Adsorbents, methods of making and using the same

Abstract

The present application relates to raw material purification field, disclose a kind of adsorbent, the adsorbent contains with weight fraction: a) 1~8 parts alkali metal;B) 2~10 parts zinc oxide;C) 5~15 parts copper oxide;D) 60~90 parts alumina;Optionally e) 0-10 parts silicon oxide.The adsorbent of the present application is low in cost, good in performance, simple in process.The preparation method of the adsorbent and its application are disclosed.The adsorbent can remove AsH3, PH3, COS, CS2 and H2S simultaneously, and can be used for removing AsH3, PH3, COS and H2S in natural gas, synthesis gas, light gas and liquid hydrocarbon.

Description

Technical Field

[0001] This invention relates to the field of raw material purification, specifically to an adsorbent, its preparation method, and its application. Background Technology

[0002] Industrial raw materials derived from natural gas, coal, and petroleum often contain impurities such as sulfur (S), asluene (As), and phosphorus (P). For example, CO produced from coal contains organic sulfur compounds such as carbonyl sulfide (COS) and carbon disulfide (CS2), as well as hydrogen sulfide (H2S). Propylene produced from petroleum contains impurities such as AsH3, PH3, COS, and H2S. The presence of these impurities can poison downstream catalysts. Impurities in CO can cause poisoning and deactivation of downstream polycarbonate catalysts, and impurities in propylene can cause poisoning and deactivation of polypropylene catalysts. Therefore, these raw materials need to be purified. Adsorption methods are widely used due to their simple operation and mild reaction conditions.

[0003] CN101602642A discloses an arsenic removal and purification agent for propylene and ethylene light hydrocarbon materials. This agent uses alumina as a carrier, copper oxide as the active component, and zinc oxide as an auxiliary agent. It contains 32-35% CuO and 33-40% ZnO by weight, with the balance being alumina. This purifier can be directly used in production processes involving the removal of arsenic from propylene and ethylene light hydrocarbon materials at high space velocities and high arsine concentrations. The purifier can be used at room temperature, normal pressure, and a space velocity of 1200-2100 hr. -1 This is equivalent to a liquid air velocity of 4.5-8.0 hr. -1 Under suitable conditions, it features high arsenic removal precision and large arsenic capacity. It can remove arsenic from raw materials from 1000 ppm to below 5 ppb at room temperature and pressure, with a saturated arsenic capacity exceeding 30% and an industrial effective capacity greater than 15%. It also possesses strong desulfurization capabilities.

[0004] CN108970611A discloses a natural gas organic sulfur hydrolysis catalyst and its preparation method. The catalyst uses alumina, titanium dioxide, and silica as supports, and sodium and cerium salts as active components. The prepared catalyst has a specific surface area greater than 300 m². 2 With a pore volume of 0.45 ml / g, it exhibits good activity and stability, and an organic sulfur hydrolysis rate ≥99%. However, this technology incorporates titanium dioxide as a carrier, resulting in higher production costs, and the reaction temperature is 60℃, which does not meet the requirements for low-temperature applications.

[0005] CN104907104B discloses a method for low-temperature removal of CS2 using a core-shell catalyst. This invention uses activated carbon nanoparticles as the core of the catalyst and wraps a layer of Fe2O3 around the core as the shell to prepare a catalyst that is inexpensive and readily available and has low-temperature catalytic activity for CS2. When this catalyst is used for the removal of CS2 gas, it has high low-temperature catalytic activity and can effectively degrade CS2 in industrial exhaust gas.

[0006] While the above technologies can remove AsH3, COS, and CS2, they cannot remove these impurities simultaneously. In industrial applications, multiple protective beds need to be connected in series to remove all impurities. Summary of the Invention

[0007] The purpose of this invention is to overcome the problem that existing technologies require multiple adsorbents to be used in series for different impurities, resulting in overly complex processes. This invention provides an adsorbent that is low in cost, has good performance, and is simple to process, and can simultaneously remove AsH3, PH3, COS, CS2 and H2S.

[0008] To achieve the above objectives, the present invention provides an adsorbent containing, by weight,: a) 1 to 8 parts of alkali metal; b) 2 to 10 parts of zinc oxide; c) 5 to 15 parts of copper oxide; d) 60 to 90 parts of aluminum oxide; and optionally e) 0 to 10 parts of silicon oxide.

[0009] A second aspect of the present invention provides a method for preparing the adsorbent of the present invention, the method comprising:

[0010] (1) Co-precipitate a solution containing copper and aluminum (I) and an alkaline solution (II) in a reactor in parallel flow to obtain a mixed solution;

[0011] (2) Add boehmite to the mixed solution to obtain the precursor;

[0012] (3) The above precursor was calcined to obtain component A;

[0013] (4) Mix component A, solid aluminum source and / or solid silicon source, grind into powder, shape and dry to obtain adsorbent particles B;

[0014] (5) The adsorbent particles B were immersed in a zinc salt solution, dried and calcined to obtain adsorbent particles C;

[0015] (6) Immerse adsorbent particles C in an alkali metal solution and dry to obtain the adsorbent.

[0016] The adsorbent of this invention can simultaneously remove AsH3, PH3, COS, CS2 and H2S.

[0017] A third aspect of the present invention provides the application of the adsorbent of the present invention in the adsorption and removal of one or more of AsH3, PH3, COS, CS2 and H2S from one or more raw materials such as natural gas, syngas, coke oven gas, and light gas liquid hydrocarbons.

[0018] The adsorbent of this invention can be used to remove AsH3, PH3, COS and H2S from raw materials such as natural gas, syngas, light gas and liquid hydrocarbons. Attached Figure Description

[0019] Figure 1 This is the XRD pattern of the copper oxide prepared in Example 1. Detailed Implementation

[0020] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0021] The present invention provides an adsorbent containing, by weight,: a) 1 to 8 parts of alkali metal; b) 2 to 10 parts of zinc oxide; c) 5 to 15 parts of copper oxide; d) 60 to 90 parts of aluminum oxide; and optionally e) 0 to 10 parts of silicon oxide.

[0022] In this invention, alkali metals exist in the form of alkaline compounds, such as KOH, Na2CO3, NaOH, and K2CO3, and the content of alkali metals is determined by ICP.

[0023] The adsorbent of this invention can simultaneously remove AsH3, PH3, COS, CS2 and H2S.

[0024] In this invention, the grain size of the copper oxide is not particularly important as long as the objective of the invention is achieved. According to a particularly preferred embodiment of the invention, the adsorbent has copper oxide grains of less than or equal to 15 nm. By adopting the aforementioned preferred embodiment, the desorption effect of the adsorbent can be further improved.

[0025] To further improve the desorption effect of the adsorbent, the copper oxide has a grain size of 8–13 nm.

[0026] According to a particularly preferred embodiment of the present invention, the adsorbent, by weight, contains 2 to 6 parts of alkali metal, 3 to 9 parts of zinc oxide, 8 to 12 parts of copper oxide, 65 to 85 parts of aluminum oxide, and optionally 0 to 8 parts of silicon oxide.

[0027] In this invention, as long as the objective of the invention can be achieved, there are no special requirements for the specific surface area of ​​the adsorbent. According to a particularly preferred embodiment of the invention, the specific surface area of ​​the adsorbent is greater than 110 m². 2 / g, preferably 120-160m 2 / g. By adopting the aforementioned preferred scheme, the desorption effect of the adsorbent can be further improved.

[0028] In this invention, the pore volume of the adsorbent is not particularly required as long as the objective of the invention can be achieved. According to a particularly preferred embodiment of the invention, the pore volume of the adsorbent is greater than 0.2 cm³. 3 / g, preferably 0.25-0.4cm 3 / g. By adopting the aforementioned preferred scheme, the desorption effect of the adsorbent can be further improved.

[0029] In this invention, any adsorbent possessing the aforementioned characteristics can achieve the objective of this invention. There are no particular requirements for the preparation method of the adsorbent. According to a preferred embodiment of this invention, the preparation method of the adsorbent includes:

[0030] (1) Co-precipitate a solution containing copper and aluminum (I) and an alkaline solution (II) in a reactor in parallel flow to obtain a mixed solution;

[0031] (2) Add boehmite to the mixed solution to obtain the precursor;

[0032] (3) The above precursor was calcined to obtain component A;

[0033] (4) Mix component A, solid aluminum source and / or solid silicon source, grind into powder, shape and dry to obtain adsorbent particles B;

[0034] (5) The adsorbent particles B were immersed in a zinc salt solution, dried and calcined to obtain adsorbent particles C;

[0035] (6) Immerse adsorbent particles C in an alkali metal solution and dry to obtain the adsorbent.

[0036] This invention employs the addition of an auxiliary agent during the co-precipitation process, resulting in smaller copper oxide crystallites and increased specific surface area and pore volume of the adsorbent, which is beneficial for improving adsorbent performance. Simultaneously, this invention disperses CuO in alumina, which can improve the utilization rate of the active component and reduce adsorbent costs.

[0037] According to a preferred embodiment of the present invention, in the preparation method, step (1) involves co-precipitating a copper and aluminum solution I and an alkaline solution II into a reactor containing an aqueous dispersant solution, preferably one or more of polyethylene glycol 6000, polyethylene glycol 2000, and polyethylene glycol 600.

[0038] According to a preferred embodiment of the present invention, in the preparation method, the amount of dispersant used in step (1) is 0.1-3% of the combined mass of the added copper compound and aluminum compound. By adopting the aforementioned preferred scheme, the oxide can be better dispersed.

[0039] In this invention, the precipitation conditions in step (1) can be conventionally chosen in the art. According to a preferred embodiment of this invention, the precipitation conditions in step (1) include: pH 6-11, temperature 40-90°C, and time 0.5-3 hours. By adopting the aforementioned preferred scheme, the crystallization state of the precursor can be controlled to obtain an ideal precursor.

[0040] To further improve the desorption effect of the adsorbent, the precipitation conditions in step (1) include: pH 9 to 11.

[0041] In this invention, as long as the objective of this invention can be achieved, there are no special requirements for the copper and aluminum-containing solution I in step (1). According to a particularly preferred embodiment of this invention, in the copper and aluminum-containing solution I in step (1), the molar concentration of Cu is 0.5–1.0 mol / L; and the molar concentration of Al is 0.1–0.6 mol / L. By adopting the aforementioned preferred scheme, an ideal precursor crystal phase can be obtained.

[0042] In order to obtain a more ideal precursor crystal phase, the Cu / Al molar ratio in the copper and aluminum solution I in step (1) is 1 to 10.

[0043] In this invention, as long as the purpose of this invention can be achieved, there are no special requirements for the alkaline solution II in step (1). According to a particularly preferred embodiment of this invention, the molar concentration of alkaline solution II in step (1) is 1.0 to 1.5 mol / L.

[0044] According to a particularly preferred embodiment of the present invention, the copper is derived from one or more of copper nitrate, copper sulfate, and copper acetate.

[0045] According to a particularly preferred embodiment of the invention, the aluminum is derived from one or more of aluminum nitrate and aluminum sulfate.

[0046] According to a particularly preferred embodiment of the present invention, the alkaline substance in the alkaline solution II is selected from one or more of sodium carbonate, sodium bicarbonate and ammonium carbonate.

[0047] By adopting the aforementioned preferred scheme, an ideal precursor can be obtained, thereby obtaining an ideal oxide.

[0048] In this invention, as long as the objective of this invention can be achieved, there are no special requirements for the mixing conditions in step (2). According to a particularly preferred embodiment of this invention, in step (2), the amount of boehmite added is 20% to 30% of the mass of copper added in step (1) based on copper oxide, and the mixing time is 0.25 to 1 hour. By adopting the aforementioned preferred scheme, the precursor can be further dispersed.

[0049] In this invention, the roasting conditions in step (3) can be conventional choices in the art. According to a preferred embodiment of this invention, the roasting conditions in step (3) include: a roasting temperature of 300 to 500°C.

[0050] According to a preferred embodiment of the present invention, in step (3), component A contains 60% to 80% copper oxide and 20% to 40% aluminum oxide by mass fraction. By adopting the aforementioned preferred scheme, copper oxide with smaller grains can be obtained.

[0051] According to a preferred embodiment of the present invention, there are no special requirements for the types of solid aluminum source and / or solid silicon source. For the present invention, it is preferred that the solid aluminum source is alumina and the solid silicon source is silicon oxide, silica sol or other silicon-containing substances.

[0052] In this invention, the drying conditions in step (5) can be conventionally chosen in the art. According to a preferred embodiment of the invention, the drying conditions in step (5) include a drying temperature of 50–150°C. By adopting the aforementioned preferred solution, the decomposition of the precursor can be avoided.

[0053] In this invention, the calcination conditions in step (5) can be conventionally chosen in the art. According to a preferred embodiment of this invention, the calcination conditions in step (5) include a calcination temperature of 400–500°C. By adopting the aforementioned preferred scheme, the decomposition temperature can be controlled, and grain agglomeration and growth can be avoided.

[0054] In this invention, as long as the objective of this invention can be achieved, there are no special requirements for the zinc loading in step (5). According to a particularly preferred embodiment of this invention, the zinc loading in step (5) is 2 to 10% by weight. By adopting the aforementioned preferred scheme, the adsorbent can have appropriate alkaline centers without causing pore blockage due to excessive loading.

[0055] In this invention, the drying conditions in step (6) can be conventionally chosen in the art. According to a preferred embodiment of the invention, the drying conditions in step (6) include a drying temperature of 50–150°C. By adopting the aforementioned preferred solution, the removal of moisture from the adsorbent can be guaranteed.

[0056] In this invention, as long as the objective of this invention can be achieved, there are no special requirements for the alkali metal loading in step (6). According to a particularly preferred embodiment of this invention, the alkali metal loading in step (6) is 1 to 8% by weight. By adopting the aforementioned preferred scheme, the adsorbent can have appropriate alkali centers without causing pore blockage due to excessive loading.

[0057] In this invention, as long as the objective of this invention can be achieved, the alkali metal compound in step (6) can be any conventional choice in the art. According to a particularly preferred embodiment of this invention, in step (6), the alkali metal compound in the alkali metal solution is one of KOH, Na2CO3, NaOH, and K2CO3, preferably KOH and / or K2CO3. By adopting the aforementioned preferred scheme, the adsorbent can have more alkaline centers.

[0058] A third aspect of the present invention provides the application of the adsorbent of the present invention in the adsorption and removal of one or more of AsH3, PH3, COS, CS2 and H2S from one or more raw materials such as natural gas, syngas, coke oven gas, and light gas liquid hydrocarbons.

[0059] The adsorbent of this invention combines the CuO component that removes AsH3 and PH3 with organic compounds that remove COS, CS2 alkali metals and transition metal zinc, achieving the effect of simultaneously removing AsH3, PH3, COS, CS2 and H2S.

[0060] The present invention will be further described below through specific embodiments. The scope of the present invention is not limited to the scope covered by the embodiments. The XRD patterns were determined using a Rigaku D / MAX-1400 X-ray powder diffractometer (Japan). Cu Kα lines were used as the X-ray source. A nickel filter was used, with a 2θ scanning range of 5–70°, an operating voltage of 40 kV, a current of 40 mA, and a scanning rate of 10° / min to obtain XRD patterns. The grain size of the sample was calculated using the Scherrer equation based on the XRD patterns.

[0061] Example 1

[0062] 200 ml of distilled water and 0.33 g of polyethylene glycol 6000 were added to a 2000 ml coprecipitation reactor and stirred until homogeneous. A mixed solution of 0.8 mol / L copper nitrate and 0.2 mol / L aluminum nitrate was added at a rate of 20 ml / min, while a 1.2 mol / L sodium carbonate solution was added dropwise to maintain the pH at 10. The addition was carried out over 30 minutes. After the addition was complete, the reaction was carried out at 60 °C for 1 hour to obtain a mixed solution. Subsequently, 10 g of boehmite was added to the coprecipitation reactor, and the reaction was continued for 0.5 hours to obtain a precipitate. The precipitate was washed and dried to obtain a precursor containing basic copper carbonate.

[0063] The above precursor was calcined at 400°C for 5 hours to obtain component A containing CuO (containing 74% by weight of copper oxide and 26% by weight of aluminum oxide). Figure 1 The XRD pattern of component A is given. Based on the diffraction peaks of the (111) crystal plane of copper oxide, the grain size of copper oxide is calculated to be 11 nm using the Scherrer formula.

[0064] 21g of component A and 94g of alumina were mixed, shaped, dried, and calcined to obtain adsorbent particles B. A solution of 22g zinc nitrate and 30g water was prepared, and adsorbent B was impregnated in it, dried at 100℃, and calcined at 450℃ to obtain adsorbent particles C. A solution of 8g potassium hydroxide and 40g water was prepared, and adsorbent particles C were impregnated in it, dried at 120℃ to obtain adsorbent particles C. The weight composition of the adsorbent is: K 4.5%, ZnO 4.7%, CuO 9.4%, Al₂O₃ 79.3%. The specific surface area of ​​the adsorbent is 160 m². 2 / g, pore volume 0.32cm 3 / g.

[0065] The adsorbent particles were ground to 20-40 mesh, and 5g was weighed and loaded into a fixed-bed reactor. At room temperature and pressure, nitrogen gas containing 100 μmol / mol COS + 20 μmol / mol CS2 + 50 μmol / mol H2S + 10 μmol / mol AsH3 + 10 μmol / mol PH3 was introduced at a rate of 100 ml / min. The concentration of each impurity at the bed outlet was detected using a helium ion detector. When the outlet concentration of any substance exceeded 1 μmol / mol, it was considered that the substance had penetrated. The sulfur capacity and (arsenic + phosphorus) capacity of the adsorbent were calculated based on the penetration time. The sulfur capacity of the adsorbent was 2.57%; the (arsenic + phosphorus) capacity was 0.69%.

[0066] Example 2

[0067] 200 ml of distilled water and 0.72 g of polyethylene glycol 2000 were added to a 2000 ml coprecipitation reactor and stirred until homogeneous. A mixed solution of 0.9 mol / L copper nitrate and 0.1 mol / L aluminum nitrate was added at a rate of 20 ml / min, while a 1.1 mol / L sodium carbonate solution was added dropwise to maintain the pH at 9. The addition was carried out over 30 minutes. After the addition was complete, the reaction was carried out at 50 °C for 1.5 hours to obtain a mixed solution. Subsequently, 10 g of boehmite was added to the coprecipitation reactor, and the reaction was continued for 0.5 hours to obtain a precipitate. The precipitate was washed and dried to obtain a precursor containing basic copper carbonate.

[0068] The above precursor was calcined at 500°C for 4 hours to obtain component A containing CuO (containing 80% copper oxide and 20% aluminum oxide). Figure 1 The XRD pattern of component A is given. Based on the diffraction peaks of the (111) crystal plane of copper oxide, the grain size of copper oxide is calculated to be 13 nm using the Scherrer formula.

[0069] 21g of component A and 94g of alumina were mixed, shaped, dried, and calcined to obtain adsorbent particles B. A solution of 22g zinc nitrate and 30g water was prepared, and adsorbent B was impregnated in it, dried at 130℃, and calcined at 500℃ to obtain adsorbent particles C. A solution of 8g potassium hydroxide and 40g water was prepared, and adsorbent particles C were impregnated in it, dried at 80℃ to obtain adsorbent particles C. Adsorbent composition: K 4.5%, Zn 4.7%, CuO 10.2%, Al₂O₃ 78.5%. The specific surface area of ​​the adsorbent is 146 m². 2 / g, pore volume 0.27cm 3 / g.

[0070] The adsorbent particles were ground to 20-40 mesh, and 5g was weighed and loaded into a fixed-bed reactor. At room temperature and pressure, nitrogen gas containing 100 μmol / mol COS + 20 μmol / mol CS2 + 50 μmol / mol H2S + 10 μmol / mol AsH3 + 10 μmol / mol PH3 was introduced at a rate of 100 ml / min. The concentration of each impurity at the bed outlet was detected using a helium ion detector. When the outlet concentration of any substance exceeded 1 μmol / mol, it was considered that the substance had penetrated. The sulfur capacity and (arsenic + phosphorus) capacity of the adsorbent were calculated based on the penetration time. The sulfur capacity of the adsorbent was 2.46%; the (arsenic + phosphorus) capacity was 0.57%.

[0071] Example 3

[0072] 200 ml of distilled water and 0.66 g of polyethylene glycol 600 were added to a 2000 ml coprecipitation reactor and stirred until homogeneous. A mixed solution of 0.7 mol / L copper nitrate and 0.3 mol / L aluminum nitrate was added at a rate of 20 ml / min, while a 1.0 mol / L sodium carbonate solution was added dropwise to maintain the pH at 8. The addition was carried out over 30 minutes. After the addition was complete, the reaction was carried out at 80 °C for 0.5 hours to obtain a mixed solution. Subsequently, 10 g of boehmite was added to the coprecipitation reactor, and the reaction was continued for 0.5 hours to obtain a precipitate. The precipitate was washed and dried to obtain a precursor containing basic copper carbonate.

[0073] The above precursor was calcined at 300°C for 6 hours to obtain component A containing CuO (containing 71% by weight of copper oxide and 29% by weight of aluminum oxide). Figure 1 The XRD pattern of component A is given. Based on the diffraction peaks of the (111) crystal plane of copper oxide, the grain size of copper oxide is calculated to be 10 nm using the Scherrer formula.

[0074] 21g of component A and 94g of alumina were mixed, shaped, dried, and calcined to obtain adsorbent particles B. A solution of 22g zinc nitrate and 30g water was prepared, and adsorbent B was impregnated in it, dried at 70℃, and calcined at 400℃ to obtain adsorbent particles C. A solution of 8g potassium hydroxide and 40g water was prepared, and adsorbent particles C were impregnated in it, dried at 100℃ to obtain adsorbent particles C. The weight composition of the adsorbent is: K 4.5%, ZnO 4.7%, CuO 8.4%, Al₂O₃ 80.3%. The specific surface area of ​​the adsorbent is 160 m². 2 / g, pore volume 0.32cm 3 / g.

[0075] The adsorbent particles were ground to 20-40 mesh, and 5g was weighed and loaded into a fixed-bed reactor. At room temperature and pressure, nitrogen gas containing 100 μmol / mol COS + 20 μmol / mol CS2 + 50 μmol / mol H2S + 10 μmol / mol AsH3 + 10 μmol / mol PH3 was introduced at a rate of 100 ml / min. The concentration of each impurity at the bed outlet was detected using a helium ion detector. When the outlet concentration of any substance exceeded 1 μmol / mol, it was considered that the substance had penetrated. The sulfur capacity and (arsenic + phosphorus) capacity of the adsorbent were calculated based on the penetration time. The sulfur capacity of the adsorbent was 2.47%; the (arsenic + phosphorus) capacity was 0.59%.

[0076] Example 4

[0077] 200 ml of distilled water was added to a 2000 ml coprecipitation reactor. A mixed solution of 0.8 mol / L copper nitrate and 0.2 mol / L aluminum nitrate was added at a rate of 20 ml / min, while a 1.2 mol / L sodium carbonate solution was added dropwise, maintaining the pH at 10. The addition was carried out over 30 minutes. After the addition was complete, the reaction was carried out at 60 °C for 1 hour to obtain a mixed solution. Subsequently, 10 g of boehmite was added to the coprecipitation reactor, and the reaction was continued for 0.5 hours to obtain a precipitate. The precipitate was washed and dried to obtain a precursor containing basic copper carbonate.

[0078] The above precursor was calcined at 400°C for 5 hours to obtain component A containing CuO (containing 74% by weight of copper oxide and 26% by weight of aluminum oxide). Figure 1 The XRD pattern of component A is given. Based on the diffraction peaks of the (111) crystal plane of copper oxide, the grain size of copper oxide is calculated to be 14 nm using the Scherrer formula.

[0079] 21g of component A and 94g of alumina were mixed, shaped, dried, and calcined to obtain adsorbent particles B. A solution of 22g zinc nitrate and 30g water was prepared, and adsorbent B was impregnated in it, dried at 100℃, and calcined at 450℃ to obtain adsorbent particles C. A solution of 8g potassium hydroxide and 40g water was prepared, and adsorbent particles C were impregnated in it, dried at 120℃ to obtain adsorbent particles C. The weight composition of the adsorbent is: K 4.5%, ZnO 4.7%, CuO 9.4%, Al₂O₃ 79.3%. The specific surface area of ​​the adsorbent is 139 m². 2 / g, pore volume 0.28cm 3 / g.

[0080] The adsorbent particles were ground to 20-40 mesh, and 5g was weighed and loaded into a fixed-bed reactor. At room temperature and pressure, nitrogen gas containing 100 μmol / mol COS + 20 μmol / mol CS2 + 50 μmol / mol H2S + 10 μmol / mol AsH3 + 10 μmol / mol PH3 was introduced at a rate of 100 ml / min. The concentration of each impurity at the bed outlet was detected using a helium ion detector. When the outlet concentration of any substance exceeded 1 μmol / mol, it was considered that the substance had penetrated. The sulfur capacity and (arsenic + phosphorus) capacity of the adsorbent were calculated based on the penetration time. The sulfur capacity of the adsorbent was 2.34%; the (arsenic + phosphorus) capacity was 0.43%.

[0081] Example 5

[0082] 200 ml of distilled water and 0.33 g of polyethylene glycol 6000 were added to a 2000 ml coprecipitation reactor and stirred until homogeneous. A mixed solution of 0.8 mol / L copper nitrate and 0.2 mol / L aluminum nitrate was added at a rate of 20 ml / min, while a 1.2 mol / L sodium carbonate solution was added dropwise to maintain the pH at 8. The addition was carried out over 30 minutes. After the addition was complete, the reaction was carried out at 60 °C for 1 hour to obtain a mixed solution. Subsequently, 10 g of boehmite was added to the coprecipitation reactor, and the reaction was continued for 0.5 hours to obtain a precipitate. The precipitate was washed and dried to obtain a precursor containing basic copper carbonate.

[0083] The above precursor was calcined at 400°C for 5 hours to obtain component A containing CuO (containing 74% copper oxide and 26% aluminum oxide). Figure 1 The XRD pattern of component A is given. Based on the diffraction peaks of the (111) crystal plane of copper oxide, the grain size of copper oxide is calculated to be 13 nm using the Scherrer formula.

[0084] 21g of component A and 94g of alumina were mixed, shaped, dried, and calcined to obtain adsorbent particles B. A solution of 22g zinc nitrate and 30g water was prepared, and adsorbent B was impregnated in it, dried at 100℃, and calcined at 450℃ to obtain adsorbent particles C. A solution of 8g potassium hydroxide and 40g water was prepared, and adsorbent particles C were impregnated in it, dried at 120℃ to obtain adsorbent particles C. Adsorbent composition: K 4.5%, ZnO 4.7%, CuO 9.4%, Al₂O₃ 79.3%. The specific surface area of ​​the adsorbent is 136 m². 2 / g, pore volume 0.29cm 3 / g.

[0085] The adsorbent particles were ground to 20-40 mesh, and 5g was weighed and loaded into a fixed-bed reactor. At room temperature and pressure, nitrogen gas containing 100 μmol / mol COS + 20 μmol / mol CS2 + 50 μmol / mol H2S + 10 μmol / mol AsH3 + 10 μmol / mol PH3 was introduced at a rate of 100 ml / min. The concentration of each impurity at the bed outlet was detected using a helium ion detector. When the outlet concentration of any substance exceeded 1 μmol / mol, it was considered that the substance had penetrated. The sulfur capacity and (arsenic + phosphorus) capacity of the adsorbent were calculated based on the penetration time. The sulfur capacity of the adsorbent was 2.29%; the (arsenic + phosphorus) capacity was 0.43%.

[0086] Example 6

[0087] 200 ml of distilled water and 0.33 g of polyethylene glycol 6000 were added to a 2000 ml coprecipitation reactor and stirred until homogeneous. A mixed solution of 0.8 mol / L copper nitrate and 0.2 mol / L aluminum nitrate was added at a rate of 20 ml / min, while a 1.2 mol / L sodium carbonate solution was added dropwise to maintain the pH at 10. The addition was carried out over 30 minutes. After the addition was complete, the reaction was carried out at 60 °C for 1 hour to obtain a mixed solution. Subsequently, 5 g of boehmite was added to the coprecipitation reactor, and the reaction was continued for 0.5 hours to obtain a precipitate. The precipitate was washed and dried to obtain a precursor containing basic copper carbonate.

[0088] The above precursor was calcined at 400°C for 5 hours to obtain component A containing CuO (containing 81% copper oxide and 18% aluminum oxide by weight). Figure 1 The XRD pattern of component A is given. Based on the diffraction peaks of the (111) crystal plane of copper oxide, the grain size of copper oxide is calculated to be 12 nm using the Scherrer formula.

[0089] 21g of component A and 94g of alumina were mixed, shaped, dried, and calcined to obtain adsorbent particles B. A solution of 22g zinc nitrate and 30g water was prepared, and adsorbent B was impregnated in it, dried at 100℃, and calcined at 450℃ to obtain adsorbent particles C. A solution of 8g potassium hydroxide and 40g water was prepared, and adsorbent particles C were impregnated in it, dried at 120℃ to obtain adsorbent particles C. The weight composition of the adsorbent is: K 5.0%, ZnO 4.7%, CuO 10%, Al₂O₃ 77.9%. The specific surface area of ​​the adsorbent is 127 m². 2 / g, pore volume 0.29cm 3 / g.

[0090] The adsorbent particles were ground to 20-40 mesh, and 5g was weighed and loaded into a fixed-bed reactor. At room temperature and pressure, nitrogen gas containing 100 μmol / mol COS + 20 μmol / mol CS2 + 50 μmol / mol H2S + 10 μmol / mol AsH3 + 10 μmol / mol PH3 was introduced at a rate of 100 ml / min. The concentration of each impurity at the bed outlet was detected using a helium ion detector. When the outlet concentration of any substance exceeded 1 μmol / mol, it was considered that the substance had penetrated. The sulfur capacity and (arsenic + phosphorus) capacity of the adsorbent were calculated based on the penetration time. The sulfur capacity of the adsorbent was 2.45%; the (arsenic + phosphorus) capacity was 0.52%.

[0091] Example 7

[0092] 200 ml of distilled water and 0.33 g of polyethylene glycol 6000 were added to a 2000 ml coprecipitation reactor and stirred until homogeneous. A mixed solution of 0.8 mol / L copper nitrate and 0.2 mol / L aluminum nitrate was added at a rate of 20 ml / min, while a 1.2 mol / L sodium carbonate solution was added dropwise to maintain the pH at 10. The addition was carried out over 30 minutes. After the addition was complete, the reaction was carried out at 60 °C for 1 hour to obtain a mixed solution. Subsequently, 10 g of boehmite was added to the coprecipitation reactor, and the reaction was continued for 0.5 hours to obtain a precipitate. The precipitate was washed and dried to obtain a precursor containing basic copper carbonate.

[0093] The above precursor was calcined at 400°C for 5 hours to obtain component A containing CuO (containing 74% by weight of copper oxide and 26% by weight of aluminum oxide). Figure 1 The XRD pattern of component A is given. Based on the diffraction peaks of the (111) crystal plane of copper oxide, the grain size of copper oxide is calculated to be 11 nm using the Scherrer formula.

[0094] 21g of component A and 94g of alumina were mixed, shaped, dried, and calcined to obtain adsorbent particles B. A solution of 9g zinc nitrate and 30g water was prepared, and adsorbent B was impregnated in it, dried at 100℃, and calcined at 450℃ to obtain adsorbent particles C. A solution of 8g potassium hydroxide and 40g water was prepared, and adsorbent particles C were impregnated in it, dried at 120℃ to obtain adsorbent particles C. The weight composition of the adsorbent is: K 5.1%, ZnO 2.0%, CuO 9.6%, Al₂O₃ 81%. The specific surface area of ​​the adsorbent is 146 m². 2 / g, pore volume 0.31cm 3 / g.

[0095] The adsorbent particles were ground to 20-40 mesh, and 5g was weighed and loaded into a fixed-bed reactor. At room temperature and pressure, nitrogen gas containing 100 μmol / mol COS + 20 μmol / mol CS2 + 50 μmol / mol H2S + 10 μmol / mol AsH3 + 10 μmol / mol PH3 was introduced at a rate of 100 ml / min. The concentration of each impurity at the bed outlet was detected using a helium ion detector. When the outlet concentration of any substance exceeded 1 μmol / mol, it was considered that the substance had penetrated. The sulfur capacity and (arsenic + phosphorus) capacity of the adsorbent were calculated based on the penetration time. The sulfur capacity of the adsorbent was 2.33%; the (arsenic + phosphorus) capacity was 0.38%.

[0096] Example 8

[0097] 200 ml of distilled water and 0.33 g of polyethylene glycol 6000 were added to a 2000 ml coprecipitation reactor and stirred until homogeneous. A mixed solution of 0.8 mol / L copper nitrate and 0.2 mol / L aluminum nitrate was added at a rate of 20 ml / min, while a 1.2 mol / L sodium carbonate solution was added dropwise to maintain the pH at 10. The addition was carried out over 30 minutes. After the addition was complete, the reaction was carried out at 60 °C for 1 hour to obtain a mixed solution. Subsequently, 10 g of boehmite was added to the coprecipitation reactor, and the reaction was continued for 0.5 hours to obtain a precipitate. The precipitate was washed and dried to obtain a precursor containing basic copper carbonate.

[0098] The above precursor was calcined at 400°C for 5 hours to obtain component A containing CuO (containing 74% by weight of copper oxide and 26% by weight of aluminum oxide). Figure 1 The XRD pattern of component A is given. Based on the diffraction peaks of the (111) crystal plane of copper oxide, the grain size of copper oxide is calculated to be 11 nm using the Scherrer formula.

[0099] 21g of component A and 94g of alumina were mixed, shaped, dried, and calcined to obtain adsorbent particles B. A solution of 22g zinc nitrate and 30g water was prepared, and adsorbent B was impregnated in it, dried at 100℃, and calcined at 450℃ to obtain adsorbent particles C. A solution of 12g potassium hydroxide and 40g water was prepared, and adsorbent particles C were impregnated in it, dried at 120℃ to obtain adsorbent particles C. The weight composition of the adsorbent is: K 6.5%, ZnO 4.6%, CuO 9.1%, Al₂O₃ 76.8%. The specific surface area of ​​the adsorbent is 123 m². 2 / g, pore volume 0.25cm 3 / g.

[0100] The adsorbent particles were ground to 20-40 mesh, and 5g was weighed and loaded into a fixed-bed reactor. At room temperature and pressure, nitrogen gas containing 100 μmol / mol COS + 20 μmol / mol CS2 + 50 μmol / mol H2S + 10 μmol / mol AsH3 + 10 μmol / mol PH3 was introduced at a rate of 100 ml / min. The concentration of each impurity at the bed outlet was detected using a helium ion detector. When the outlet concentration of any substance exceeded 1 μmol / mol, it was considered that the substance had penetrated. The sulfur capacity and (arsenic + phosphorus) capacity of the adsorbent were calculated based on the penetration time. The sulfur capacity of the adsorbent was 2.26%; the (arsenic + phosphorus) capacity was 0.39%.

[0101] Example 9

[0102] 200 ml of distilled water and 0.33 g of polyethylene glycol 6000 were added to a 2000 ml coprecipitation reactor and stirred until homogeneous. A mixed solution of 0.8 mol / L copper nitrate and 0.2 mol / L aluminum nitrate was added at a rate of 20 ml / min, while a 1.2 mol / L sodium carbonate solution was added dropwise to maintain the pH at 10. The addition was carried out over 30 minutes. After the addition was complete, the reaction was carried out at 60 °C for 1 hour to obtain a mixed solution. Subsequently, 10 g of boehmite was added to the coprecipitation reactor, and the reaction was continued for 0.5 hours to obtain a precipitate. The precipitate was washed and dried to obtain a precursor containing basic copper carbonate.

[0103] The above precursor was calcined at 400°C for 5 hours to obtain component A containing CuO (containing 74% by weight of copper oxide and 26% by weight of aluminum oxide). Figure 1 The XRD pattern of component A is given. Based on the diffraction peaks of the (111) crystal plane of copper oxide, the grain size of copper oxide is calculated to be 11 nm using the Scherrer formula.

[0104] 21g of component A, 94g of alumina, and 10g of silica were mixed, shaped, dried, and calcined to obtain adsorbent particles B. A solution of 22g zinc nitrate and 30g water was prepared, and adsorbent B was impregnated in it, dried at 100℃, and calcined at 450℃ to obtain adsorbent particles C. A solution of 9g potassium hydroxide and 40g water was prepared, and adsorbent particles C were impregnated in it, dried at 120℃ to obtain adsorbent particles C. The weight composition of the adsorbent is: K 4.6%, ZnO 4.4%, CuO 8.6%, Al₂O₃ 72.8%, SiO₂ 7.4%. The specific surface area of ​​the adsorbent is 119 μm. 2 / g, pore volume 0.23cm 3 / g.

[0105] The adsorbent particles were ground to 20-40 mesh, and 5g was weighed and loaded into a fixed-bed reactor. At room temperature and pressure, nitrogen gas containing 100 μmol / mol COS + 20 μmol / mol CS2 + 50 μmol / mol H2S + 10 μmol / mol AsH3 + 10 μmol / mol PH3 was introduced at a rate of 100 ml / min. The concentration of each impurity at the bed outlet was detected using a helium ion detector. When the outlet concentration of any substance exceeded 1 μmol / mol, it was considered that the substance had penetrated. The sulfur capacity and (arsenic + phosphorus) capacity of the adsorbent were calculated based on the penetration time. The sulfur capacity of the adsorbent was 2.18%; the (arsenic + phosphorus) capacity was 0.74%.

[0106] Comparative Example 1

[0107] 200 ml of distilled water and 0.33 g of polyethylene glycol 6000 were added to a 2000 ml coprecipitation reactor and stirred until homogeneous. A 0.8 mol / L copper nitrate solution was added at a rate of 20 ml / min, while a 1.2 mol / L sodium carbonate solution was added dropwise, maintaining the pH at 10. The addition was carried out over 30 minutes. After the addition was complete, the reaction was carried out at 60 °C for 1 hour to obtain a mixed solution. Subsequently, 10 g of boehmite was added to the coprecipitation reactor, and the reaction was continued for 0.5 hours to obtain a precipitate. The precipitate was washed and dried to obtain a precursor containing basic copper carbonate.

[0108] The above precursor was calcined at 400°C for 5 hours to obtain component A containing CuO (containing 84% by weight of copper oxide and 16% by weight of aluminum oxide). Figure 1 The XRD pattern of component A is given. Based on the diffraction peaks of the (111) crystal plane of copper oxide, the grain size of copper oxide is calculated to be 32 nm using the Scherrer formula.

[0109] 21g of component A and 94g of alumina were mixed, shaped, dried, and calcined to obtain adsorbent particles B. A solution of 22g zinc nitrate and 30g water was prepared, and adsorbent B was impregnated in it, dried at 100℃, and calcined at 450℃ to obtain adsorbent particles C. A solution of 9g potassium hydroxide and 40g water was prepared, and adsorbent particles C were impregnated in it, dried at 120℃ to obtain adsorbent particles C. The weight composition of the adsorbent is: K 4.6%, ZnO 4.4%, CuO 10.5%, Al₂O₃ 77.4%. The specific surface area of ​​the adsorbent is 110 m². 2 / g, pore volume 0.23cm 3 / g.

[0110] The adsorbent particles were ground to 20-40 mesh, and 5g was weighed and loaded into a fixed-bed reactor. At room temperature and pressure, nitrogen gas containing 100 μmol / mol COS + 20 μmol / mol CS2 + 50 μmol / mol H2S + 10 μmol / mol AsH3 + 10 μmol / mol PH3 was introduced at a rate of 100 ml / min. The concentration of each impurity at the bed outlet was detected using a helium ion detector. When the outlet concentration of any substance exceeded 1 μmol / mol, it was considered that the substance had penetrated. The sulfur capacity and (arsenic + phosphorus) capacity of the adsorbent were calculated based on the penetration time. The sulfur capacity of the adsorbent was 1.2%; the (arsenic + phosphorus) capacity was 0.21%.

[0111] Comparative Example 2

[0112] Add 200 ml of distilled water to a 2000 ml coprecipitation reactor, add 0.33 g of polyethylene glycol 6000, stir well, and add a mixed solution of 0.8 mol / L copper nitrate and 0.2 mol / L aluminum nitrate at a rate of 20 ml / min. At the same time, add 1.2 mol / L sodium carbonate solution dropwise, maintain pH = 10, and add the mixture over 30 minutes. After the addition is complete, react at 60 °C for 1 hour to obtain a mixed solution. Continue the reaction for 0.5 hours to obtain a precipitate. Wash and dry the precipitate to obtain a precursor containing basic copper carbonate.

[0113] The above precursor was calcined at 400°C for 5 hours to obtain component A containing CuO (containing 86% by weight of copper oxide and 13% by weight of aluminum oxide). Figure 1 The XRD pattern of component A is given. Based on the diffraction peaks of the (111) crystal plane of copper oxide, the grain size of zinc oxide is calculated to be 18 nm using the Scherrer formula.

[0114] 21g of component A and 94g of alumina were mixed, shaped, dried, and calcined to obtain adsorbent particles B. A solution of 2g zinc nitrate and 30g water was prepared, and adsorbent B was impregnated in it, dried at 100℃, and calcined at 450℃ to obtain adsorbent particles C. A solution of 1g potassium hydroxide and 40g water was prepared, and adsorbent particles C were impregnated in it, dried at 120℃ to obtain adsorbent particles C. The weight composition of the adsorbent is: K 0.6%, ZnO 0.4%, CuO 10.4%, Al₂O₃ 88.2%. The specific surface area of ​​the adsorbent is 10⁶ m². 2 / g, pore volume 0.17cm 3 / g.

[0115] The adsorbent particles were ground to 20-40 mesh, and 5g was weighed and loaded into a fixed-bed reactor. At room temperature and pressure, nitrogen gas containing 100 μmol / mol COS + 20 μmol / mol CS2 + 50 μmol / mol H2S + 10 μmol / mol AsH3 + 10 μmol / mol PH3 was introduced at a rate of 100 ml / min. The concentration of each impurity at the bed outlet was detected using a helium ion detector. When the outlet concentration of any substance exceeded 1 μmol / mol, it was considered that the substance had penetrated. The sulfur capacity and (arsenic + phosphorus) capacity of the adsorbent were calculated based on the penetration time. The sulfur capacity of the adsorbent was 1.5%; the (arsenic + phosphorus) capacity was 0.29%.

[0116] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. An adsorbent, characterized in that, The adsorbent contains, by weight: a) 2-6 parts alkali metal; b) 3-9 parts zinc oxide; c) 8-12 parts copper oxide; d) 65-85 parts aluminum oxide; and optionally e) 0-8 parts silicon oxide; The copper oxide has a grain size of 8-13 nm; the adsorbent has a specific surface area of ​​120-160 m². 2 / g; pore volume is 0.25-0.4cm³ 3 / g.

2. The method for preparing the adsorbent according to claim 1, characterized in that, The method includes: (1) Copper and aluminum solution I and alkaline solution II are added concurrently to a reactor containing an aqueous solution of dispersant, and the pH is controlled at 10-11 for co-precipitation to obtain a mixed solution; wherein the dispersant is one or more of polyethylene glycol 6000, polyethylene glycol 2000 and polyethylene glycol 600; (2) Add boehmite to the mixed solution to obtain the precursor; the amount of boehmite added is 20%~30% of the mass of copper added in step (1) based on copper oxide; (3) The above precursor was calcined to obtain component A; (4) Mix component A, solid aluminum source and / or solid silicon source, grind into powder, shape and dry to obtain adsorbent particles B; (5) The adsorbent particles B were immersed in a zinc salt solution, dried and calcined to obtain adsorbent particles C; (6) Immerse adsorbent particles C in an alkali metal solution and dry them to obtain the adsorbent.

3. The preparation method according to claim 2, wherein, Coprecipitation conditions include: temperature 40~90℃, time 0.5~3 hours; and / or In solution I containing copper and aluminum, the molar concentration of Cu is 0.5–1.0 mol / L; the molar concentration of Al is 0.1–0.6 mol / L; and / or In the alkaline solution II, the molar concentration of alkaline solution II is 1.0~1.5 mol / L; and / or In alkaline solution II, the alkaline substance is selected from one or more of sodium carbonate, sodium bicarbonate, and ammonium carbonate; and / or The copper is derived from one or more of copper nitrate, copper sulfate, and copper acetate; and / or The aluminum is derived from one or more of aluminum nitrate and aluminum sulfate.

4. The preparation method according to claim 2 or 3, wherein, The amount of dispersant used is 0.1-3% of the combined mass of the copper compound and aluminum compound added; and / or In solution I containing copper and aluminum, the Cu / Al molar ratio is 1~10.

5. The preparation method according to claim 2 or 3, wherein, In step (2), The mixing time is 0.25 to 1 hour.

6. The preparation method according to claim 2 or 3, wherein, In step (3), The roasting temperature is 300℃~500℃.

7. The preparation method according to claim 2 or 3, wherein, In step (5), The drying temperature is 50℃-150℃, and / or; The roasting temperature is 400℃-500℃.

8. The preparation method according to claim 2 or 3, wherein, In step (6), The drying temperature is 50℃-150℃; and / or The alkali metal compound in the alkali metal solution is one of KOH, Na2CO3, NaHCO3, or K2CO3.

9. The preparation method according to claim 8, wherein, In step (6), The alkali metal compound in the alkali metal solution is KOH or K2CO3.

10. The application of the adsorbent of claim 1 in the adsorption and removal of one or more of AsH3, PH3, COS, CS2 and H2S from one or more raw materials such as natural gas, syngas, coke oven gas, light gas, and liquid hydrocarbons.

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