, including:
[0071] 1) 30 mL of the adsorbent prepared in Example 2 was loaded into a fixed-bed reactor to contain 1000 mg / Nm³. 3 Hydrogen gas was used as the feed gas for methyl ethyl ketone (MEK). The feed gas was introduced into a fixed-bed reactor at a flow rate of 400 mL / min and adsorbed by contacting the adsorbent under room temperature and atmospheric pressure conditions. The content of MEK in the outlet gas was detected by gas chromatograph. When the content of MEK in the outlet gas exceeded 1 ppm, it was considered that the adsorbent had broken through. The breakthrough adsorption capacity of MEK was calculated to be 10.4%.
[0072] 2) The permeated adsorbent sample was regenerated in a nitrogen atmosphere at 200°C for 5 hours to obtain a regenerated adsorbent. The regenerated adsorbent was then used as an adsorbent for the adsorption of the feed gas according to step 1). The permeation adsorption capacity of the regenerated adsorbent for methyl ethyl ketone was 10.3%.
[0073] Example 3
[0074] This embodiment provides an adsorbent for oxygen-containing compounds in hydrogen, which is prepared by the following method:
[0075] 9 kg of ZSM-5 molecular sieve, 15 kg of activated alumina, 6 kg of coconut shell carbon powder and 0.2 kg of guar gum powder were mixed evenly, and then an appropriate amount of deionized water was added to extrude the mixture into strips to obtain a sample with a diameter of 1.5 mm and a length of 3 mm. The sample was dried at 120 °C for 12 h and calcined at 550 °C for 4 h under a nitrogen atmosphere to obtain the adsorbent carrier.
[0076] 4.2 g of anhydrous cobalt nitrate was dissolved in 80 g of deionized water and stirred thoroughly until dissolved. The solution was then dispersed on 100 g of the prepared adsorbent support and impregnated at room temperature for 20 hours. The impregnated support was dried at 120 °C for 12 hours and calcined at 550 °C for 4 hours under a nitrogen atmosphere to obtain an adsorbent for oxygen-containing compounds in hydrogen. The prepared adsorbent, based on the mass of the adsorbent support (100%), had a CoO loading of 1.6 wt%.
[0077] This embodiment provides a method for removing oxygen-containing compounds from industrial by-product hydrogen gas, including:
[0078] 1) 30 mL of the adsorbent prepared in Example 3 was loaded into a fixed-bed reactor to contain 1000 mg / Nm³ of adsorbent. 3 Hydrogen gas was used as the feed gas for methyl ethyl ketone (MEK). The feed gas was introduced into a fixed-bed reactor at a flow rate of 400 mL / min and adsorbed by contacting the adsorbent under room temperature and atmospheric pressure conditions. The content of MEK in the outlet gas was detected by gas chromatograph. When the content of MEK in the outlet gas exceeded 1 ppm, it was considered that the adsorbent had broken through. The breakthrough adsorption capacity of MEK was calculated to be 9.9%.
[0079] 2) The permeated adsorbent sample was regenerated at 200°C for 5 hours under a nitrogen atmosphere to obtain a regenerated adsorbent. The regenerated adsorbent was then used as an adsorbent for the adsorption of the feed gas according to step 1). The permeation adsorption capacity of the regenerated adsorbent for methyl ethyl ketone was 9.8%.
[0080] Example 4
[0081] This embodiment provides an adsorbent for oxygen-containing compounds in hydrogen, which is prepared by the following method:
[0082] 9 kg of SBA-5 molecular sieve, 15 kg of attapulgite clay, 6 kg of coconut shell carbon powder and 0.2 kg of guar gum powder were mixed evenly, and then an appropriate amount of deionized water was added to extrude the mixture into strips to obtain a sample with a diameter of 1.5 mm and a length of 3 mm. The sample was dried at 120 °C for 12 h and calcined at 550 °C for 4 h under a nitrogen atmosphere to obtain the adsorbent carrier.
[0083] 5.6 g of anhydrous copper nitrate was dissolved in 80 g of deionized water and stirred thoroughly. The solution was then dispersed on 100 g of the prepared adsorbent support and impregnated at room temperature for 20 hours. The impregnated support was dried at 120 °C for 12 hours and calcined at 550 °C for 4 hours under a nitrogen atmosphere to obtain an adsorbent for oxygen-containing compounds in hydrogen. The prepared adsorbent, based on the mass of the adsorbent support (100%), had a CuO loading of 2.3 wt%.
[0084] This embodiment provides a method for removing oxygen-containing compounds from industrial by-product hydrogen gas, including:
[0085] 1) 30 mL of the adsorbent prepared in Example 4 was loaded into a fixed-bed reactor to contain 1000 mg / Nm³. 3 Hydrogen gas was used as the feed gas for methyl ethyl ketone (MEK). The feed gas was introduced into a fixed-bed reactor at a flow rate of 400 mL / min and adsorbed by contacting the adsorbent under room temperature and atmospheric pressure conditions. The content of MEK in the outlet gas was detected by gas chromatograph. When the content of MEK in the outlet gas exceeded 1 ppm, it was considered that the adsorbent had broken through. The breakthrough adsorption capacity of MEK was calculated to be 10.9%.
[0086] 2) The permeated adsorbent sample was regenerated at 200°C for 5 hours under a nitrogen atmosphere to obtain a regenerated adsorbent. The regenerated adsorbent was then used as an adsorbent for the adsorption of the feed gas according to step 1). The permeation adsorption capacity of the regenerated adsorbent for methyl ethyl ketone was 10.5%.
[0087] Example 5
[0088] This embodiment provides an adsorbent for oxygen-containing compounds in hydrogen, which is prepared by the following method:
[0089] 9 kg of ZSM-5 was mixed evenly with 13X composite molecular sieve, 15 kg of attapulgite, 6 kg of coal-derived carbon powder and 0.2 kg of guar gum powder. Then, an appropriate amount of deionized water was added and the mixture was extruded to form a sample with a diameter of 1.5 mm and a length of 3 mm. The sample was dried at 120 °C for 12 h and calcined at 550 °C for 4 h under a nitrogen atmosphere to obtain the adsorbent carrier.
[0090] 6.3 g of anhydrous nickel nitrate was dissolved in 80 g of deionized water and stirred thoroughly until dissolved. The solution was then dispersed on 100 g of the prepared adsorbent support and impregnated at room temperature for 20 hours. The impregnated support was dried at 120 °C for 12 hours and calcined at 550 °C for 4 hours under a nitrogen atmosphere to obtain an adsorbent for oxygen-containing compounds in hydrogen. The prepared adsorbent, based on the mass of the adsorbent support (100%), had a NiO loading of 2.5 wt%.
[0091] This embodiment provides a method for removing oxygen-containing compounds from industrial by-product hydrogen gas, including:
[0092] 1) 30 mL of the adsorbent prepared in Example 5 was loaded into a fixed-bed reactor to contain 1000 mg / Nm³. 3 Hydrogen gas was used as the feed gas for methyl ethyl ketone (MEK). The feed gas was introduced into a fixed-bed reactor at a flow rate of 400 mL / min and adsorbed by contacting the adsorbent under room temperature and atmospheric pressure conditions. The content of MEK in the outlet gas was detected by gas chromatograph. When the content of MEK in the outlet gas exceeded 1 ppm, it was considered that the adsorbent had broken through. The breakthrough adsorption capacity of MEK was calculated to be 9.7%.
[0093] 2) The permeated adsorbent sample was regenerated at 200°C for 5 hours under a nitrogen atmosphere to obtain a regenerated adsorbent. The regenerated adsorbent was then used as an adsorbent for the adsorption of the feed gas according to step 1). The permeation adsorption capacity of the regenerated adsorbent for methyl ethyl ketone was 9.3%.
[0094] Example 6
[0095] This embodiment provides an adsorbent for oxygen-containing compounds in hydrogen, which is prepared by the following method:
[0096] 9 kg of NaY molecular sieve, 15 kg of diatomaceous earth, 6 kg of wood carbon powder and 0.2 kg of hydroxypropyl cellulose were mixed evenly, and then an appropriate amount of deionized water was added to extrude the mixture into strips to obtain a sample with a diameter of 1.5 mm and a length of 3 mm. The sample was dried at 120 °C for 12 h and calcined at 550 °C for 4 h under a nitrogen atmosphere to obtain the adsorbent carrier.
[0097] 5.6 g of magnesium nitrate was dissolved in 80 g of deionized water and stirred thoroughly. The solution was then dispersed on 100 g of the prepared adsorbent support and impregnated at room temperature for 20 hours. The impregnated support was dried at 120 °C for 12 hours and calcined at 550 °C for 4 hours under a nitrogen atmosphere to obtain an adsorbent for oxygen-containing compounds in hydrogen. The prepared adsorbent, based on the mass of the adsorbent support (100%), had a MgO loading of 1.4 wt%.
[0098] This embodiment provides a method for removing oxygen-containing compounds from industrial by-product hydrogen gas, including:
[0099] 1) 30 mL of the adsorbent prepared in Example 6 was loaded into a fixed-bed reactor to contain 1000 mg / Nm³. 3 Hydrogen gas was used as the feed gas for methyl ethyl ketone (MEK). The feed gas was introduced into a fixed-bed reactor at a flow rate of 400 mL / min and adsorbed by contacting the adsorbent under room temperature and atmospheric pressure conditions. The content of MEK in the outlet gas was detected by gas chromatograph. When the content of MEK in the outlet gas exceeded 1 ppm, it was considered that the adsorbent had broken through. The breakthrough adsorption capacity of MEK was calculated to be 10.2%.
[0100] 2) The permeated adsorbent sample was regenerated at 200°C for 5 hours under a nitrogen atmosphere to obtain a regenerated adsorbent. The regenerated adsorbent was then used as an adsorbent for the adsorption of the feed gas according to step 1). The permeation adsorption capacity of the regenerated adsorbent for methyl ethyl ketone was 9.9%.
[0101] Example 7
[0102] This embodiment provides an adsorbent for oxygen-containing compounds in hydrogen, which is prepared by the following method:
[0103] 9 kg of 13X molecular sieve, 15 kg of boehmite, 6 kg of coal-derived carbon powder and 0.2 kg of hydroxypropyl cellulose were mixed evenly, and then an appropriate amount of deionized water was added to extrude the mixture into strips to obtain a sample with a diameter of 1.5 mm and a length of 3 mm. The sample was dried at 120 °C for 12 h and calcined at 550 °C for 4 h under a nitrogen atmosphere to obtain the adsorbent carrier.
[0104] 3.5 g of anhydrous zinc nitrate was dissolved in 80 g of deionized water and stirred thoroughly until dissolved. The solution was then dispersed on 100 g of the prepared adsorbent support and impregnated at room temperature for 20 hours. The impregnated support was dried at 120 °C for 12 hours and calcined at 550 °C for 4 hours under a nitrogen atmosphere to obtain an adsorbent for oxygen-containing compounds in hydrogen. The prepared adsorbent, based on the mass of the adsorbent support (100%), had a ZnO loading of 1.4 wt%.
[0105] This embodiment provides a method for removing oxygen-containing compounds from industrial by-product hydrogen gas, including:
[0106] 1) 30 mL of the adsorbent prepared in Example 7 was loaded into a fixed-bed reactor to contain 1000 mg / Nm³. 3 Hydrogen gas was used as the feed gas for methyl ethyl ketone (MEK). The feed gas was introduced into a fixed-bed reactor at a flow rate of 400 mL / min and adsorbed by contacting the adsorbent under room temperature and atmospheric pressure conditions. The content of MEK in the outlet gas was detected by gas chromatograph. When the content of MEK in the outlet gas exceeded 1 ppm, it was considered that the adsorbent had broken through. The breakthrough adsorption capacity of MEK was calculated to be 11.8%.
[0107] 2) The permeated adsorbent sample was regenerated at 200°C for 5 hours under a nitrogen atmosphere to obtain a regenerated adsorbent. The regenerated adsorbent was then used as an adsorbent for the adsorption of the feed gas according to step 1). The permeation adsorption capacity of the regenerated adsorbent for methyl ethyl ketone was 11.3%.
[0108] Example 8
[0109] This embodiment provides an adsorbent for oxygen-containing compounds in hydrogen, which is prepared by the following method:
[0110] 9 kg of 13X molecular sieve, 15 kg of boehmite, 6 kg of coal-derived carbon powder and 0.2 kg of hydroxypropyl cellulose were mixed evenly, and then an appropriate amount of deionized water was added to extrude the mixture into strips to obtain a sample with a diameter of 1.5 mm and a length of 3 mm. The sample was dried at 120 °C for 12 h and calcined at 550 °C for 4 h under a nitrogen atmosphere to obtain the adsorbent carrier.
[0111] 3.5 g of anhydrous zinc nitrate was dissolved in 80 g of deionized water and stirred thoroughly until dissolved. The solution was then dispersed on 100 g of the prepared adsorbent support and impregnated at room temperature for 20 hours. The impregnated support was dried at 120 °C for 12 hours and calcined at 550 °C for 4 hours under a nitrogen atmosphere to obtain an adsorbent for oxygen-containing compounds in hydrogen. The prepared adsorbent, based on the mass of the adsorbent support (100%), had a ZnO loading of 1.4 wt%.
[0112] This embodiment provides a method for removing oxygen-containing compounds from industrial by-product hydrogen gas, including:
[0113] 1) 30 mL of the adsorbent prepared in Example 8 was loaded into a fixed-bed reactor to contain 2000 mg / Nm³. 3 Hydrogen gas was used as the feed gas for sec-butanol. The feed gas was introduced into a fixed bed reactor at a flow rate of 400 mL / min and adsorbed by contacting the adsorbent under room temperature and atmospheric pressure conditions. The content of sec-butanol in the outlet gas was detected by gas chromatograph. When the content of sec-butanol in the outlet gas exceeded 1 ppm, it was considered that the adsorbent had broken through. The breakthrough adsorption capacity of sec-butanol was calculated to be 21.8%.
[0114] 2) The permeated adsorbent sample was regenerated at 200°C for 5 hours under a nitrogen atmosphere to obtain a regenerated adsorbent. The regenerated adsorbent was then used as an adsorbent for the adsorption of the feed gas according to step 1). The SBA adsorbent permeation adsorption capacity of the regenerated adsorbent was 21.4%.
[0115] Example 9
[0116] This embodiment provides an adsorbent for oxygen-containing compounds in hydrogen, which is prepared by the following method:
[0117] 9 kg of 13X molecular sieve, 15 kg of boehmite, 6 kg of coal-derived carbon powder and 0.2 kg of hydroxypropyl cellulose were mixed evenly, and then an appropriate amount of deionized water was added to extrude the mixture into strips to obtain a sample with a diameter of 1.5 mm and a length of 3 mm. The sample was dried at 120 °C for 12 h and calcined at 550 °C for 4 h under a nitrogen atmosphere to obtain the adsorbent carrier.
[0118] 3.5 g of anhydrous zinc nitrate was dissolved in 80 g of deionized water and stirred thoroughly until dissolved. The solution was then dispersed on 100 g of the prepared adsorbent support and impregnated at room temperature for 20 hours. The impregnated support was dried at 120 °C for 12 hours and calcined at 550 °C for 4 hours under a nitrogen atmosphere to obtain an adsorbent for oxygen-containing compounds in hydrogen. The prepared adsorbent, based on the mass of the adsorbent support (100%), had a ZnO loading of 1.4 wt%.
[0119] This embodiment provides a method for removing oxygen-containing compounds from industrial by-product hydrogen gas, including:
[0120] 1) 30 mL of the adsorbent prepared in Example 9 was loaded into a fixed-bed reactor to contain 1500 mg / Nm³. 3 Acetaldehyde gas was used as the feed gas. The feed gas was introduced into the fixed bed reactor at a flow rate of 400 mL / min and adsorbed with the adsorbent under room temperature and atmospheric pressure conditions. The amount of acetaldehyde in the outlet gas was detected by gas chromatograph. When the amount of acetaldehyde in the outlet gas exceeded 1 ppm, it was considered that the adsorbent had broken through. The acetaldehyde permeation adsorption capacity was calculated to be 24.4%.
[0121] 2) The permeated adsorbent sample was regenerated at 200°C for 5 hours under a nitrogen atmosphere to obtain a regenerated adsorbent. The regenerated adsorbent was then used as an adsorbent for the adsorption of the feed gas according to step 1). The permeation adsorption capacity of the regenerated adsorbent for acetaldehyde was 24.0%.
[0122] Example 10
[0123] This embodiment provides an adsorbent for oxygen-containing compounds in hydrogen, which is prepared by the following method:
[0124] 9 kg of 13X molecular sieve, 15 kg of boehmite, 6 kg of coal-derived carbon powder and 0.2 kg of hydroxypropyl cellulose were mixed evenly, and then an appropriate amount of deionized water was added to extrude the mixture into strips to obtain a sample with a diameter of 1.5 mm and a length of 3 mm. The sample was dried at 120 °C for 12 h and calcined at 550 °C for 4 h under a nitrogen atmosphere to obtain the adsorbent carrier.
[0125] 3.5 g of anhydrous zinc nitrate was dissolved in 80 g of deionized water and stirred thoroughly until dissolved. The solution was then dispersed on 100 g of the prepared adsorbent support and impregnated at room temperature for 20 hours. The impregnated support was dried at 120 °C for 12 hours and calcined at 550 °C for 4 hours under a nitrogen atmosphere to obtain an adsorbent for oxygen-containing compounds in hydrogen. The prepared adsorbent, based on the mass of the adsorbent support (100%), had a ZnO loading of 1.4 wt%.
[0126] This embodiment provides a method for removing oxygen-containing compounds from industrial by-product hydrogen gas, including:
[0127] 1) 30 mL of the adsorbent prepared in Example 10 was loaded into a fixed-bed reactor to contain 2000 mg / Nm³. 3 Dimethyl ether was used as the feed gas. The feed gas was introduced into the fixed bed reactor at a flow rate of 400 mL / min. It was contacted with the adsorbent for adsorption under room temperature and atmospheric pressure conditions. The amount of dimethyl ether in the outlet gas was detected by gas chromatograph. When the amount of dimethyl ether in the outlet gas exceeded 1 ppm, it was considered that the adsorbent had broken through. The dimethyl ether permeation adsorption capacity was calculated to be 8.7%.
[0128] 2) The permeated adsorbent sample was regenerated at 200°C for 5 hours under a nitrogen atmosphere to obtain a regenerated adsorbent. The regenerated adsorbent was then used as an adsorbent for the adsorption of the feed gas according to step 1). The permeation adsorption capacity of the regenerated adsorbent for acetaldehyde was 8.2%.
[0129] Comparative Example 1
[0130] This comparative example provides an adsorbent for oxygen-containing compounds in hydrogen, which is prepared by the following method:
[0131] 12 kg of 13X molecular sieve, 18 kg of boehmite, and 0.2 kg of hydroxypropyl cellulose were mixed evenly, and then an appropriate amount of deionized water was added to extrude the mixture into strips to obtain a sample with a diameter of 1.5 mm and a length of 3 mm. The sample was dried at 120 °C for 12 h and calcined at 550 °C for 4 h under a nitrogen atmosphere to obtain the adsorbent carrier.
[0132] 5.0 g of sodium nitrate was dissolved in 80 g of deionized water and stirred thoroughly. The solution was then dispersed on 100 g of the prepared adsorbent support and impregnated at room temperature for 20 hours. The impregnated support was dried at 120 °C for 12 hours and calcined at 550 °C for 4 hours under a nitrogen atmosphere to obtain an adsorbent for oxygen-containing compounds in hydrogen. The prepared adsorbent, based on the mass of the adsorbent support (100%), had a Na₂O loading of 2.8 wt%.
[0133] Comparative Example 1 provides a method for removing oxygen-containing compounds from industrial by-product hydrogen gas, comprising:
[0134] 1) 30 mL of the adsorbent prepared in Comparative Example 1 was loaded into a fixed-bed reactor to contain 1000 mg / Nm³ of adsorbent. 3 Hydrogen gas was used as the feed gas for methyl ethyl ketone (MEK). The feed gas was introduced into a fixed-bed reactor at a flow rate of 400 mL / min and adsorbed by contacting the adsorbent under room temperature and atmospheric pressure conditions. The content of MEK in the outlet gas was detected by gas chromatograph. When the content of MEK in the outlet gas exceeded 1 ppm, it was considered that the adsorbent had broken through. The breakthrough adsorption capacity of MEK was calculated to be 1.7%.
[0135] 2) The permeated adsorbent sample was regenerated at 200°C for 5 hours under a nitrogen atmosphere to obtain a regenerated adsorbent. The regenerated adsorbent was then used as an adsorbent for the adsorption of the feed gas according to step 1). The permeation adsorption capacity of the regenerated adsorbent for methyl ethyl ketone was 0.3%.
[0136] Compared with the comparative adsorbent, the adsorbent with added carbon powder in the carrier provided by the present invention has a higher breakthrough adsorption capacity for methyl ethyl ketone and better regeneration performance.
[0137] Comparative Example 2
[0138] This comparative example provides an adsorbent for oxygen-containing compounds in hydrogen, which is prepared by the following method:
[0139] 9 kg of 13X molecular sieve, 15 kg of boehmite, and 6 kg of coal-derived carbon powder were mixed evenly, and then an appropriate amount of deionized water was added. The mixture was extruded into strips to obtain samples with a diameter of 1.5 mm and a length of 3 mm. The samples were dried at 120 °C for 12 h and calcined at 550 °C for 4 h under a nitrogen atmosphere to obtain the adsorbent carrier. The calcined carrier was then loaded with 1.4% adsorbent using an equal-volume impregnation method.
[0140] 3.5 g of anhydrous zinc nitrate was dissolved in 80 g of deionized water and stirred thoroughly until dissolved. The solution was then dispersed on 100 g of the prepared adsorbent support and impregnated at room temperature for 20 hours. The impregnated support was dried at 120 °C for 12 hours and calcined at 550 °C for 4 hours under a nitrogen atmosphere to obtain an adsorbent for oxygen-containing compounds in hydrogen. The prepared adsorbent, based on the mass of the adsorbent support (100%), had a ZnO loading of 1.4 wt%.
[0141] Comparative Example 2 provides a method for removing oxygen-containing compounds from industrial by-product hydrogen gas, including:
[0142] 1) 30 mL of the adsorbent prepared in Comparative Example 2 was loaded into a fixed-bed reactor to contain 2000 mg / Nm³ of adsorbent. 3 Dimethyl ether was used as the feed gas. The feed gas was introduced into the fixed bed reactor at a flow rate of 400 mL / min. It was contacted with the adsorbent for adsorption under room temperature and atmospheric pressure conditions. The amount of dimethyl ether in the outlet gas was detected by gas chromatograph. When the amount of dimethyl ether in the outlet gas exceeded 1 ppm, it was considered that the adsorbent had broken through. The dimethyl ether permeation adsorption capacity was calculated to be 1.4%.
[0143] 2) The permeated adsorbent sample was regenerated at 200°C for 5 hours under a nitrogen atmosphere to obtain a regenerated adsorbent. The regenerated adsorbent was then used as an adsorbent for the adsorption of the feed gas according to step 1). The permeation adsorption capacity of the regenerated adsorbent for acetaldehyde was 1.0%.
[0144] Compared with the comparative adsorbent, the adsorbent with added hydroxypropyl cellulose in the carrier provided by the present invention has a higher breakthrough adsorption capacity for methyl ethyl ketone and better regeneration performance.
Claims
1. An adsorbent for oxygen-containing compounds in hydrogen gas, wherein, The adsorbent comprises a support and an active metal oxide component loaded on the support; Based on the total mass of the raw material components of the adsorbent carrier as 100%, the raw material components of the adsorbent carrier include 20-80 wt% molecular sieve, 10-70 wt% binder, 2-10 wt% first auxiliary agent and 1-6 wt% second auxiliary agent; based on the mass of the adsorbent carrier as 100%, the loading of the metal oxide active component is 1.0-6.0 wt%. The first additive is toner; The second auxiliary agent is hydroxypropyl cellulose; The molecular sieve includes at least one of 13X molecular sieve, NaY molecular sieve, ZSM-5 molecular sieve, composite molecular sieve of SBA-15 and ZSM-5, and composite molecular sieve of 13X and ZSM-5. The active metal oxide component includes at least one of sodium oxide, magnesium oxide, zinc oxide, copper oxide, and nickel oxide. The oxygen-containing compound adsorbent in hydrogen can be prepared by a method including the following steps: 1) Molecular sieve, binder, first auxiliary agent, second auxiliary agent and water are mixed and shaped, and then dried and calcined at 300-600℃ under a protective atmosphere to obtain the carrier of the adsorbent; 2) The precursor salt of the active component of metal oxide is loaded onto the carrier of the adsorbent, and then dried and calcined at 300-600℃ under a protective atmosphere to obtain the oxygen-containing compound adsorbent in hydrogen.
2. The adsorbent according to claim 1, wherein, The first additive includes at least one of coal-derived carbon powder, wood-based carbon powder, and coconut shell carbon powder.
3. The adsorbent according to claim 1, wherein, The binder includes at least one of boehmite, diatomaceous earth, attapulgite, and activated alumina.
4. The adsorbent according to claim 1, wherein, The forming process is extrusion forming.
5. The adsorbent according to claim 4, wherein, The outer diameter of the molded part is 1.5-3mm and the length is 3-5mm.
6. The adsorbent according to claim 1, wherein, In step 1), the protective atmosphere is a nitrogen atmosphere.
7. The method for preparing the oxygen-containing compound adsorbent in hydrogen according to any one of claims 1-6, wherein, The preparation method includes: 1) Molecular sieve, binder, first auxiliary agent, second auxiliary agent and water are mixed and shaped, and then dried and calcined at 300-600℃ under a protective atmosphere to obtain the carrier of the adsorbent; 2) The precursor salt of the active component of metal oxide is loaded onto the carrier of the adsorbent, and then dried and calcined at 300-600℃ under a protective atmosphere to obtain the oxygen-containing compound adsorbent in hydrogen.
8. The preparation method according to claim 7, wherein, In step 2), The protective atmosphere is a nitrogen atmosphere.
9. The preparation method according to claim 7, wherein, In step 2), the loading of the precursor salt of the metal oxide active component onto the adsorbent support is achieved in the following manner: The carrier of the adsorbent is impregnated with a precursor salt solution of the active metal oxide component; The precursor salt solution of the metal oxide active component has a molar concentration of 0.2-1.5 mol / L, based on the volume of the solution.
10. A method for removing oxygen-containing compounds from industrial by-product hydrogen gas, wherein, This method uses the oxygen-containing compound adsorbent in hydrogen as described in any one of claims 1-6 to adsorb oxygen-containing compounds in industrial by-product hydrogen to be treated.
11. The method according to claim 10, wherein, The oxygen-containing compounds in the industrial by-product hydrogen include at least one of alcohols, ketones, acids, esters, aldehydes, and furans.
12. The method according to claim 11, wherein, Based on the mass of industrial by-product hydrogen as 100%, the mass percentage of oxygen-containing compounds in the industrial by-product hydrogen is 0.1-5%.
13. The method according to claim 10, wherein, The industrial by-product hydrogen includes at least one of the following: hydrogen produced by dehydrogenation of sec-butanol, hydrogen produced by dehydrogenation of butanediol, and hydrogen produced by dehydrogenation of ethanol.
14. The method of claim 10, wherein, The adsorption of oxygen-containing compounds from industrial by-product hydrogen using the aforementioned oxygen-containing compound adsorbent includes: The industrial by-product hydrogen to be treated is passed into the oxygen-containing compound adsorbent of hydrogen as described in any one of claims 1-6 for adsorption.
15. The method according to claim 14, wherein, Adsorption occurs at room temperature.
16. The method of claim 14, wherein, Adsorption occurs at atmospheric pressure.
17. The method of claim 14, wherein, The flow rate of the industrial by-product hydrogen to be processed is 200-600 mL / min.
18. The method according to claim 10, wherein, The method further includes regenerating the exhausted adsorbent in a protective atmosphere at 150-350°C and then reusing it to adsorb oxygen-containing compounds in the industrial by-product hydrogen to be treated.
19. The method according to claim 18, wherein, The protective atmosphere is a nitrogen atmosphere.
20. The method according to claim 18, wherein, The failed adsorbent is a permeated adsorbent; wherein, when the content of oxygen-containing compounds in the adsorbed product exceeds 1 ppm, the adsorbent permeates.