CN108940188B - Preparation method of binder-free all-silicon MCM-41 molecular sieve adsorbent - Google Patents
Preparation method of binder-free all-silicon MCM-41 molecular sieve adsorbent Download PDFInfo
- Publication number
- CN108940188B CN108940188B CN201810698179.0A CN201810698179A CN108940188B CN 108940188 B CN108940188 B CN 108940188B CN 201810698179 A CN201810698179 A CN 201810698179A CN 108940188 B CN108940188 B CN 108940188B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- mcm
- silicon
- binder
- sieve adsorbent
- 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.)
- Active
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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
-
- 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
- C10G5/00—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas
- C10G5/02—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas with solid adsorbents
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Abstract
The invention discloses a preparation method of a binder-free all-silicon MCM-41 molecular sieve adsorbent, which comprises the following steps: taking macroporous all-silicon MCM-41 molecular sieve raw powder as an active adsorption component, adding a binder, and carrying out ball rolling forming, drying and roasting to obtain spherical particles with the particle size range of 0.3-0.8 mm; and then sequentially adding the template agent, the pH regulator and the silicon source into deionized water, stirring uniformly at room temperature, adding the spherical particles, controlling the liquid-solid ratio to be (10-30): 1, statically crystallizing at 80-160 ℃ for 24-84 h, taking out and washing after crystallization is finished until the pH is 7-8, and drying and roasting to obtain the MCM-41 molecular sieve adsorbent. The invention prepares the binder-free MCM-41 all-silicon molecular sieve adsorbent by recrystallizing spherical particles, the adsorbent has high thermal stability, large adsorption capacity and high diffusion speed, and the separation of three components of naphthenic hydrocarbon, monocyclic aromatic hydrocarbon and polycyclic aromatic hydrocarbon in a diesel component can be realized by utilizing a simulated moving bed adsorption separation process.
Description
Technical Field
The invention relates to a preparation method of a binder-free all-silicon MCM-41 molecular sieve adsorbent.
Background
In recent years, the proportion of poor-quality raw materials processed by a catalytic cracking unit is gradually increased due to the increasing weight and deterioration of global petroleum resources, so that the yield of catalytic cracking diesel oil is greatly increased, and the diesel-steam ratio of a refinery is higher. With the continuous decline of domestic consumption of diesel-gasoline ratio, the comprehensive utilization of diesel oil becomes increasingly important. The diesel mainly comprises straight-run diesel, coking diesel, catalytic cracking diesel and residual oil hydrogenated diesel, has the characteristics of high aromatic hydrocarbon content and low cetane number generally, and is difficult to meet the national VI diesel standard to be comprehensively implemented. The diesel oil is processed mainly by hydrofining and hydrofining technologies, and the hydrofining technology has over high hydrogen consumption and can not greatly improve the cetane number of the diesel oil; the hydrogenation modification technology has the advantages of great modification to the existing device, relatively high investment and unobvious economic benefit. The molecular sieve adsorbent is adopted to adsorb and separate diesel oil through a Simulated Moving Bed (SMB) to obtain high-purity aromatic hydrocarbon and high-purity naphthenic hydrocarbon components, so that molecular management of the diesel oil components can be realized, market demand change can be responded in a more targeted manner, the diesel-steam ratio of an oil refinery is reduced, and economic benefits are improved.
The diesel oil has complex components, the difference of the motion diameters of different components is large, a molecular sieve adsorbent with a specific pore size is needed for improving the diffusion speed and the separation degree, and MCM-41 is a mesoporous molecular sieve which has a hexagonal ordered pore structure, and the pore size is uniform and adjustable between 1nm and 10 nm. The large-aperture MCM-41 molecular sieve can be obtained by hydrothermal treatment, recrystallization technology and mixed surfactant technology, has high specific surface area, high porosity and large adsorption capacity, is favorable for organic molecule diffusion, has a surface rich in faintly acid silicon hydroxyl, does not need to add active components, can selectively and preferentially adsorb aromatic hydrocarbon molecules, and is an excellent adsorption and separation material. However, MCM-41 molecular sieve has thin sieve pore wall (<1nm), poor thermal stability and is not beneficial to high-temperature roasting regeneration; the SMB adsorption separation process needs spherical particle adsorbent in a certain size range, and the formed adsorbent contains a large amount of binder, so that the problems of small adsorption capacity, low adsorption rate and poor adsorption effect can be caused.
The patent CN103184065A discloses a method for adsorbing and removing nitrogen-containing compounds in diesel oil, wherein an Al-MCM-41 molecular sieve adsorbent and the diesel oil are subjected to contact adsorption denitrification in an intermittent reaction device or a fixed bed reaction device at the temperature of 75-110 ℃, and Al-MCM-41 in the patent is molecular sieve raw powder and is not subjected to a forming process. The patent CN101381086A discloses a preparation method of a Si-MCM-41 mesoporous molecular sieve, the method utilizes fly ash to prepare sodium silicate as a silicon source, a template agent is added, and the Si-MCM-41 mesoporous molecular sieve prepared by a hydrothermal method has a mesopore structure and a micropore structure, has a higher specific surface area, and reaches 1030m2The catalyst can be used for adsorbing and separating metal ions and organic matters, and can also be used as a catalyst carrier. Patent CN1401568A discloses a pressurized hydrothermal synthesis method of MCM-41 mesoporous molecular sieve, which comprises mixing template agent, water, alkali catalyst and silicon source to obtain crystallized mother liquor, placing the crystallized mother liquor into a high-pressure reaction kettle with polytetrafluoroethylene lining, charging nitrogen gas, heating the system for crystallization, and improving the thermal and hydrothermal stability of the synthesized MCM-41 mesoporous molecular sieve.
Disclosure of Invention
The invention aims to solve the technical problems of reduced adsorption capacity, reduced diffusion rate and poor adsorption and separation effects caused by the use of a binder for forming an MCM-41 molecular sieve and the problems of thin screen pore wall, poor thermal stability and reduced regeneration performance for diesel oil adsorption and separation of the MCM-41 molecular sieve in the prior art, and provides a preparation method of a binder-free all-silicon MCM-41 molecular sieve adsorbent for diesel oil adsorption and separation.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a preparation method of a binder-free all-silicon MCM-41 molecular sieve adsorbent comprises the following steps:
1) molding: taking full-silicon MCM-41 molecular sieve raw powder as an active adsorption component, adding a binder, and carrying out ball rolling forming, drying and roasting to obtain spherical particles with the particle size range of 0.3-0.8mm, wherein the MCM-41 molecular sieve content in the spherical particles is 85-95 wt%;
2) and (3) recrystallization: sequentially adding a template agent, a pH regulator and a silicon source into deionized water, and uniformly stirring at room temperature to obtain a mixture with the total molar composition of Na2O:SiO2:Q1:H2O (0.1 to 0.5):1 (0.5 to 1.0): 250 to 400, wherein Na2Adding the spherical particles prepared in the step 1) into a template agent Q1 with the alkalinity represented by O, the liquid-solid ratio (10-30) to 1, statically crystallizing at 80-160 ℃ for 24-84 h, taking out and washing after crystallization till the pH value is 7-8, and drying and roasting to obtain an MCM-41 molecular sieve adsorbent;
wherein the pore diameter of the all-silicon MCM-41 molecular sieve raw powder calculated by a BJH model is larger than 5 nm;
the forming binder is at least one selected from water glass and silica sol.
In the above technical solution, the template agent Q1 is preferably at least one selected from the group consisting of dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium chloride.
In the above technical solution, the silicon source is preferably at least one selected from ethyl orthosilicate, sodium silicate, and silica sol.
In the technical scheme, the crystallization temperature is preferably 100-150 ℃, and the crystallization time is preferably 36-72 h.
In the technical scheme, the all-silicon MCM-41 molecular sieve raw powder is preferably prepared by the following method:
(1) sequentially dissolving a template agent and a pore-expanding agent in deionized water, adding a pH regulator, and uniformly stirring at room temperature to obtain a solution A;
(2) slowly adding silicon source into the solution A under stirring to obtain white gel mixture with total molar composition of Na2O:SiO2:Q2:E:H2O ═ 0.05 to 0.5, 1 (0.1 to 0.5): (0.1-1.0): (60-150), wherein Na2O represents alkalinity, Q2 represents a template agent, and E represents a pore-expanding agent;
(3) and transferring the white gel into a reaction kettle for hydrothermal reaction, dynamically crystallizing at 80-160 ℃ for 24-84 h, taking out and washing after crystallization is finished until the pH value is 7-8, and drying and roasting to obtain MCM-41 molecular sieve raw powder.
In the technical scheme of the all-silicon MCM-41 molecular sieve raw powder, the template Q2 is preferably selected from at least one of hexadecyl triethyl ammonium bromide, hexadecyl triethyl ammonium chloride, octadecyl triethyl ammonium bromide and octadecyl triethyl ammonium chloride.
In the technical scheme of the all-silicon MCM-41 molecular sieve raw powder, the pore-expanding agent E is preferably at least one of 1,3, 5-Trimethylbenzene (TMB), dodecylamine and N, N-Dimethylhexadecylammonium (DMHA).
The invention also provides the binder-free all-silicon molecular sieve adsorbent prepared by the preparation method.
The invention further provides a method for selectively adsorbing and separating naphthenic hydrocarbon, monocyclic aromatic hydrocarbon and polycyclic aromatic hydrocarbon in diesel components by using the all-silicon MCM-41 molecular sieve adsorbent in the SMB process. The product separated by the method is rectified to recover the desorbent, and components rich in naphthenic hydrocarbon, monocyclic aromatic hydrocarbon and polycyclic aromatic hydrocarbon are respectively obtained.
The invention has the following beneficial effects:
1) the method adopts the large-aperture MCM-41 molecular sieve raw powder with the aperture larger than 5nm, so that the adsorbent still has a large enough main pore channel after recrystallization; secondly, the recrystallization property of the MCM-41 molecular sieve is utilized, the thickness of the sieve pore wall of the original MCM-41 molecular sieve is increased, and the stability of the prepared adsorbent during high-temperature roasting regeneration is improved;
2) the binder added in the forming process is converted into an MCM-41 molecular sieve serving as an effective adsorption component in situ, the concentration of silicon hydroxyl on the surface of the prepared adsorbent is increased, and the adsorption capacity, the molecular diffusion speed and the adsorption separation effect of the adsorbent are improved;
3) the MCM-41 molecular sieve adsorbent prepared by the method is applied to a simulated moving bed adsorption separation process, can simultaneously purify naphthenic hydrocarbon, monocyclic aromatic hydrocarbon and polycyclic aromatic hydrocarbon substances in diesel components, can achieve the product purity of over 90 percent after the desorbent is recovered by rectification, and can obtain high-purity paraffin components which are high-cetane number diesel components after the diesel is subjected to adsorption purification, and can also be used as olefin production increasing raw materials in the processes of catalytic cracking, catalytic cracking and the like.
Detailed Description
The technical scheme of the invention is further explained by combining the embodiment;
the raw materials used in the examples are paraffin-removed diesel components, the compositions are shown in Table 2, and the results of simulated moving bed evaluations are shown in Table 3;
the yield of the naphthenic hydrocarbon is equal to the quality of the naphthenic hydrocarbon of the product/the quality of the naphthenic hydrocarbon in the feed diesel oil multiplied by 100 percent;
the yield of the monocyclic aromatic hydrocarbon is equal to the mass of the monocyclic aromatic hydrocarbon in the product/mass of the monocyclic aromatic hydrocarbon in the feed diesel oil multiplied by 100 percent;
polycyclic aromatic hydrocarbon yield is equal to product polycyclic aromatic hydrocarbon quality/polycyclic aromatic hydrocarbon quality in feed diesel oil multiplied by 100%;
the purity of the cycloalkane is equal to the mass of the cycloalkane in the cycloalkane component/the total mass of the cycloalkane component multiplied by 100%;
the purity of the monocyclic aromatic hydrocarbon is equal to the mass of the monocyclic aromatic hydrocarbon in the monocyclic aromatic hydrocarbon component/the total mass of the monocyclic aromatic hydrocarbon component multiplied by 100%;
polycyclic aromatic hydrocarbon purity is polycyclic aromatic hydrocarbon mass/total polycyclic aromatic hydrocarbon component mass x 100% in the polycyclic aromatic hydrocarbon component.
Example 1
Synthesizing: weighing 81.3g of hexadecyl triethyl ammonium bromide and 48.1g of TMB, sequentially dissolving in 3600g of deionized water, adding 9.6g of NaOH, uniformly stirring at room temperature, slowly dropwise adding 416.7g of tetraethoxysilane to obtain uniform white gel, transferring the uniform white gel into a reaction kettle, stirring and crystallizing at 100 ℃ for 72 hours, taking out and washing after crystallization till the pH value is 7-8, and drying and roasting to obtain the large-aperture MCM-41 molecular sieve raw powder.
Molding: weighing the large-aperture MCM-41 molecular sieve powder on an inner rotary disc of a sugar coating machine, spraying a silica sol aqueous solution while rotating, wherein the adding amount of the silica sol aqueous solution is 5-15 wt%, sieving particles with the particle size of 0.3-0.8mm after molding, drying and roasting to obtain spherical particles.
And (3) recrystallization: weighing 37.6g of dodecyl trimethyl ammonium bromide, 2.0g of NaOH and 50.9g of ethyl orthosilicate, sequentially dissolving in 1100g of deionized water, uniformly stirring at room temperature, adding 110g of the formed spherical particles, statically crystallizing at 100 ℃ for 60 hours, taking out after crystallization, washing until the pH value is 7-8, drying and roasting to obtain the MCM-41 molecular sieve adsorbent.
Performance evaluation: a five-zone 16-column SMB device is adopted for diesel oil adsorption and separation, methylcyclohexane is adopted as a monocyclic aromatic hydrocarbon desorption agent, toluene is adopted as a polycyclic aromatic hydrocarbon desorption agent, the adsorption bed is divided into 4-2-3-5-2, the temperature of the adsorption column is 80-100 ℃, the pressure of the adsorption bed is 0.5-0.8 MPa, the switching time is 700-900 s, the mass flow rate ratio of the raw diesel oil to the desorption agent is 1: 2-1: 3, and the volume flow rate ratio of the raw diesel oil to the circulating amount is 1: 4-1: 5.
Example 2
Synthesizing: weighing 180.3g of hexadecyltriethyl ammonium chloride and 136.3g of dodecane, sequentially dissolving in 2160g of deionized water, adding 16.3g of NaOH, stirring uniformly at room temperature, slowly adding 568.4g of sodium silicate to obtain uniform white gel, transferring to a reaction kettle, stirring and crystallizing at 120 ℃ for 60 hours, taking out and washing after crystallization is finished until the pH value is 7-8, and drying and roasting to obtain the large-aperture MCM-41 molecular sieve raw powder.
Molding: weighing the large-aperture MCM-41 molecular sieve powder on an inner rotary disc of a sugar coating machine, spraying a silica sol aqueous solution while rotating, wherein the addition amount of the water glass aqueous solution is 5-15 wt%, sieving particles with the particle size of 0.3-0.8mm after molding, drying and roasting to obtain spherical particles.
And (3) recrystallization: 89.3g of decaalkyltrimethyl ammonium chloride, 4.9g of NaOH and 86.9 g of sodium silicate are sequentially dissolved in 2200g of deionized water, the mixture is uniformly stirred at room temperature, 110g of the formed spherical particles are added, static crystallization is carried out at 120 ℃ for 48 hours, the mixture is taken out after crystallization is finished and washed until the pH value is 7-8, and then the MCM-41 molecular sieve adsorbent is obtained through drying and roasting.
Performance evaluation: the process conditions were the same as described in example 1.
Example 3
Synthesizing: 260.6g of octadecyl triethyl ammonium bromide and 144.2g of TMB are weighed, dissolved in 5040g of deionized water in sequence, 32g of NaOH is added, after the mixture is stirred uniformly at room temperature, 122.4g of white carbon black is slowly added to obtain uniform white gel, the uniform white gel is transferred to a reaction kettle, stirred and crystallized for 36 hours at 150 ℃, taken out after the crystallization is finished, washed until the pH value is 7-8, and then dried and roasted to obtain the large-aperture MCM-41 molecular sieve raw powder.
Molding: weighing the large-aperture MCM-41 molecular sieve powder on an inner rotary disc of a sugar coating machine, spraying a water glass aqueous solution while rotating, wherein the adding amount of a silica sol aqueous solution is 5-15 wt%, sieving particles with the particle size of 0.3-0.8mm after molding, drying and roasting to obtain spherical particles.
And (3) recrystallization: 51.4g of dodecyl trimethyl ammonium bromide, 6.3g of NaOH and 54.62g of ethyl orthosilicate are sequentially dissolved in 1650g of deionized water, the mixture is uniformly stirred at room temperature, 110g of the formed spherical particles are added, static crystallization is carried out at 150 ℃ for 36 hours, the mixture is taken out after crystallization is finished and washed until the pH value is 7-8, and then drying and roasting are carried out to obtain the MCM-41 molecular sieve adsorbent.
Performance evaluation: the process conditions were the same as described in example 1.
Example 4
Synthesizing: 325.1g of hexadecyl triethyl ammonium bromide and 431.2g of DMHA are weighed and sequentially dissolved in 4320g of deionized water, 48g of KOH is added, stirring is carried out at room temperature, 416.7g of ethyl orthosilicate is slowly added to obtain uniform white gel, the uniform white gel is transferred to a reaction kettle, stirring and crystallization are carried out at 120 ℃ for 60 hours, after crystallization is finished, the gel is taken out and washed until the pH value is 7-8, and then drying and roasting are carried out to obtain the large-aperture MCM-41 molecular sieve raw powder.
Molding: weighing the large-aperture MCM-41 molecular sieve powder on an inner rotary disc of a sugar coating machine, spraying a water glass aqueous solution while rotating, wherein the adding amount of a silica sol aqueous solution is 5-15 wt%, sieving particles with the particle size of 0.3-0.8mm after molding, drying and roasting to obtain spherical particles.
And (3) recrystallization: 154.0g of dodecyl trimethyl ammonium chloride, 9.8g of KOH and 52.4g of silica sol are sequentially dissolved in 2750g of deionized water, the mixture is uniformly stirred at room temperature, 110g of the formed spherical particles are added, static crystallization is carried out at 120 ℃ for 48 hours, the mixture is taken out after crystallization is finished and washed until the pH value is 7-8, and then the MCM-41 molecular sieve adsorbent is obtained through drying and roasting.
Performance evaluation: the process conditions were the same as described in example 1.
Example 5
Synthesizing: 287.3g of octadecyl triethyl ammonium chloride and 102.2g of dodecane are weighed, sequentially dissolved in 2880g of deionized water, then 11.7g of KOH is added, after the mixture is uniformly stirred at room temperature, 568.4g of sodium silicate is slowly added to obtain uniform white gel, the uniform white gel is transferred to a reaction kettle, stirred and crystallized at 100 ℃ for 60 hours, after the crystallization is finished, the uniform white gel is taken out and washed until the pH value is 7-8, and then the large-aperture MCM-41 molecular sieve raw powder is obtained through drying and roasting.
Molding: weighing the MCM-41 molecular sieve powder on an inner rotary disc of a sugar coating machine, spraying a silica sol aqueous solution while rotating, wherein the addition amount of the water glass aqueous solution is 5-15 wt%, sieving particles with the particle size of 0.3-0.8mm after molding, drying and roasting to obtain spherical particles.
And (3) recrystallization: weighing 85.8g of dodecyl trimethyl ammonium bromide, 5.8g of NaOH and 144.74g of sodium silicate, sequentially dissolving in 2750g of deionized water, uniformly stirring at room temperature, adding 110g of the formed spherical particles, statically crystallizing at 100 ℃ for 48 hours, taking out after crystallization, washing until the pH value is 7-8, drying and roasting to obtain the MCM-41 molecular sieve adsorbent.
Performance evaluation: the process conditions were the same as described in example 1.
Example 6
The MCM-41 molecular sieve adsorbent after performance evaluation in example 1 is roasted at high temperature, the regeneration thermal stability of the adsorbent is tested, and the roasting conditions are as follows: in the air atmosphere, the temperature is increased to 300 ℃ at the speed of 2 ℃/min and kept for 2h, the temperature is increased to 550 ℃ at the speed of 2 ℃/min and kept for 6h, the temperature is naturally reduced, and the performance of the adsorbent after roasting is evaluated by adopting the same method and conditions as the embodiment 1.
Example 7
The MCM-41 molecular sieve adsorbent after performance evaluation in example 2 is roasted at high temperature, the regeneration thermal stability of the adsorbent is tested, and the roasting conditions are as follows: in the air atmosphere, the temperature is increased to 300 ℃ at the speed of 2 ℃/min and kept for 2h, the temperature is increased to 550 ℃ at the speed of 2 ℃/min and kept for 6h, the temperature is naturally reduced, and the performance of the adsorbent after roasting is evaluated by adopting the same method and conditions as the embodiment 1.
Comparative example 1
The synthesis process and the forming process of the MCM-41 molecular sieve are the same as those of the example 1, and the MCM-41 adsorbent containing the binder is obtained without carrying out the recrystallization process.
Performance evaluation: the process conditions were the same as described in example 1.
Comparative example 2
The synthesis process and the forming process of the MCM-41 molecular sieve are the same as those of the example 2, and the MCM-41 adsorbent containing the binder is obtained without carrying out the recrystallization process.
Performance evaluation: the process conditions were the same as described in example 1.
TABLE 1 MCM-41 molecular sieve adsorbent physical Properties
TABLE 2 Diesel feed composition
TABLE 3 evaluation results of adsorptive separation of adsorbents prepared in examples and comparative examples
Claims (6)
1. A preparation method of binder-free all-silicon MCM-41 molecular sieve adsorbent for separating three components of diesel oil, wherein the three components of the diesel oil are cycloparaffin, monocycloparaffin and polycycloalkane, and the method is characterized by comprising the following steps:
(1) molding: taking full-silicon MCM-41 molecular sieve raw powder as an active adsorption component, adding a binder, and carrying out rolling ball forming, drying and roasting to obtain spherical particles with the particle size range of 0.3-0.8 mm; wherein the MCM-41 molecular sieve content in the spherical particles is 85-95 wt%;
(2) and (3) recrystallization: sequentially adding a template agent, a pH regulator and a silicon source into deionized water, and uniformly stirring at room temperature to obtain a mixture with the total molar composition of Na2O:SiO2:Q1: H2O = (0.05-0.6): 1, (0.2-1.2): 200-500), wherein Na2O represents alkalinity, Q1 represents a template agent, the spherical particles prepared in the step (1) are added, the liquid-solid ratio is = (10-30): 1, static crystallization is carried out at 80-160 ℃ for 24-84 h, the spherical particles are taken out after crystallization is finished and washed until the pH is = 7-8, and then the MCM-41 molecular sieve adsorbent is obtained through drying and roasting;
the pore diameter of the all-silicon MCM-41 molecular sieve raw powder calculated by a BJH model is larger than 5 nm;
the forming binder is at least one of water glass and silica sol.
2. The method for preparing the all-silicon MCM-41 molecular sieve adsorbent according to claim 1, wherein the all-silicon MCM-41 molecular sieve raw powder is prepared by the following method:
(1) sequentially dissolving a template agent and a pore-expanding agent in deionized water, adding a pH regulator, and uniformly stirring at room temperature to obtain a solution A;
(2) slowly dripping a silicon source into the solution A under the stirring condition to obtain a white gel mixture, wherein the total molar composition of the mixture is Na2O:SiO2:Q2:E:H2O = (0.02-0.6): 1 (0.05-0.8): (0.05-1.5): (40-200) in which Na2O represents alkalinity, Q2 represents a template agent, and E represents a pore-expanding agent;
(3) and transferring the white gel mixture into a reaction kettle for hydrothermal reaction, dynamically crystallizing at 80-160 ℃ for 24-84 h, taking out and washing after crystallization is finished until the pH is = 7-8, and drying and roasting to obtain the all-silicon MCM-41 molecular sieve raw powder.
3. The process for preparing an all-silicon MCM-41 molecular sieve adsorbent according to claim 1, characterized in that:
the template agent is at least one of salts of dodecyl trimethyl ammonium and salts of dodecyl trimethyl ammonium;
the silicon source is at least one of tetraethoxysilane, sodium silicate and silica sol.
4. A method of preparing an all-silicon MCM-41 molecular sieve adsorbent according to claim 2, characterized in that: the template agent Q2 is at least one of hexadecyl triethyl ammonium salt and octadecyl triethyl ammonium salt; the pore-expanding agent is at least one of 1,3, 5-trimethylbenzene, dodecylamine and N, N-dimethyl hexadecyl ammonium.
5. An all-silicon MCM-41 molecular sieve adsorbent made by the method of any of claims 1-4.
6. Use of the all-silicon MCM-41 molecular sieve adsorbent of claim 5 in three-component separation of naphthenic hydrocarbon, monocyclic aromatic hydrocarbon and polycyclic aromatic hydrocarbon of diesel components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810698179.0A CN108940188B (en) | 2018-06-29 | 2018-06-29 | Preparation method of binder-free all-silicon MCM-41 molecular sieve adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810698179.0A CN108940188B (en) | 2018-06-29 | 2018-06-29 | Preparation method of binder-free all-silicon MCM-41 molecular sieve adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108940188A CN108940188A (en) | 2018-12-07 |
| CN108940188B true CN108940188B (en) | 2021-07-13 |
Family
ID=64484400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810698179.0A Active CN108940188B (en) | 2018-06-29 | 2018-06-29 | Preparation method of binder-free all-silicon MCM-41 molecular sieve adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108940188B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109351326A (en) * | 2018-12-19 | 2019-02-19 | 四川省达科特能源科技股份有限公司 | A kind of renewable mercury removal agent and preparation method thereof for natural gas |
| CN114433037B (en) * | 2020-10-20 | 2024-01-26 | 中国石油化工股份有限公司 | Preparation method of M41S mesoporous material adsorbent, M41S mesoporous material adsorbent and application |
| CN114210301A (en) * | 2021-10-29 | 2022-03-22 | 中国人民解放军63919部队 | Mesoporous solid amine adsorbent and preparation method and application thereof |
| CN114768748A (en) * | 2022-04-22 | 2022-07-22 | 山东亮剑环保新材料有限公司 | Preparation method of all-silicon micro-mesoporous composite molecular sieve VOCs adsorbent |
| CN114917865B (en) * | 2022-06-06 | 2023-08-22 | 中海油天津化工研究设计院有限公司 | Aromatic hydrocarbon adsorbent and application thereof in yield-increasing ethylene cracking raw material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348260A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Preparation of binderless MFI/FAU composite zeolite molecular sieve |
| CN101348262A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Preparation of zeolite binderless ZSM-5 |
| WO2011008920A2 (en) * | 2009-07-17 | 2011-01-20 | Exxonmobil Research And Engineering Company | Hydroprocessing of biocomponent feedstocks with fcc off-gas |
| CN103028372A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Binderless zeolite adsorbent and preparation method thereof |
| CN107512727A (en) * | 2016-06-18 | 2017-12-26 | 中国石油化工股份有限公司 | The preparation method of binder free MWW structure molecular screens |
-
2018
- 2018-06-29 CN CN201810698179.0A patent/CN108940188B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348260A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Preparation of binderless MFI/FAU composite zeolite molecular sieve |
| CN101348262A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Preparation of zeolite binderless ZSM-5 |
| WO2011008920A2 (en) * | 2009-07-17 | 2011-01-20 | Exxonmobil Research And Engineering Company | Hydroprocessing of biocomponent feedstocks with fcc off-gas |
| CN103028372A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Binderless zeolite adsorbent and preparation method thereof |
| CN107512727A (en) * | 2016-06-18 | 2017-12-26 | 中国石油化工股份有限公司 | The preparation method of binder free MWW structure molecular screens |
Non-Patent Citations (1)
| Title |
|---|
| "Hydrothermally stable restructured mesoporous silica";Robert Mokaya;《Chem. Commun.》;20010502;第933-934页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108940188A (en) | 2018-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108940188B (en) | Preparation method of binder-free all-silicon MCM-41 molecular sieve adsorbent | |
| US8791039B2 (en) | Agglomerated zeolite adsorbents and process for producing the same | |
| CN109107547B (en) | Agglomerated zeolitic adsorbents, method for their production and their use | |
| CN101003380B (en) | Method for synthesizing ZSM-5 zeolite with multilevel pore canals | |
| CN111450804A (en) | Aluminum-based metal-organic framework material, preparation method, adsorption separation device and method for separating hydrocarbon mixture | |
| CN109692656B (en) | Mesoporous Y zeolite, adsorbent and preparation method of adsorbent | |
| CN113083222A (en) | Modified adsorbent for adsorption separation and preparation method and application thereof | |
| CN111097379A (en) | 5A molecular sieve and preparation method and application thereof | |
| CN110538644A (en) | Antibacterial Zn complex-porous resin composite adsorption material and preparation method thereof | |
| CN107376835B (en) | Efficient hydrogen production adsorbent and preparation method thereof | |
| CN109692658B (en) | Binder-free spherical 5A molecular sieve adsorbent and preparation method thereof | |
| CN102451664B (en) | Preparation method of adsorbent used for whole naphtha adsorption separation process | |
| US20150105600A1 (en) | Adsorbents for the separation of para-xylene from c8 alkyl aromatic hydrocarbon mixtures, methods for separating para-xylene using the adsorbents and methods for making the adsorbents | |
| CN111097380A (en) | Adsorbent and preparation method and application thereof | |
| CN111097367A (en) | Adsorbent for adsorbing normal alkane and preparation method and application thereof | |
| CN114160096B (en) | Adsorbent for separating ethylbenzene from carbon octa-aromatic hydrocarbons and preparation method thereof | |
| CN111073683A (en) | Method for ultra-deep desulfurization and dearomatization of diesel oil | |
| CN114100564A (en) | Adsorbent for removing oxygen-containing compounds from Fischer-Tropsch synthetic oil and preparation method thereof | |
| CN108435193B (en) | Reproducible organochlorine removal catalyst and preparation method thereof | |
| CN111097368A (en) | Adsorbing material and preparation method and application thereof | |
| CN105013528B (en) | Composite molecular sieve catalyst for preparing gasoline by methanol and preparation method thereof | |
| CN107999139B (en) | Preparation method of mercury-free catalyst for improving purity of vinyl chloride crude product | |
| JP2023546276A (en) | m-xylene adsorbent and its preparation method | |
| CN108246239B (en) | Method for removing carbonyl sulfide by metal-doped KP type molecular sieve adsorbent | |
| CN114917866B (en) | Olefin adsorbent for Fischer-Tropsch light distillate oil adsorption rectification coupling process and preparation method 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |