CN111097378A - Modified molecular sieve adsorbent and preparation method and application thereof - Google Patents
Modified molecular sieve adsorbent and preparation method and application thereof Download PDFInfo
- Publication number
- CN111097378A CN111097378A CN201811264097.1A CN201811264097A CN111097378A CN 111097378 A CN111097378 A CN 111097378A CN 201811264097 A CN201811264097 A CN 201811264097A CN 111097378 A CN111097378 A CN 111097378A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- adsorbent
- temperature
- adsorption
- cyclopropane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
- C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a molecular sieve adsorbent and a preparation method and application thereof. The preparation method of the molecular sieve adsorbent comprises the following steps: (1) fully contacting a material containing cycloalkane with a 5A molecular sieve, and quickly heating to carry out carbonization treatment on the 5A molecular sieve; (2) dipping the material obtained in the step (1) by adopting an inorganic alkaline aqueous solution; (3) and (3) filtering, drying and roasting the material in the step (2) to obtain the modified 5A molecular sieve. The molecular sieve adsorbent prepared by the method has the advantages of high adsorption capacity, high adsorption rate and the like.
Description
Technical Field
The invention relates to a modified molecular sieve adsorbent, a preparation method and application thereof, in particular to a modified 5A molecular sieve adsorbent with high adsorption capacity, a preparation method and application thereof.
Background
Background
The main pore canal of the 5A molecular sieve is an internal pore volume of 0.776 nm3The size of the pore diameter of the cubic sodium lattice is about 0.5 nm, and molecules with the molecular diameter of less than 0.5 nm can be allowed to pass through. Due to its shape selective adsorption, the 5A molecular sieve is widely used in the separation process of normal paraffin and non-normal hydrocarbon in various petroleum raw materials, forming a fixed bed process of gas-solid adsorption and a simulated moving bed of liquid-solid adsorptionAnd (5) processing.
The 5A molecular sieve is a high-efficiency adsorption material for selectively separating normal paraffin in naphtha fraction. Naphtha is a mixture of various hydrocarbons such as normal paraffin, isoparaffin, naphthene and aromatic hydrocarbon. For steam cracking ethylene, different types of hydrocarbons contribute differently to the ethylene production. The yield of ethylene is highest in normal paraffin, and then in naphthene and isoparaffin, and aromatic hydrocarbon does not contribute to the generation of ethylene. On the other hand, as a catalytic reforming raw material, the reaction speed of cyclodehydrogenation of normal alkane into aromatic hydrocarbon is slow, and the conversion rate is low. Therefore, the method for analyzing the normal paraffin in the naphtha by using the 5A molecular sieve adsorbent is an effective method for fully utilizing the naphtha.
Foreign UOP company and Exxonmobil company have conducted research work for separating normal paraffins and non-normal hydrocarbons in naphtha by using a 5A molecular sieve as an adsorbent, and have achieved highly effective research results. The university of eastern China developed a 5A molecular sieve fixed bed adsorption separation process based on the concept of molecular management, which was used as raw materials for preparing ethylene by steam cracking and catalytic reforming, respectively, and the comprehensive utilization value of naphtha was improved.
CN103170304A discloses a method for preparing a 5A molecular sieve for straight-chain alkane adsorption by adopting attapulgite. Calcining attapulgite at high temperature, soaking in hydrochloric acid solution, dissolving in sodium hydroxide aqueous solution, dissolving sodium hydroxide and sodium metaaluminate in water, mixing the two liquids rapidly, stirring vigorously to obtain milky colloid, crystallizing the colloid at 80-95 deg.C for 4-6 hr, cooling, filtering, washing to pH less than 9, and oven drying to obtain 4A molecular sieve powder; and finally, carrying out ion exchange on the molecular sieve and a calcium chloride solution to obtain the 5A molecular sieve. The 5A molecular sieve has a static saturated adsorption capacity for n-decane up to 0.0716g/g, and a static saturated adsorption capacity for n-pentadecane up to 0.123 g/g. The 5A molecular sieve is prepared by cheap and easily available attapulgite resources, replaces the traditional chemical raw material method, and has good saturated adsorption capacity to straight paraffin.
CN104045095A discloses a preparation method of a 5A molecular sieve. Adding tetraethoxysilane into a sodium hydroxide aqueous solution, stirring for a period of time, adding sodium metaaluminate into the water to be fully dissolved, quickly mixing the two liquids, violently stirring to obtain a milky colloid, crystallizing the colloid at the temperature of 80-95 ℃ for 4-6 hours, cooling, filtering, washing until the pH value is less than 9, and drying to obtain 4A molecular sieve raw powder; and finally, carrying out ion exchange on the molecular sieve and a calcium chloride solution to obtain the 5A molecular sieve. The 5A molecular sieve has a static saturated adsorption capacity of n-decane up to 0.538g/g and a static saturated adsorption capacity of n-pentadecane up to 0.647 g/g. The 5A molecular sieve is prepared by adopting an organic silicon source of tetraethoxysilane as a silicon source to replace inorganic silicon source of sodium silicate, so that the pore passages of the 5A molecular sieve have diversity and the molecular sieve has good saturated adsorption capacity on straight paraffin.
CN1530167A discloses a preparation method of a high-performance pressure swing adsorption 5A molecular sieve, which comprises the following process steps: (1) mixing 80-90 parts by weight of 4A molecular sieve raw powder and 5-20 parts by weight of kaolin clay, adding 1-50 parts by weight of additive plant fiber, and granulating in a high-speed granulator. (2) And screening the granulated intermediate product according to the fineness requirement of the product, drying, and roasting at a high temperature of 200-1000 ℃. (3) Immersing the intermediate product after roasting in 4-25 wt% sodium hydroxide solution for alkali treatment, washing, and adding 2-20 wt% CaCl2Solution of Ca2+Exchanging, washing and drying, and then roasting the granular product for the second time at the temperature of 100-800 ℃ to obtain the high-performance pressure swing adsorption 5A molecular sieve product. The 5A molecular sieve prepared by the method has larger adsorption capacity, faster diffusion rate and higher mechanical strength, and is used for the aspects of pressure swing adsorption oxygen generation, hydrogen production, petroleum dewaxing and the like.
CN106861614A discloses a 5A molecular sieve adsorbent containing normal paraffin distillate oil for adsorptive separation and a preparation method thereof, the preparation method comprises the steps of adding polyquaternium as a crystallization synthesis soft template agent into a sol system mixed by a silicon source and an aluminum source, and hydrothermally synthesizing a hierarchical pore 4A molecular sieve with a micropore-mesopore structure; removing the soft template agent from the 4A molecular sieve, forming the 4A molecular sieve and a binder rolling ball into small balls with the particle size of 0.2-0.8 mm, drying, roasting, and then performing calcium ion exchange and activation to obtain a 5A molecular sieve adsorbent with a micropore-mesopore structure; in the adsorbent, the proportion of the 5A molecular sieve is 90-97 wt%, and the proportion of the binder is 3-10%. The multistage pore canal 5A molecular sieve synthesized by the method keeps higher equilibrium adsorption capacity to normal paraffin, and simultaneously remarkably improves the diffusion coefficient of the normal paraffin in the molecular sieve, thereby improving the speed of adsorption separation.
CN200510012550.6 a method for preparing a zeolite molecular sieve adsorbent with high adsorption quantity, belonging to the technical field of preparation and modification of zeolite molecular sieves. The method is characterized in that the method for preparing the zeolite molecular sieve adsorbent with high carbon monoxide adsorption quantity comprises the following steps: carrying out ion exchange on the binderless 4A molecular sieve and a calcium chloride solution to balance, washing with water, drying to prepare a 5A molecular sieve, then soaking with a dilute solution of sodium hydroxide or water glass, drying and activating to obtain the modified 5A molecular sieve adsorbent with high carbon monoxide adsorption capacity. The invention can obviously improve the adsorption performance of the 5A molecular sieve on carbon monoxide by modifying the molecular sieve by using an alkaline solution impregnation method, and the adsorption capacity of the modified adsorbent is improved by 1-15% compared with that before modification. The method is simple and easy to implement, low in cost and extremely wide in application prospect.
CN201510365330.5 discloses a modified 5A molecular sieve for removing a small amount of n-hexane in isohexane, which refers to that 5A molecular sieve to be modified is subjected to soaking dealumination treatment by using an ethanol solution of oxalic acid to obtain the modified 5A molecular sieve. Meanwhile, the invention discloses a regeneration method of the modified 5A molecular sieve after adsorbing n-hexane. The method has the advantages that: 1) the modified 5A molecular sieve has higher porosity and higher adsorption capacity to n-hexane, so that more isohexane (containing a small amount of n-hexane) can be treated; 2) the steam replacement method in the regeneration process avoids the phenomenon of carbon deposition caused by overhigh local temperature in the process of directly desorbing normal hexane by high-temperature decompression.
In summary, the adsorption capacity, adsorption rate and stability of the 5A molecular sieve adsorbent prepared in the prior art need to be further improved, and the 5A molecular sieve adsorbent impregnated with the alkaline solution or the ethanol solution of oxalic acid for modification treatment may have a certain influence on the orifice of the 5A molecular sieve adsorbent, thereby affecting the selective adsorption performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a molecular sieve adsorbent and a preparation method and application thereof. The molecular sieve adsorbent prepared by the method has the advantages of high adsorption capacity, high adsorption rate and the like.
A method for preparing a molecular sieve adsorbent comprises the following steps:
(1) fully contacting a material containing cycloalkane with a 5A molecular sieve, and quickly heating to carry out carbonization treatment on the 5A molecular sieve;
(2) dipping the material obtained in the step (1) by adopting an inorganic alkaline aqueous solution;
(3) and (3) filtering, drying and roasting the material in the step (2) to obtain the modified 5A molecular sieve.
In the above method, the 5A molecular sieve may be an existing commercial product, or may be prepared according to a method well known to those skilled in the art, for example, a calcium ion solution may be used to perform ion exchange with a 4A molecular sieve to prepare a 5A molecular sieve. The 5A molecular sieve can be prepared or selected from proper particle forms according to the use requirement, such as strips, tablets, columns, spheres and the like, and is preferably spherical. Shaping can be carried out according to the general knowledge in the art.
In the method, the cycloalkane in the cycloalkane-containing material is cyclopropane, and the cyclopropane can be directly contacted with the 5A molecular sieve or contacted with the 5A molecular sieve in the form of a mixed gas of the cyclopropane and an inert gas.
In the above method, it is preferable that a mixed gas of cyclopropane and an inert gas is contacted with the 5A molecular sieve, and the concentration of cyclopropane in the mixed gas is not higher than 60 vol%, preferably not higher than 50 vol%, more preferably 10 to 40 vol%, and still more preferably 20 to 30 vol%.
In the method, the contact mode is that the 5A molecular sieve is placed in a material containing cycloalkane to enable the material containing cycloalkane to fully contact, the placing time is generally 0.1-2h, preferably 0.5-1h, then the temperature is rapidly raised to 350-650 ℃, preferably 400-500 ℃, generally the constant time is 0.5-1.5h, the temperature raising speed is 50-100 ℃/min, preferably 60-80 ℃/min under the sealing condition. The specific operation is that the 5A molecular sieve is placed in a reaction kettle or a tubular reactor, a material containing cycloalkane is introduced to replace the air in the reaction kettle or the tubular reactor, and the temperature rise treatment is carried out after the sealing placement.
In the method, the inorganic alkaline aqueous solution is treated at 30-120 ℃ for 0.5-10 h, preferably at 40-80 ℃ for 1-8 h, the pH of the inorganic alkaline aqueous solution is 7.5-10, preferably 8-9.5, the mass ratio of the inorganic alkaline aqueous solution to the molecular sieve is 100: 1-5: 1, preferably 80: 1-20: 1, and the inorganic base is one of NaOH, KOH or ammonia water.
In the method, the treatment process of the inorganic alkaline water solution is carried out under the action of microwaves, preferably, the mixed materials are treated by adopting double-frequency microwaves, the frequency difference value of the double-frequency microwaves is 1-50 kHz, preferably 5-35 kHz, and the adsorption capacity of the modified 5A molecular sieve can be further improved by adopting a dipping treatment mode under the action of the microwaves.
In the method, the double-frequency microwave treatment can be carried out simultaneously or alternatively, the double-frequency microwave frequencies are respectively 20-50 kHz and 30-100 kHz, preferably 25-45 kHz and 35-80 kHz, and the microwave power is 0.01-20W/mL, preferably 0.05-10W/mL, based on the volume of the mixed solution.
In the above method, the drying temperature may be 50 to 200 ℃, preferably 60 to 150 ℃, and more preferably 80 to 120 ℃; the drying time is 1-24 h, preferably 4-8 h; the drying can be vacuum drying, or drying under the protection of inert gas, or drying in air atmosphere; the roasting temperature is 200-800 ℃, and preferably 400-600 ℃; the roasting time is 1-24 h, preferably 4-8 h; the carbon deposit is removed by roasting in an air atmosphere or an oxygen atmosphere.
A modified 5A molecular sieve prepared by the method. The modified 5A molecular sieve is applied as an adsorbent, and the adsorption conditions are as follows: taking naphtha containing 5-45% of normal alkane in percentage by weight as a raw material, and performing heat treatment at the temperature of 100-300 ℃ and the pressure of 0.5-2.5 Mpa in a bed layer at a mass space velocity of 0.2-4 h-1Under the normal condition, the raw material is contacted with an adsorbent, wherein the used adsorbent particles are 1.6 mm-2.3 mm.
According to the method, firstly, cycloalkane with a large molecular diameter is adopted to carry out carbonization treatment on the outer surface of the 5A molecular sieve and a large pore path in the 5A molecular sieve, the purpose of the carbonization treatment is to stabilize the pore opening of the 5A molecular sieve through a small amount of carbon deposition to ensure that the subsequent pore-enlarging treatment damages the pore opening of the molecular sieve so as to influence selective adsorption performance, then, inorganic base pore-enlarging treatment is carried out on the 5A molecular sieve to enlarge and modify the internal micropore of the 5A molecular sieve, finally, the carbon deposition is burnt off to recover the normal structure of the pore path of the 5A molecular sieve, and the adsorption capacity of the 5A molecular sieve is remarkably improved.
Detailed Description
The technical solution and the technical effects obtained by the present invention will be further described with reference to the following examples, but the present invention is not limited thereto.
Example 1
(1) An appropriate amount of spherical 5A molecular sieve ((commercial product, main properties are as follows: specific surface: 680 cm)2The pore volume per gram: 0.18cm3Per g, average pore diameter: 1.7nm, particle diameter: 1.6 mm-2.3 mm), placing a 5A molecular sieve in a tubular furnace, introducing a mixed gas of cyclopropane and an inert gas to completely replace air in the tubular furnace, sealing, wherein the concentration of the cyclopropane in the mixed gas is 20 volume percent, placing for 0.5h after sealing, rapidly heating to 400 ℃ under a sealing condition, keeping constant for 0.5h, and then cooling to normal temperature at the heating speed of 60 ℃/min;
(2) mixing the material obtained in the step (1) with a NaOH aqueous solution with the pH value of 8 according to a mass ratio of 1:20, and continuously treating the mixed solution by adopting microwaves with frequencies of 30kHz and 50kHz respectively at the same time, wherein the treatment temperature is 60 ℃ and the treatment time is 4 hours;
(2) and (3) filtering after the treatment in the step (2), drying the sample at 120 ℃ in vacuum for 4h, and roasting at 600 ℃ for 4 h. Roasting in air atmosphere to obtain the modified 5A molecular sieve.
Evaluation of static properties of modified 5A molecular sieve adsorbent: drying the modified 5A molecular sieve adsorbent, activating for 2h at 350 ℃, and cooling to room temperature for later use; at room temperature and adsorbent: the weight ratio of the adsorption liquid is 3: 5, under the condition of rapid stirring, measuring the adsorption quantity of the adsorbent to normal paraffin in the standard solution and the initial adsorption rate of 5 minutes by taking a cyclohexane solution containing 10 percent of normal hexane by weight percent as an adsorbent to evaluate the standard solution, wherein the evaluation result of the static adsorption performance of the adsorbent is shown in table 1.
Dynamic evaluation of the adsorbent on a fixed bed adsorption apparatus: the laboratory material is naphtha, wherein the total weight content of the normal paraffin of C4 to C8 is 21.25 percent; the experimental conditions are that the temperature of the adsorbent bed layer is 240 ℃, the pressure of the bed layer is 0.4Mpa, the packing content of the adsorbent is 25g, the height of the bed layer is 25cm, and the mass space velocity is 1.5h-1Under the conditions, the raw material was contacted with an adsorbent, and the adsorption amount of n-paraffins in naphtha at the breakthrough point was measured with the n-paraffin content of 1wt% in the raffinate oil as the breakthrough point, and the results are shown in Table 1.
Example 2
(1) An appropriate amount of spherical 5A molecular sieve ((commercial product, main properties are as follows: specific surface: 680 cm)2The pore volume per gram: 0.18cm3Per g, average pore diameter: 1.7nm, particle diameter: 1.6 mm-2.3 mm), placing a 5A molecular sieve in a tubular furnace, introducing a mixed gas of cyclopropane and an inert gas to completely replace air in the tubular furnace, sealing, wherein the concentration of the cyclopropane in the mixed gas is 30 volume percent, placing for 1h after sealing, rapidly heating to 500 ℃ under a sealing condition, keeping the temperature constant for 1.5h, and then cooling to normal temperature at the heating speed of 80 ℃/min;
(2) mixing the sample obtained in the step (1) with a NaOH aqueous solution with the pH of 9.5 in a mass ratio of 1:20, and continuously treating the mixed solution by adopting microwaves with frequencies of 30kHz and 50kHz respectively at the treatment temperature of 60 ℃ for 4 hours;
(3) and (3) filtering after the treatment in the step (2), drying the sample at 80 ℃ in vacuum for 8h, and roasting at 400 ℃ for 8 h. Roasting in air atmosphere to obtain the modified 5A molecular sieve.
Evaluation of static properties of modified 5A molecular sieve adsorbent: drying the modified 5A molecular sieve adsorbent, activating for 2h at 350 ℃, and cooling to room temperature for later use; at room temperature and adsorbent: the weight ratio of the adsorption liquid is 3: 5, under the condition of rapid stirring, measuring the adsorption quantity of the adsorbent to normal paraffin in the standard solution and the initial adsorption rate of 5 minutes by taking a cyclohexane solution containing 10 percent of normal hexane by weight percent as an adsorbent to evaluate the standard solution, wherein the evaluation result of the static adsorption performance of the adsorbent is shown in table 1.
Dynamic evaluation of the adsorbent on a fixed bed adsorption apparatus: the laboratory material is naphtha, wherein the total weight content of the normal paraffin of C4 to C8 is 21.25 percent; the experimental conditions are that the temperature of the adsorbent bed layer is 240 ℃, the pressure of the bed layer is 0.4Mpa, the packing content of the adsorbent is 25g, the height of the bed layer is 25cm, and the mass space velocity is 1.5h-1Under the conditions, the raw material was contacted with an adsorbent, and the adsorption amount of n-paraffins in naphtha at the breakthrough point was measured with the n-paraffin content of 1wt% in the raffinate oil as the breakthrough point, and the results are shown in Table 1.
Example 3
(1) An appropriate amount of spherical 5A molecular sieve ((commercial product, main properties are as follows: specific surface: 680 cm)2The pore volume per gram: 0.18cm3Per g, average pore diameter: 1.7nm, particle diameter: 1.6 mm-2.3 mm), placing a 5A molecular sieve in a tubular furnace, introducing a mixed gas of cyclopropane and an inert gas to completely replace air in the tubular furnace, sealing, wherein the concentration of the cyclopropane in the mixed gas is 50 volume percent, placing for 1h after sealing, rapidly heating to 550 ℃ under a sealing condition, keeping constant for 0.5h, and then cooling to normal temperature at the heating speed of 70 ℃/min;
(2) mixing the sample obtained in the step (1) with a NaOH aqueous solution with the pH of 8.5 in a mass ratio of 1:10, and continuously treating the mixed solution by adopting microwaves with frequencies of 35kHz and 50kHz respectively at 65 ℃ for 4 hours;
(3) and after the treatment is finished, filtering, drying the sample for 6 hours at 100 ℃ under the protection of inert gas, roasting the sample for 6 hours at 500 ℃, and roasting the sample in air atmosphere to obtain the modified 5A molecular sieve.
Evaluation of static properties of modified 5A molecular sieve adsorbent: drying the modified 5A molecular sieve adsorbent, activating for 2h at 350 ℃, and cooling to room temperature for later use; at room temperature and adsorbent: the weight ratio of the adsorption liquid is 3: 5, under the condition of rapid stirring, measuring the adsorption quantity of the adsorbent to normal paraffin in the standard solution and the initial adsorption rate of 5 minutes by taking a cyclohexane solution containing 10 percent of normal hexane by weight percent as an adsorbent to evaluate the standard solution, wherein the evaluation result of the static adsorption performance of the adsorbent is shown in table 1.
Dynamic evaluation of the adsorbent on a fixed bed adsorption apparatus: the laboratory material is naphtha, wherein the total weight content of the normal paraffin of C4 to C8 is 21.25 percent; the experimental conditions are that the temperature of the adsorbent bed layer is 240 ℃, the pressure of the bed layer is 0.4Mpa, the packing content of the adsorbent is 25g, the height of the bed layer is 25cm, and the mass space velocity is 1.5h-1Under the conditions, the raw material was contacted with an adsorbent, and the adsorption amount of n-paraffins in naphtha at the breakthrough point was measured with the n-paraffin content of 1wt% in the raffinate oil as the breakthrough point, and the results are shown in Table 1.
Example 4
(1) An appropriate amount of spherical 5A molecular sieve ((commercial product, main properties are as follows: specific surface: 680 cm)2The pore volume per gram: 0.18cm3Per g, average pore diameter: 1.7nm, particle diameter: 1.6 mm-2.3 mm), placing a 5A molecular sieve in a tubular furnace, introducing a mixed gas of cyclopropane and an inert gas to completely replace air in the tubular furnace, sealing, wherein the concentration of the cyclopropane in the mixed gas is 40 volume percent, placing for 1h after sealing, rapidly heating to 500 ℃ under a sealing condition, keeping the temperature constant for 0.5h, and then cooling to normal temperature at the heating speed of 65 ℃/min;
(2) mixing the sample obtained in the step (1) with a KOH aqueous solution with the pH of 9.0 in a mass ratio of 1:15, and continuously treating the mixed solution by adopting microwaves with frequencies of 30kHz and 40kHz respectively at the same time, wherein the treatment temperature is 55 ℃ and the treatment time is 3 hours;
(3) and after the treatment is finished, filtering, drying the sample at 80 ℃ for 8h in vacuum, roasting the sample at 350 ℃ for 8h, and roasting the sample in an air atmosphere to obtain the modified 5A molecular sieve.
Evaluation of static properties of modified 5A molecular sieve adsorbent: drying the modified 5A molecular sieve adsorbent, activating for 2h at 350 ℃, and cooling to room temperature for later use; at room temperature and adsorbent: the weight ratio of the adsorption liquid is 3: 5, under the condition of rapid stirring, measuring the adsorption quantity of the adsorbent to normal paraffin in the standard solution and the initial adsorption rate of 5 minutes by taking a cyclohexane solution containing 10 percent of normal hexane by weight percent as an adsorbent to evaluate the standard solution, wherein the evaluation result of the static adsorption performance of the adsorbent is shown in table 1.
Dynamic evaluation of the adsorbent on a fixed bed adsorption apparatus: the laboratory material is naphtha, wherein the total weight content of the normal paraffin of C4 to C8 is 21.25 percent; the experimental conditions are that the temperature of the adsorbent bed layer is 240 ℃, the pressure of the bed layer is 0.4Mpa, the packing content of the adsorbent is 25g, the height of the bed layer is 25cm, and the mass space velocity is 1.5h-1Under the conditions, the raw material was contacted with an adsorbent, and the adsorption amount of n-paraffins in naphtha at the breakthrough point was measured with the n-paraffin content of 1wt% in the raffinate oil as the breakthrough point, and the results are shown in Table 1.
Example 5
(1) An appropriate amount of spherical 5A molecular sieve ((commercial product, main properties are as follows: specific surface: 680 cm)2The pore volume per gram: 0.18cm3Per g, average pore diameter: 1.7nm, particle diameter: 1.6 mm-2.3 mm), placing a 5A molecular sieve in a tubular furnace, introducing a mixed gas of cyclopropane and an inert gas to completely replace air in the tubular furnace, sealing, wherein the concentration of the cyclopropane in the mixed gas is 25 volume percent, placing for 1.5h after sealing, rapidly heating to 500 ℃ under a sealing condition, keeping constant for 0.5h, and then cooling to normal temperature at the heating speed of 65 ℃/min;
(2) mixing the sample obtained in the step (1) with a KOH aqueous solution with the pH of 9.5 according to the mass ratio of 1:60, and continuously treating the mixed solution by adopting microwaves with the frequencies of 25kHz and 60kHz respectively at the treatment temperature of 750 ℃ for 8 hours.
(3) And after the treatment is finished, filtering, drying the sample at 70 ℃ for 9h in vacuum, roasting the sample at 350 ℃ for 6h, and roasting the sample in an air atmosphere to obtain the modified 5A molecular sieve.
Example 6
(1) An appropriate amount of spherical 5A molecular sieve ((commercial product, main properties are as follows: specific surface: 680 cm)2The pore volume per gram: 0.18cm3Per g, average pore diameter: 1.7nm, particle diameter: 1.6 mm-2.3 mm), placing a 5A molecular sieve in a tube furnace, introducing a mixed gas of cyclopropane and inert gas to completely replace the air in the tube furnace, sealing, wherein the concentration of the cyclopropane in the mixed gas is 20 volume percent, the standing time after sealing is 0.5h, and then rapidly placing the mixture in a sealed conditionHeating to 400 deg.C for 0.5h, and cooling to normal temperature at a heating rate of 60 deg.C/min;
(2) mixing the material obtained in the step (1) with a NaOH aqueous solution with the pH value of 8 in a mass ratio of 1:20, and treating the mixed solution by using microwaves with the frequency of 50kHz at the treatment temperature of 60 ℃ for 4 hours;
(2) and (3) filtering after the treatment in the step (2), drying the sample at 120 ℃ in vacuum for 4h, and roasting at 600 ℃ for 4 h. Roasting in air atmosphere to obtain the modified 5A molecular sieve.
Evaluation of static properties of modified 5A molecular sieve adsorbent: drying the modified 5A molecular sieve adsorbent, activating for 2h at 350 ℃, and cooling to room temperature for later use; at room temperature and adsorbent: the weight ratio of the adsorption liquid is 3: 5, under the condition of rapid stirring, measuring the adsorption quantity of the adsorbent to normal paraffin in the standard solution and the initial adsorption rate of 5 minutes by taking a cyclohexane solution containing 10 percent of normal hexane by weight percent as an adsorbent to evaluate the standard solution, wherein the evaluation result of the static adsorption performance of the adsorbent is shown in table 1.
Dynamic evaluation of the adsorbent on a fixed bed adsorption apparatus: the laboratory material is naphtha, wherein the total weight content of the normal paraffin of C4 to C8 is 21.25 percent; the experimental conditions are that the temperature of the adsorbent bed layer is 240 ℃, the pressure of the bed layer is 0.4Mpa, the packing content of the adsorbent is 25g, the height of the bed layer is 25cm, and the mass space velocity is 1.5h-1Under the conditions, the raw material was contacted with an adsorbent, and the adsorption amount of n-paraffins in naphtha at the breakthrough point was measured with the n-paraffin content of 1wt% in the raffinate oil as the breakthrough point, and the results are shown in Table 1.
Example 7
(1) An appropriate amount of spherical 5A molecular sieve ((commercial product, main properties are as follows: specific surface: 680 cm)2The pore volume per gram: 0.18cm3Per g, average pore diameter: 1.7nm, particle diameter: 1.6 mm-2.3 mm), placing a 5A molecular sieve in a tubular furnace, introducing a mixed gas of cyclopropane and inert gas to completely replace the air in the tubular furnace, sealing, wherein the concentration of the cyclopropane in the mixed gas is 20 volume percent, placing for 0.5h after sealing, rapidly heating to 400 ℃ under a sealing condition, keeping constant for 0.5h, then cooling to normal temperature at a heating speed of 60 DEG C/min;
(2) Mixing the material obtained in the step (1) with a NaOH aqueous solution with the pH value of 8 according to a mass ratio of 1:20, and then treating at the temperature of 60 ℃ for 4 hours;
(3) and (3) filtering after the treatment in the step (2), drying the sample at 120 ℃ in vacuum for 4h, and roasting at 600 ℃ for 4 h. Roasting in air atmosphere to obtain the modified 5A molecular sieve.
Evaluation of static properties of modified 5A molecular sieve adsorbent: drying the modified 5A molecular sieve adsorbent, activating for 2h at 350 ℃, and cooling to room temperature for later use; at room temperature and adsorbent: the weight ratio of the adsorption liquid is 3: 5, under the condition of rapid stirring, measuring the adsorption quantity of the adsorbent to normal paraffin in the standard solution and the initial adsorption rate of 5 minutes by taking a cyclohexane solution containing 10 percent of normal hexane by weight percent as an adsorbent to evaluate the standard solution, wherein the evaluation result of the static adsorption performance of the adsorbent is shown in table 1.
Dynamic evaluation of the adsorbent on a fixed bed adsorption apparatus: the laboratory material is naphtha, wherein the total weight content of the normal paraffin of C4 to C8 is 21.25 percent; the experimental conditions are that the temperature of the adsorbent bed layer is 240 ℃, the pressure of the bed layer is 0.4Mpa, the packing content of the adsorbent is 25g, the height of the bed layer is 25cm, and the mass space velocity is 1.5h-1Under the conditions, the raw material was contacted with an adsorbent, and the adsorption amount of n-paraffins in naphtha at the breakthrough point was measured with the n-paraffin content of 1wt% in the raffinate oil as the breakthrough point, and the results are shown in Table 1.
Example 8
(1) An appropriate amount of spherical 5A molecular sieve ((commercial product, main properties are as follows: specific surface: 680 cm)2The pore volume per gram: 0.18cm3Per g, average pore diameter: 1.7nm, particle diameter: 1.6 mm-2.3 mm), placing a 5A molecular sieve in a tubular furnace, introducing a mixed gas of cyclopropane and an inert gas to completely replace air in the tubular furnace, sealing, wherein the concentration of the cyclopropane in the mixed gas is 20 volume percent, placing for 0.5h after sealing, rapidly heating to 400 ℃ under a sealing condition, keeping constant for 0.5h, and then cooling to normal temperature at the heating speed of 60 ℃/min;
(2) mixing the material obtained in the step (1) with a NaOH aqueous solution with the pH value of 8 in a mass ratio of 1:20, and treating the mixed solution by using microwaves with the frequency of 30kHz at the treatment temperature of 60 ℃ for 8 hours;
(2) and (3) filtering after the treatment in the step (2), drying the sample at 120 ℃ in vacuum for 4h, and roasting at 600 ℃ for 4 h. Roasting in air atmosphere to obtain the modified 5A molecular sieve.
Evaluation of static properties of modified 5A molecular sieve adsorbent: drying the modified 5A molecular sieve adsorbent, activating for 2h at 350 ℃, and cooling to room temperature for later use; at room temperature and adsorbent: the weight ratio of the adsorption liquid is 3: 5, under the condition of rapid stirring, measuring the adsorption quantity of the adsorbent to normal paraffin in the standard solution and the initial adsorption rate of 5 minutes by taking a cyclohexane solution containing 10 percent of normal hexane by weight percent as an adsorbent to evaluate the standard solution, wherein the evaluation result of the static adsorption performance of the adsorbent is shown in table 1.
Dynamic evaluation of the adsorbent on a fixed bed adsorption apparatus: the laboratory material is naphtha, wherein the total weight content of the normal paraffin of C4 to C8 is 21.25 percent; the experimental conditions are that the temperature of the adsorbent bed layer is 240 ℃, the pressure of the bed layer is 0.4Mpa, the packing content of the adsorbent is 25g, the height of the bed layer is 25cm, and the mass space velocity is 1.5h-1Under the conditions, the raw material was contacted with an adsorbent, and the adsorption amount of n-paraffins in naphtha at the breakthrough point was measured with the n-paraffin content of 1wt% in the raffinate oil as the breakthrough point, and the results are shown in Table 1.
Comparative example 1
(1) An appropriate amount of spherical 5A molecular sieve ((commercial product, main properties are as follows: specific surface: 680 cm)2The pore volume per gram: 0.18cm3Per g, average pore diameter: 1.7nm, particle diameter: 1.6 mm-2.3 mm), placing a 5A molecular sieve in a tubular furnace, introducing a mixed gas of cyclopropane and an inert gas to completely replace air in the tubular furnace, sealing, wherein the concentration of the cyclopropane in the mixed gas is 20 volume percent, placing for 0.5h after sealing, rapidly heating to 400 ℃ under a sealing condition, keeping constant for 0.5h, and then cooling to normal temperature at the heating speed of 60 ℃/min;
(2) and (2) drying the sample treated in the step (1) at 120 ℃ in vacuum for 4h, and roasting at 600 ℃ for 4 h. Roasting in air atmosphere to obtain the modified 5A molecular sieve.
Evaluation of static properties of modified 5A molecular sieve adsorbent: drying the modified 5A molecular sieve adsorbent, activating for 2h at 350 ℃, and cooling to room temperature for later use; at room temperature and adsorbent: the weight ratio of the adsorption liquid is 3: 5, under the condition of rapid stirring, measuring the adsorption quantity of the adsorbent to normal paraffin in the standard solution and the initial adsorption rate of 5 minutes by taking a cyclohexane solution containing 10 percent of normal hexane by weight percent as an adsorbent to evaluate the standard solution, wherein the evaluation result of the static adsorption performance of the adsorbent is shown in table 1.
Dynamic evaluation of the adsorbent on a fixed bed adsorption apparatus: the laboratory material is naphtha, wherein the total weight content of the normal paraffin of C4 to C8 is 21.25 percent; the experimental conditions are that the temperature of the adsorbent bed layer is 240 ℃, the pressure of the bed layer is 0.4Mpa, the packing content of the adsorbent is 25g, the height of the bed layer is 25cm, and the mass space velocity is 1.5h-1Under the conditions, the raw material was contacted with an adsorbent, and the adsorption amount of n-paraffins in naphtha at the breakthrough point was measured with the n-paraffin content of 1wt% in the raffinate oil as the breakthrough point, and the results are shown in Table 1.
Comparative example 2
(1) An appropriate amount of spherical 5A molecular sieve ((commercial product, main properties are as follows: specific surface: 680 cm)2The pore volume per gram: 0.18cm3Per g, average pore diameter: 1.7nm, particle diameter: 1.6 mm-2.3 mm) and NaOH aqueous solution with the pH value of 8 in a mass ratio of 1:20, and continuously treating the mixed solution by microwaves with the frequencies of 30kHz and 50kHz respectively at the temperature of 60 ℃ for 4 hours;
(2) and (2) filtering after the treatment in the step (1), drying the sample at 120 ℃ in vacuum for 4h, and roasting at 600 ℃ for 4 h. Roasting in air atmosphere to obtain the modified 5A molecular sieve.
Evaluation of static properties of modified 5A molecular sieve adsorbent: drying the modified 5A molecular sieve adsorbent, activating for 2h at 350 ℃, and cooling to room temperature for later use; at room temperature and adsorbent: the weight ratio of the adsorption liquid is 3: 5, under the condition of rapid stirring, measuring the adsorption quantity of the adsorbent to normal paraffin in the standard solution and the initial adsorption rate of 5 minutes by taking a cyclohexane solution containing 10 percent of normal hexane by weight percent as an adsorbent to evaluate the standard solution, wherein the evaluation result of the static adsorption performance of the adsorbent is shown in table 1.
Dynamic evaluation of the adsorbent on a fixed bed adsorption apparatus: the laboratory material is naphtha, wherein the total weight content of the normal paraffin of C4 to C8 is 21.25 percent; the experimental conditions are that the temperature of the adsorbent bed layer is 240 ℃, the pressure of the bed layer is 0.4Mpa, the packing content of the adsorbent is 25g, the height of the bed layer is 25cm, and the mass space velocity is 1.5h-1Under the conditions, the raw material was contacted with an adsorbent, and the adsorption amount of n-paraffins in naphtha at the breakthrough point was measured with the n-paraffin content of 1wt% in the raffinate oil as the breakthrough point, and the results are shown in Table 1.
Comparative example 3
Weighing appropriate amount of spherical 5A molecular sieve for direct evaluation (commercial product, main properties are as follows: specific surface: 680 cm)2The pore volume per gram: 0.18cm3Per g, average pore diameter: 1.7nm, particle diameter: 1.6 mm-2.3 mm).
Evaluation of static properties of 5A molecular sieve adsorbent: drying the 5A molecular sieve adsorbent, activating for 2h at 350 ℃, and cooling to room temperature for later use; at room temperature and adsorbent: the weight ratio of the adsorption liquid is 3: 5, under the condition of rapid stirring, measuring the adsorption quantity of the adsorbent to normal paraffin in the standard solution and the initial adsorption rate of 5 minutes by taking a cyclohexane solution containing 10 percent of normal hexane by weight percent as an adsorbent to evaluate the standard solution, wherein the evaluation result of the static adsorption performance of the adsorbent is shown in table 1.
Dynamic evaluation of the adsorbent on a fixed bed adsorption apparatus: the laboratory material is naphtha, wherein the total weight content of the normal paraffin of C4 to C8 is 21.25 percent; the experimental conditions are that the temperature of the adsorbent bed layer is 240 ℃, the pressure of the bed layer is 0.4Mpa, the packing content of the adsorbent is 25g, the height of the bed layer is 25cm, and the mass space velocity is 1.5h-1Under the conditions, the raw material was contacted with an adsorbent, and the adsorption amount of n-paraffins in naphtha at the breakthrough point was measured with the n-paraffin content of 1wt% in the raffinate oil as the breakthrough point, and the results are shown in Table 1.
TABLE 1 evaluation results
Claims (19)
1. A preparation method of a molecular sieve adsorbent is characterized by comprising the following steps: the method comprises the following steps:
(1) fully contacting a material containing cycloalkane with a 5A molecular sieve, and quickly heating to carry out carbonization treatment on the 5A molecular sieve;
(2) dipping the material obtained in the step (1) by adopting an inorganic alkaline aqueous solution;
(3) and (3) filtering, drying and roasting the material in the step (2) to obtain the modified 5A molecular sieve.
2. The method of claim 1, wherein: the 5A molecular sieves are currently commercially available products or are prepared according to methods well known to those skilled in the art.
3. The method of claim 2, wherein: the 5A molecular sieve is one of a strip, a sheet, a column or a sphere.
4. The method of claim 1, wherein: the cycloalkane in the cycloalkane-containing material is cyclopropane, and the cyclopropane is directly contacted with the 5A molecular sieve or the mixed gas of the cyclopropane and the inert gas is contacted with the 5A molecular sieve.
5. The method of claim 4, wherein: a mixed gas of cyclopropane and inert gas is contacted with the 5A molecular sieve, and the concentration of the cyclopropane in the mixed gas is not higher than 60% by volume.
6. The method of claim 5, wherein: the concentration of cyclopropane in the mixed gas is 10-40 vol%.
7. The method of claim 1, wherein: the contact mode is that the 5A molecular sieve is placed in a material containing cycloalkane to enable the material containing cycloalkane to be in full contact, the placing time is 0.1-2h, then the temperature is rapidly raised to 350-650 ℃ under a sealed condition, the constant time is 0.5-1.5h, and the temperature raising speed is 50-100 ℃/min.
8. The method of claim 7, wherein: standing for 0.5-1h, and then rapidly heating to 400-500 ℃ under a sealed condition at a heating rate of 60-80 ℃/min.
9. The method of claim 7, wherein: placing the 5A molecular sieve in a reaction kettle or a tubular reactor, introducing a material containing cycloalkane to replace air in the reaction kettle or the tubular reactor, sealing and placing, and then heating.
10. The method of claim 1, wherein: the inorganic alkaline water solution is treated at the temperature of 30-120 ℃ for 0.5-10 h under the dipping condition, the pH of the inorganic alkaline water solution is 7.5-10, the mass ratio of the inorganic alkaline water solution to the molecular sieve is 100: 1-5: 1, and the inorganic alkali is one of NaOH, KOH or ammonia water.
11. The method of claim 10, wherein: the inorganic alkaline water solution is treated for 1-8 hours at 40-80 ℃, the pH of the inorganic alkaline water solution is 8-9.5, and the mass ratio of the inorganic alkaline water solution to the molecular sieve is 80: 1-20: 1.
12. The method of claim 1, wherein: the treatment process of the inorganic alkaline water solution is carried out under the action of microwaves.
13. The method of claim 12, wherein: the inorganic alkaline water solution treatment process adopts double-frequency microwave treatment, and the frequency difference of the double-frequency microwave is 1-50 kHz.
14. The method of claim 13, wherein: the dual-frequency microwave treatment is carried out simultaneously or alternatively, and the dual-frequency microwave frequency is 20-50 kHz and 30-100 kHz respectively.
15. The method of claim 1, wherein: the drying temperature is 50-200 ℃; the drying time is 1-24 h; the roasting temperature is 200-800 ℃; the roasting time is 1-24 h.
16. The method of claim 15, wherein: the drying temperature is 60-150 ℃; the drying time is 4-8 h; the roasting temperature is 400-600 ℃; the roasting time is 4-8 h.
17. A modified 5A molecular sieve whenever prepared by a process as claimed in any one of claims 1 to 16.
18. Use of the modified 5A molecular sieve of claim 17 as an adsorbent.
19. Use according to claim 18, characterized in that: the adsorption conditions were as follows: taking naphtha containing 5-45% of normal alkane in percentage by weight as a raw material, and performing heat treatment at the temperature of 100-300 ℃ and the pressure of 0.5-2.5 Mpa in a bed layer at a mass space velocity of 0.2-4 h-1Under normal conditions, the raw material is contacted with the adsorbent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811264097.1A CN111097378A (en) | 2018-10-29 | 2018-10-29 | Modified molecular sieve adsorbent and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811264097.1A CN111097378A (en) | 2018-10-29 | 2018-10-29 | Modified molecular sieve adsorbent and preparation method and application thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111097378A true CN111097378A (en) | 2020-05-05 |
Family
ID=70419784
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811264097.1A Pending CN111097378A (en) | 2018-10-29 | 2018-10-29 | Modified molecular sieve adsorbent and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111097378A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114682237A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Preparation method of 5A molecular sieve adsorbent |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150018196A1 (en) * | 2012-10-29 | 2015-01-15 | China Petroleum & Chemical Corporation | 5A Molecular Sieve Adsorbent and Method for Preparation of the Same |
CN104888695A (en) * | 2015-06-29 | 2015-09-09 | 岳阳金瀚高新技术股份有限公司 | Modified 5A molecular sieve used for removing small-amount n-hexane from isohexane and regeneration method thereof |
CN105621444A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Modified Y molecular sieve and preparation method thereof |
CN106669773A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Method for modifying Y-type molecular sieve |
CN106669774A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method and application of modified Y molecular sieve |
CN106809857A (en) * | 2017-03-15 | 2017-06-09 | 武汉理工大学 | The synthetic method of the mesoporous micropore multi-stage porous Y type Si-Al molecular sieves of ordered big hole |
-
2018
- 2018-10-29 CN CN201811264097.1A patent/CN111097378A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150018196A1 (en) * | 2012-10-29 | 2015-01-15 | China Petroleum & Chemical Corporation | 5A Molecular Sieve Adsorbent and Method for Preparation of the Same |
CN105621444A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Modified Y molecular sieve and preparation method thereof |
CN104888695A (en) * | 2015-06-29 | 2015-09-09 | 岳阳金瀚高新技术股份有限公司 | Modified 5A molecular sieve used for removing small-amount n-hexane from isohexane and regeneration method thereof |
CN106669773A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Method for modifying Y-type molecular sieve |
CN106669774A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method and application of modified Y molecular sieve |
CN106809857A (en) * | 2017-03-15 | 2017-06-09 | 武汉理工大学 | The synthetic method of the mesoporous micropore multi-stage porous Y type Si-Al molecular sieves of ordered big hole |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114682237A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Preparation method of 5A molecular sieve adsorbent |
CN114682237B (en) * | 2020-12-31 | 2023-09-01 | 中国石油化工股份有限公司 | Preparation method of 5A molecular sieve adsorbent |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104364008B (en) | A kind of thermally treated adsorbent composition | |
US8680344B2 (en) | Molecular sieve adsorbent blends and uses thereof | |
CN105056896B (en) | A kind of MOFs adsorbents and application | |
KR102038759B1 (en) | Zeolite adsorbents having a high external surface area and uses thereof | |
CN103611495B (en) | A kind ofly remove adsorbent of organic chloride in hydrocarbonaceous stream and preparation method thereof | |
TWI629098B (en) | Zeolitic adsorbents with large external surface area, method of preparation thereof and uses thereof | |
JP6545314B2 (en) | Novel carbon molecular sieve and pellet compositions useful for C2-C3 alkane / alkene separation | |
CN101495225A (en) | Agglomerated zeolitic adsorbents, their method of preapration and their uses | |
CN111097379A (en) | 5A molecular sieve and preparation method and application thereof | |
CN108940188B (en) | Preparation method of binder-free all-silicon MCM-41 molecular sieve adsorbent | |
CN105728027B (en) | A kind of absorbing desulfurization catalyst and preparation method thereof | |
US20180264437A1 (en) | Adsorbent mixture having improved thermal capacity | |
CN104492405B (en) | Core-shell type molecular sieve microsphere as well as preparation method and application thereof | |
KR20170083116A (en) | Zeolite adsorbents made from x zeolite with low binder content and low external surface area, method for preparation of same and uses thereof | |
CN106423114A (en) | Purification adsorbent for hydrocarbon impurities, preparing method and application | |
CN106423047B (en) | Spherical normal alkane adsorbent and preparation method thereof | |
CN109692658B (en) | Binder-free spherical 5A molecular sieve adsorbent and preparation method thereof | |
CN111097380A (en) | Adsorbent and preparation method and application thereof | |
CN111302358B (en) | Binder-free FAU type molecular sieve particles and preparation method and application thereof | |
CN111097378A (en) | Modified molecular sieve adsorbent and preparation method and application thereof | |
CN111097367A (en) | Adsorbent for adsorbing normal alkane and preparation method and application thereof | |
CN111097375A (en) | Modified molecular sieve and preparation method and application thereof | |
CN111097368A (en) | Adsorbing material and preparation method and application thereof | |
CN114288810B (en) | Application of microporous carbon material in adsorption separation of olefin and alkane | |
CN111097376A (en) | Molecular sieve for adsorbing normal alkane and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200505 |
|
WD01 | Invention patent application deemed withdrawn after publication |