CN115888637A - Adsorbent and preparation method and application thereof - Google Patents
Adsorbent and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of adsorbents, and discloses an adsorbent, a preparation method and application thereof, wherein the adsorbent comprises the following components: metal component, molecular sieve, pseudoboehmite and alumina, B acid/L acid is below 0.1, and the metal component is selected from alkali metal component and/or alkaline earth metal component. The preparation method of the adsorbent comprises the following steps: 1) Kneading and extruding the molecular sieve, the pseudo-boehmite, the alumina, the peptizing agent and the extrusion aid, drying and roasting to obtain adsorbent raw particles A; 2) Adding the adsorbent raw particles A into a solution containing alkali metal components and/or alkaline earth metal components, carrying out ion exchange, filtering, washing and drying to obtain the adsorbent. The adsorbent provided by the invention provides proper acidity, so that the adsorption capacity of the adsorbent is improved, polar compounds can be desorbed below 200 ℃, in-situ online regeneration is realized, the adsorbent has large pore volume and small strong acid content, and the risk of olefin polymerization caused by local temperature rise in the adsorption process can be prevented.
Description
Technical Field
The invention relates to an adsorbent, a preparation method thereof and application thereof in removing polar compounds in olefin.
Background
C2-C4 low-carbon olefins such as ethylene, propylene and butylene are important industrial raw materials and are basic raw materials for synthesizing high-value-added chemical products such as polyolefin, ethylene oxide, propylene oxide, bisphenol A, polycarbonate and the like. However, various impurities, such as basic nitrogen, sulfur and oxygen-containing compounds, are commonly present in these chemical raw materials, and the presence of these impurities can cause poisoning of downstream catalysts, decrease the quality of downstream products, and make the devices unable to operate stably and safely. Therefore, it is necessary to design a purification unit in the reaction system to purify the olefin feedstock by the adsorbent in order to protect the main catalyst and maintain the stable operation of the apparatus. The development of the high-efficiency adsorbent has important significance.
CN 102451746A discloses a modified 13X zeolite molecular sieve nitrogen oxide purification catalyst and a preparation method thereof. The nitrogen oxide purification catalyst comprises the following components in percentage by mass: 52.17 to 89.11 percent of 13X zeolite molecular sieve, 9.9 to 34.78 percent of gamma-alumina (gamma-A12O 3) and 0.99 to 13.05 percent of metal oxide. The nitrogen oxide purification catalyst prepared by the invention is prepared by taking a mixture of a 13X zeolite molecular sieve and gamma-alumina (gamma-A12O 3) as a carrier, soaking a metal nitrate solution in equal volume, drying and roasting. The purification catalyst is used for catalytically converting nitrogen oxides.
CN105457600A discloses a method for preparing a denitrified adsorbent, which is an adsorbent obtained by treating a complex liquid containing mixed fluorine acid with a molecular sieve as a carrier, and the adsorbent improves the polarity and the acidity, thereby being beneficial to the removal of nitrogen-containing compounds. Used for removing nitrogen-containing compounds in naphtha.
CN103418164B discloses a method for removing oxygen-containing compounds from hydrocarbon streams by using a porous metal organic compound as a solid adsorbent to remove oxygen-containing compound impurities from hydrocarbon streams, the solid adsorbent being a porous metal organic compound having a chemical composition formula of M 3 (BTC) 2 (L) 3 M, wherein M is a transition metal element and is selected from at least one of Cu, co, fe, ni, zn and Cr, BTC represents deprotonated trimesic acid, L is a solvent molecule and is selected from at least one of H2O, NH3, CH3OH, DMF, THF and C2H5OH, M represents the number of solvent molecules bound on average per metal ion, and M is less than or equal to 0 and less than or equal to 1.
However, in the prior art, the problems of low adsorption capacity of the adsorbent, incapability of regenerating the adsorbent, large solid waste discharge amount, obvious adsorption heat release and easy olefin polymerization exist in the process of removing polar compounds such as nitrogen-containing compounds, sulfur, oxygen-containing compounds and the like.
Disclosure of Invention
The invention aims to solve the problems that the adsorbent in the prior art is low in adsorption capacity, cannot be regenerated, is obvious in adsorption heat release and is easy to cause olefin polymerization. An adsorbent and a method for preparing the same are provided. The adsorbent is prepared by blending molecular sieve, pseudo-boehmite and alumina, and can further exchange protonic acid through ion exchange of alkali metal/alkaline earth metal-containing solution, and simultaneously can further reduce the using amount of the molecular sieve, the adsorption capacity of the adsorbent is not reduced, and the carbon deposition amount of the adsorbent after multiple regeneration is less.
According to a first aspect of the present invention, there is provided an adsorbent comprising: metal component, molecular sieve, pseudoboehmite and alumina, B acid/L acid is below 0.1, and the metal component is selected from alkali metal component and/or alkaline earth metal component.
According to a second aspect of the present invention, there is provided a process for the preparation of the adsorbent according to the present invention, which comprises:
1) Kneading and extruding the molecular sieve, the pseudo-boehmite, the alumina, the peptizing agent and the extrusion aid, drying and roasting to obtain adsorbent raw particles A;
2) Adding the adsorbent raw particles A into a solution containing an alkali metal component compound and/or an alkaline earth metal component compound, carrying out ion exchange, filtering, washing and drying to obtain the adsorbent.
According to a third aspect of the present invention, there is provided the use of the adsorbent of the present invention for removing polar compounds from olefins; preferably, the olefin is a C2-C4 olefin, preferably one or more of ethylene, propylene and butylene, and the polar compound is selected from H 2 O, methanol, ammonia, H 2 One or more of S and COS.
The adsorbent provided by the invention is prepared by reasonably combining the metal components, the molecular sieve, the pseudoboehmite and the alumina, wherein the molecular sieve is mainly microporous and has a strong electrostatic field, the pseudoboehmite and the alumina are mainly mesoporous and provide excellent diffusion performance for the adsorbent, and the alkali metal modification can reduce the B acid content of the adsorbent, reduce the surface activity of the adsorbent and reduce the risk of olefin polymerization in the adsorption process.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The present invention provides an adsorbent comprising: metal component, molecular sieve, pseudoboehmite and alumina, B acid/L acid is below 0.1, and the metal component is selected from alkali metal component and/or alkaline earth metal component. The adsorbent with the characteristics has larger adsorption capacity, the amount of B acid is reduced, the surface activity of the adsorbent is reduced, and the risk of olefin polymerization is reduced.
According to a preferred embodiment of the invention, the adsorbent has a B acid/L acid of 0.001 to 0.095, preferably 0.03 to 0.08. This can further increase the adsorption amount of the adsorbent and reduce the surface activity of the adsorbent.
According to a preferred embodiment of the present invention, the adsorbent comprises: metal component 0.002-1 wt%, molecular sieve 5-30 wt%, pseudoboehmite 20-50 wt%, and alumina 20-50 wt%; this can further increase the adsorption amount of the adsorbent and reduce the surface activity of the adsorbent.
According to a preferred embodiment of the present invention, preferably, the adsorbent contains: metal component 0.01-0.8 wt%, molecular sieve 10-25 wt%, pseudoboehmite 30-45 wt%, and alumina 30-45 wt%; this can further increase the adsorption amount of the adsorbent and reduce the surface activity of the adsorbent.
According to a preferred embodiment of the present invention, preferably, the metal component is selected from one or more of sodium, potassium, calcium.
According to a preferred embodiment of the present invention, preferably, the molecular sieve is selected from one or more of an X-type molecular sieve and a Y-type molecular sieve; preferably one or more selected from 13X molecular sieves and NaY molecular sieves. By using the preferred molecular sieve, the adsorption amount of the adsorbent can be further increased.
The adsorbent having the aforementioned characteristics of the present invention can achieve the object of the present invention, and there is no particular requirement for the preparation method thereof, and the present invention is directed to an improvement of the preparation method of the adsorbent according to the present invention, the method comprising:
1) Kneading and extruding the molecular sieve, the pseudo-boehmite, the alumina, the peptizing agent and the extrusion aid, drying and roasting to obtain adsorbent raw particles A;
2) Adding the adsorbent raw particles A into a solution containing an alkali metal component compound and/or an alkaline earth metal component compound, carrying out ion exchange, filtering, washing and drying to obtain the adsorbent. The invention further reduces the amount of protonic acid through alkali metal exchange, and can reduce propylene polymerization caused by heat release.
According to a preferred embodiment of the present invention, in step 1), the conditions of calcination include: the temperature is 200 to 400 ℃, preferably 300 to 350 ℃, and the adsorption amount of the adsorbent can be further increased by the preferred roasting method.
According to a preferred embodiment of the present invention, in step 1), the conditions of calcination include: the time is 2 to 10 hours, preferably 4 to 6 hours.
According to a preferred embodiment of the present invention, in step 2), the drying conditions include: the temperature is 50-150 ℃.
According to a preferred embodiment of the present invention, in step 2), the drying conditions include: the time is 2-12h.
According to a preferred embodiment of the invention, the conditions of the ion exchange comprise: ion exchange is carried out for 2 to 5 hours at room temperature.
According to a preferred embodiment of the present invention, the alkali metal component compound and/or alkaline earth metal component compound may be selected from a wide range of species, and for the present invention, one or more selected from nitrate, carbonate, acetate and hydroxide is preferred. Sodium hydroxide is exemplified as an illustration in the examples of the present invention, but the scope of the present invention is not limited thereby.
According to a preferred embodiment of the present invention, the solid-liquid mass ratio of the raw adsorbent particles a to the solution containing the alkali metal component compound and/or the alkaline earth metal component compound is 0.3 to 0.1.
According to a preferred embodiment of the present invention, the concentration of the solution containing the alkali metal component compound and/or the alkaline earth metal component compound is 0.02 to 0.5% by weight, preferably 0.1 to 0.4% by weight.
According to a preferred embodiment of the present invention, the method of the present invention comprises, a) the preparation of the pseudoboehmite comprises: and adding 0.5-1.5 mol/L sodium metaaluminate solution and 0.5-1.5 mol/L nitric acid solution in a concurrent flow manner, controlling the reaction pH to be 6-8, the reaction temperature to be 40-90 ℃, and the reaction time to be 0.5-3 hours to obtain a precipitate, and washing and drying the precipitate to obtain the pseudoboehmite. The pseudo-boehmite prepared by the method is used for the invention, and the mechanical strength and the capacity of the adsorbent can be further improved.
According to a preferred embodiment of the present invention, the method of the present invention comprises, b) the preparation of the alumina comprises: uniformly mixing pseudo-boehmite and a polyacrylic acid solution, drying and roasting; the preparation of the preferred pseudoboehmite comprises: and adding 0.5-1.5 mol/L sodium metaaluminate solution and 0.5-1.5 mol/L nitric acid solution in a concurrent flow manner, controlling the reaction pH to be 6-8, the reaction temperature to be 40-90 ℃, and the reaction time to be 0.5-3 hours to obtain precipitates, and washing and drying the precipitates. Thereby enabling further improvement in the adsorbent adsorption capacity.
According to a preferred embodiment of the present invention, the polyacrylic acid solution in step b) preferably has a mass concentration of 0.5 to 1.5%. Thereby enabling further improvement in the adsorbent adsorption capacity.
According to a preferred embodiment of the present invention, the solid-liquid mass ratio of the pseudo-boehmite to the polyacrylic acid solution is preferably 1. Thereby enabling further improvement in the adsorbent adsorption capacity.
The invention provides application of the adsorbent in removing polar compounds in olefin; preferably the olefin is a C2-C4 olefin, more preferably one or more of ethylene, propylene and butene, and the polar compound is selected from H 2 O, methanol, ammonia, H 2 One or more of S and COS.
The adsorbent of the invention can be used for removing polar compounds in olefin. Is preferably used for removing H from low-carbon olefins such as ethylene, propylene, butylene and the like 2 O, methanol, ammonia, H 2 S, COS and the like. In the examples of the present invention, ammonia, H 2 The adsorption of S is exemplified.
The invention is further illustrated by the following examples.
The acid center of the sample is subjected to NH treatment on a PX200A type temperature programmed thermal desorption device of the Technology ltd, pengxi 3 TPD test, ammonia adsorption temperature of 100 ℃, he as carrier gas, flow rate of 30mL min -1 The heating rate is 10 ℃ min -1 . The acid center is weak acid center when the temperature is less than 300 ℃, and the acid center is strong acid center when the temperature is more than 300 ℃. The total acid amount is obtained by weighing through a microbalance. Integral fitting ofThe acid amount of the strong acid center and the acid amount of the weak acid center are obtained.
Measuring B acid and L acid of the sample with Nicolet380 model FT-IR instrument, scanning range (4 000-1 300) cm-1, resolution of 4.0cm-1, sample of about 8mg, and temperature of 1.33 × 10 at 400 deg.C -2 And (3) after Pa vacuum dehydration is carried out for 2h, the temperature is reduced to 200 ℃, sample body scanning is carried out, pyridine is adsorbed for 5min, after balance, vacuum pumping is carried out for 0.5h, unadsorbed pyridine is removed, and finally infrared scanning is carried out at 200 ℃,300 ℃ and 400 ℃ respectively.
And (3) measuring the surface activity of the sample: 20mg of adsorbent is filled in a pulse micro-reactor, the temperature of the reactor is 300 ℃, 1-hexene is taken as a probe molecule, the sample injection amount is 0.4 mu L, and an Agilent gas phase is used for detecting a reaction product. 1-hexene conversion = 1-hexene content in the product. The surface activity is high when the conversion rate of 1-hexene is high, and the surface activity is low when the conversion rate of 1-hexene is low.
Comparative example 1
Pulverizing 10 kg of 13X (commercially available from Jianlong micro-nano), 15 kg of pseudoboehmite (commercially available from Jiangsu three-agent chemical assistant factory), 15 kg of alumina (commercially available from Shandongtong Nineng) and 0.3 kg of sesbania powder, mixing, and adding 5 kg of HNO 3 Kneading with an aqueous solution (3 wt%), extruding into strips, and drying at 120 ℃ for 12 hours. And roasting the extruded strip forming sample at 300 ℃ for 5 hours to obtain the adsorbent. The adsorbent B acid/L acid is 0.21, and the 1-hexene conversion rate at 300 ℃ is 80%, thereby indicating that higher B acid content can result in higher 1-hexene conversion rate and high adsorbent surface activity.
Adsorbent NH 3 、H 2 Measurement of S adsorption amount: 5g of the adsorbent were charged to a fixed-bed reactor, each with a 1000ppm NH content 3 And 1000ppmH 2 The nitrogen of S is used as raw material gas, the room temperature is 20 ℃, the normal pressure is realized, the flow rate is 100ml/min, and a sulfur-nitrogen analyzer is used for measuring H in the outlet gas 2 S、NH 3 Content of (D) as the outlet gas NH 3 、H 2 The S content exceeding 1ppm is regarded as the breakthrough of the adsorbent, and the NH is calculated from the breakthrough curve 3 The breakthrough adsorption amount of (2.8%; H) 2 The amount of S penetrating the adsorbent was 1.5%.
Example 1
10 kg of 13X (quotient)Purchased from Jianlong micro-nano), 15 kg of pseudo-boehmite (purchased from Jiangsu three-agent chemical assistant factory, not specially described, the same in the following examples), 15 kg of alumina (purchased from Shandong Ningneng, not specially described, the same in the following examples) and 0.3 kg of sesbania powder, and after being uniformly mixed, 5 kg of HNO is added 3 Kneading with an aqueous solution (3 wt%), extruding into strips, and drying at 120 ℃ for 12 hours. The extruded sample is calcined at 300 deg.C for 5 hours to obtain the adsorbent raw particles. 10 kg of the adsorbent raw particles were exchanged with 50 kg of 0.2 wt% NaOH solution for 3 hours, filtered and dried at 100 ℃ to obtain the adsorbent. The adsorbent B acid/L acid was 0.08, and the 1-hexene conversion at 300 ℃ was 1.8%. Therefore, after the alkali solution exchange, the B acid content of the sample is reduced, the 1-hexene conversion rate is low, and the adsorbent surface activity is low.
Adsorbent NH 3 、H 2 Measurement of S adsorption amount: 5g of the adsorbent were charged to a fixed-bed reactor, each with a 1000ppm NH content 3 And 1000ppmH 2 The nitrogen of S is used as raw material gas, the room temperature is 20 ℃, the normal pressure is realized, the flow rate is 100ml/min, and a sulfur-nitrogen analyzer is used for measuring H in the outlet gas 2 S、NH 3 Content of (D) as the outlet gas NH 3 、H 2 The S content exceeding 1ppm is regarded as the breakthrough of the adsorbent, and the NH is calculated from the breakthrough curve 3 The breakthrough adsorption amount of (2) was 3.0%, H 2 The amount of S penetrating the adsorbent was 1.7%.
Example 2
Pulverizing 10 kg of 13X, 20 kg of pseudo-boehmite, 10 kg of alumina and 0.3 kg of sesbania powder, mixing uniformly, and adding 5 kg of HNO 3 Kneading with an aqueous solution (3 wt%), extruding into strips, and drying at 120 ℃ for 12 hours. The extruded sample is roasted for 5 hours at 350 ℃ to obtain the adsorbent raw particles. 10 kg of the adsorbent raw particles were exchanged with 50 kg of 0.1 wt% NaOH solution for 3 hours, filtered and dried at 80 ℃ to obtain the adsorbent. The adsorbent B acid/L acid was 0.05, and the 1-hexene conversion at 300 ℃ was 0.4%. Thus, the low B acid content, the low 1-hexene conversion rate and the low adsorbent surface activity are shown.
Adsorbent NH 3 、H 2 Measurement of S adsorption amount: 5g of the adsorbent are charged into a fixed-bed reactor, respectivelyContaining 1000ppm NH 3 And 1000ppmH 2 The nitrogen of S is used as raw material gas, the room temperature is 20 ℃, the normal pressure is realized, the flow rate is 100ml/min, and a sulfur-nitrogen analyzer is used for measuring H in the outlet gas 2 S、NH 3 Content of (D) as the outlet gas NH 3 、H 2 The S content exceeding 1ppm is regarded as the breakthrough of the adsorbent, and the NH is calculated from the breakthrough curve 3 The breakthrough adsorption amount of (2.9%; H) 2 The amount of S penetrating the adsorbent was 1.7%.
Example 3
Pulverizing 10 kg of 13X, 10 kg of pseudo-boehmite, 20 kg of alumina and 0.3 kg of sesbania powder, mixing uniformly, and adding 5 kg of HNO 3 Kneading with an aqueous solution (3 wt%), extruding into strips, and drying at 120 ℃ for 12 hours. The extruded sample is roasted for 5 hours at 350 ℃ to obtain the adsorbent raw particles. Exchanging 10 kg of raw particles of the adsorbent with 50 kg of 0.4% NaOH solution for 3 hours, filtering, and drying at 120 ℃ to obtain the adsorbent. The adsorbent B acid/L acid was 0.05, and the 1-hexene conversion at 300 ℃ was 0.7%. Therefore, under the condition of higher alumina content, after the alkali solution exchange, the B acid content of the sample is reduced, the 1-hexene conversion rate is low, and the surface activity of the adsorbent is low.
Adsorbent NH 3 、H 2 Measurement of S adsorption amount: 5g of the adsorbent were charged to a fixed-bed reactor, each with a 1000ppm NH content 3 And 1000ppmH 2 The nitrogen of S is used as raw material gas, the room temperature is 20 ℃, the normal pressure is realized, the flow rate is 100ml/min, and a sulfur-nitrogen analyzer is used for measuring H in the outlet gas 2 S、NH 3 Content of (D) as the outlet gas NH 3 、H 2 The content of S exceeding 1ppm is regarded as the breakthrough of the adsorbent, and NH is calculated from the breakthrough curve 3 The breakthrough adsorption amount of (2%) was 3.2%, H 2 The amount of S penetrating the adsorbent was 3.0%.
Example 4
Adding 200ml of distilled water into a coprecipitation reactor (2000 ml), adding 1.0mol/L sodium metaaluminate solution at the speed of 10ml/min, simultaneously adding 1.0mol/L nitric acid solution, controlling the adding speed of the nitric acid solution to ensure that the pH =8 for reaction, wherein the reaction temperature is 50 ℃, the reaction time is 1 hour, obtaining precipitate, and washing and drying the precipitate to obtain the pseudoboehmite.
Pulverizing 10 kg of 13X and 15 kg of pseudo-boehmite prepared by the scheme, 15 kg of alumina and 0.3 kg of sesbania powder, mixing uniformly, and adding 5 kg of HNO 3 Kneading with an aqueous solution (3 wt%), extruding into strips, and drying at 120 ℃ for 12 hours. The extruded sample is calcined at 300 deg.C for 5 hours to obtain the adsorbent raw particles. 10 kg of the adsorbent raw particles were exchanged with 50 kg of 0.2 wt% NaOH solution for 3 hours, filtered and dried at 100 ℃ to obtain the adsorbent. The adsorbent B acid/L acid was 0.03, and the 1-hexene conversion at 300 ℃ was 0.2%. Therefore, after the alkali solution exchange, the B acid content of the sample is reduced, the 1-hexene conversion rate is low, and the adsorbent surface activity is low.
Adsorbent NH 3 、H 2 Measurement of S adsorption amount: 5g of the adsorbent were charged into fixed-bed reactors, each with a 1000ppm NH content 3 And 1000ppmH 2 The nitrogen of S is used as raw material gas, the room temperature is 20 ℃, the normal pressure is realized, the flow rate is 100ml/min, and a sulfur-nitrogen analyzer is used for measuring H in the outlet gas 2 S、NH 3 Content of (b) when gas NH is discharged 3 、H 2 The S content exceeding 1ppm is regarded as the breakthrough of the adsorbent, and the NH is calculated from the breakthrough curve 3 The breakthrough adsorption amount of (2) was 3.5%, H 2 The breakthrough adsorption of S was 2.0%.
Example 5
Adding 200ml of distilled water into a coprecipitation reactor (2000 ml), adding 1.0mol/L sodium metaaluminate solution at the speed of 10ml/min, simultaneously adding 1.0mol/L nitric acid solution, controlling the adding speed of the nitric acid solution to ensure that the pH =8 for reaction, wherein the reaction temperature is 50 ℃, the reaction time is 1 hour, obtaining precipitate, and washing and drying the precipitate to obtain the pseudoboehmite.
And (3) adding 20 kg of the pseudo-boehmite into 20 kg of a polyacrylic acid solution with the mass concentration of 1.0%, uniformly mixing, drying at 100 ℃ for 8 hours, and calcining at 550 ℃ for 6 hours to obtain the alumina.
Pulverizing 10 kg of 13X and 15 kg of pseudo-boehmite (commercially available from Jiangsu three-agent chemical auxiliary agent factory), 15 kg of alumina prepared by the above scheme and 0.3 kg of sesbania powder, mixing uniformly, and adding 5 kg of HNO 3 Aqueous solution (3)Weight percent), extruding and molding after kneading, and drying for 12 hours at 120 ℃. The extruded sample is calcined at 300 deg.C for 5 hours to obtain the adsorbent raw particles. 10 kg of the adsorbent raw particles were exchanged with 50 kg of 0.2 wt% NaOH solution for 3 hours, filtered and dried at 100 ℃ to obtain the adsorbent. The adsorbent B acid/L acid was 0.04, and the 1-hexene conversion at 300 ℃ was 0.3%. Therefore, after the alkali solution exchange, the B acid content of the sample is reduced, the 1-hexene conversion rate is low, and the surface activity of the adsorbent is low.
Adsorbent NH 3 、H 2 Measurement of S adsorption amount: 5g of the adsorbent were charged into fixed-bed reactors, each with a 1000ppm NH content 3 And 1000ppmH 2 S nitrogen is used as raw material gas, the room temperature is 20 ℃, the normal pressure is realized, the flow rate is 100ml/min, and a sulfur and nitrogen analyzer is used for measuring H in outlet gas 2 S、NH 3 Content of (b) when gas NH is discharged 3 、H 2 The S content exceeding 1ppm is regarded as the breakthrough of the adsorbent, and the NH is calculated from the breakthrough curve 3 The breakthrough adsorption amount of (2%) was 3.2%, H 2 The amount of S penetrating the adsorbent was 1.8%.
Example 6
Pulverizing 10 kg of 13X, 15 kg of pseudo-boehmite, 15 kg of alumina and 0.3 kg of sesbania powder, mixing uniformly, and adding 5 kg of HNO 3 Aqueous solution (3 wt%) was kneaded, and after kneading, extrusion molding was performed, and drying was performed at 120 ℃ for 12 hours. The extruded sample was calcined at 400 ℃ for 5 hours to obtain the original adsorbent particles. 10 kg of the adsorbent raw particles were exchanged with 50 kg of 0.4 wt% NaOH solution for 3 hours, filtered, and dried at 100 ℃ to obtain the adsorbent. The adsorbent B acid/L acid was 0.06, and the 1-hexene conversion at 300 ℃ was 0.8%. Therefore, after the alkali solution exchange, the B acid content of the sample is reduced, the 1-hexene conversion rate is low, and the surface activity of the adsorbent is low.
Adsorbent NH 3 、H 2 Measurement of S adsorption amount: 5g of the adsorbent were charged to a fixed-bed reactor, each with a 1000ppm NH content 3 And 1000ppmH 2 The nitrogen of S is used as raw material gas, the room temperature is 20 ℃, the normal pressure is realized, the flow rate is 100ml/min, and a sulfur-nitrogen analyzer is used for measuring H in the outlet gas 2 S、NH 3 Content of (D) as the outlet gas NH 3 、H 2 The content of S exceeds 1ppm is taken as the sorbent breakthrough and NH is calculated from the breakthrough curve 3 The breakthrough adsorption amount of (3.1%), H 2 The amount of S penetrating the adsorbent was 1.8%.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. An adsorbent, comprising: metal component, molecular sieve, pseudoboehmite and alumina, B acid/L acid is below 0.1, and the metal component is selected from alkali metal component and/or alkaline earth metal component.
2. The adsorbent according to claim 1, wherein the adsorbent has a B acid/L acid of 0.001 to 0.095, preferably 0.03 to 0.08.
3. The adsorbent according to claim 1 or 2,
the adsorbent contains: metal component 0.002-1 wt%, molecular sieve 5-30 wt%, pseudoboehmite 20-50 wt%, and alumina 20-50 wt%;
preferably, the first and second electrodes are formed of a metal,
the adsorbent contains: calculated by metal oxide, the metal component accounts for 0.01 to 0.8 weight percent, the molecular sieve accounts for 10 to 25 weight percent, the pseudo-boehmite accounts for 30 to 45 weight percent, and the alumina accounts for 30 to 45 weight percent.
4. The adsorbent according to any one of claims 1 to 3,
the metal component is selected from one or more of sodium, potassium and calcium; and/or
The molecular sieve is selected from one or more of X-type molecular sieve and Y-type molecular sieve; preferably one or more selected from the group consisting of 13X molecular sieves and NaY molecular sieves.
5. A method for producing the adsorbent according to any one of claims 1 to 4, characterized in that the method comprises:
1) Kneading and extruding the molecular sieve, the pseudo-boehmite, the alumina, the peptizing agent and the extrusion aid, drying and roasting to obtain adsorbent raw particles A;
2) Adding the adsorbent raw particles A into a solution containing an alkali metal component compound and/or an alkaline earth metal component compound, carrying out ion exchange, filtering, washing and drying to obtain the adsorbent.
6. The production method according to claim 5, wherein,
in the step 1), the step (A) is carried out,
the roasting conditions include: the temperature is 200-400 ℃, preferably 300-350 ℃; for a period of 2 to 10 hours, preferably 4 to 6 hours; and/or
In the step 2), the step (c) is carried out,
the drying conditions include: the temperature is 50-150 ℃; and/or
The conditions for ion exchange include: ion exchange is carried out for 2 to 5 hours at room temperature.
7. The production method according to claim 5 or 6, wherein the alkali metal component compound and/or alkaline earth metal component compound is selected from one or more of nitrate, carbonate, acetate and hydroxide, preferably sodium hydroxide.
8. The production method according to any one of claims 5 to 7, wherein the solid-liquid mass ratio of the raw adsorbent particles A to the solution containing the alkali metal component compound and/or the alkaline earth metal component compound is 0.3 to 0.1, and the concentration of the solution containing the alkali metal component compound and/or the alkaline earth metal component compound is 0.02 to 0.5% by weight, preferably 0.1 to 0.4% by weight.
9. The production method according to any one of claims 5 to 8,
a) The preparation of the pseudoboehmite comprises the following steps: adding 0.5-1.5 mol/L sodium metaaluminate solution and 0.5-1.5 mol/L nitric acid solution in a concurrent flow manner, controlling the reaction pH to be 6-8, the reaction temperature to be 40-90 ℃, and the reaction time to be 0.5-3 hours to obtain precipitate, and washing and drying the precipitate to obtain pseudo-boehmite;
b) The preparation of the alumina comprises the following steps: uniformly mixing pseudo-boehmite and a polyacrylic acid solution, drying and roasting;
preferably, the preparation of the pseudoboehmite comprises: adding 0.5-1.5 mol/L sodium metaaluminate solution and 0.5-1.5 mol/L nitric acid solution in a concurrent flow manner, controlling the reaction pH to be 6-8, the reaction temperature to be 40-90 ℃, and the reaction time to be 0.5-3 hours, obtaining precipitate, washing and drying the precipitate;
preferably, the mass concentration of the polyacrylic acid solution in the step b) is 0.5-1.5%, and the solid-liquid mass ratio of the pseudo-boehmite to the polyacrylic acid solution is 1.
10. Use of the adsorbent according to any one of claims 1 to 4 for removing polar compounds from olefins; preferably, the olefin is a C2-C4 olefin, preferably one or more of ethylene, propylene and butylene, and the polar compound is selected from H 2 O, methanol, ammonia, H 2 One or more of S and COS.
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