CN115536040B - Nano lotus leaf-shaped aluminum-rich mordenite molecular sieve, and synthetic method and application thereof - Google Patents
Nano lotus leaf-shaped aluminum-rich mordenite molecular sieve, and synthetic method and application thereof Download PDFInfo
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Abstract
A nanometer lotus leaf-shaped aluminum-rich mordenite molecular sieve, a synthesis method and application thereof, wherein the preparation steps of the zeolite molecular sieve are as follows: adding an aluminum source into a NaOH solution, and uniformly mixing to obtain a solution A; sequentially adding a template agent, a silicon source, an aluminum-rich agent and a crystal growth inhibitor into the solution A, and stirring until a uniform sol B is formed; finally, stirring the sol B to a dry gel state, adding water, transferring the dry gel state into a reaction kettle, and forming uniform and stable gel under the condition of high-temperature vibration; the nano lotus leaf-shaped aluminum-rich MOR molecular sieve with the sheet thickness of 10-100 nm is obtained through washing, filtering, drying, roasting, ammonia exchange and roasting. The catalyst is used for methanol carbonylation reaction, has the characteristic of high acetic acid selectivity, and has simple preparation process, low cost and good application prospect.
Description
Technical Field
The invention belongs to zeolite molecular sieves, synthesis thereof and application thereof in the field of catalysis, and in particular relates to a synthesis method of a nano lotus leaf-shaped aluminum-rich mordenite molecular sieve and application thereof in carbonylation reaction.
Background
Acetic acid is an important large-scale chemical product and is widely applied to the fields of solvents, synthetic coatings, fragrances, foods, medicines and the like, and downstream products comprise methyl acetate, ethanol, acetic anhydride acetone, polyvinyl acetate and the like. Acetic acid is currently produced industrially mainly by the methanol homogeneous carbonylation process (J.Catal., 1972, 27:389-396), which process routeThe line contributes to 70% of the current acetic acid production, but the main catalysts Ir and Rh are expensive, the cocatalyst iodide severely corrodes equipment, and a large amount of water exists in a reaction system, so that the product separation is difficult. Therefore, research into synthesizing acetic acid by methanol heterogeneous carbonylation has attracted attention in recent years. Vine et al (Angew.chem.int.ed., 2006,45:1617-1620; U.S. 4612387) propose that zeolite molecular sieves (e.g., H-MOR, py-H-MOR, H-ZSM-5, cu/H-MOR, cu/H-ZSM-5) can still catalyze methanol carbonylation to produce acetic acid without the addition of iodine adjuvants, wherein MOR molecular sieve is a halogen-free solid acid catalytic material, can realize 90% methanol conversion and 80% acetic acid selectivity at lower temperature and pressure conditions, and has good development prospects. However, the stability of the current MOR molecular sieve methanol carbonylation is still inadequate, performance is difficult to maintain for more than 100 hours, and the required CO/CH 3 The OH is higher and the performance still needs to be further improved.
The research shows that the catalytic active sites of the MOR molecular sieve are mainly distributed on aluminum sites in the pore canal, so that besides the acidic characteristic, the special pore canal of the molecular sieve and the side pocket formed by the interconnection of the pore canals play a decisive role in the generation of reaction intermediate products and the trend of reaction paths; the long and narrow pore canal of the molecular sieve is unfavorable for the diffusion of reactants and resultant molecules, even the pore canal length of several micrometers is likely to cause a great amount of aggregation of the resultant molecules or the occurrence of secondary reaction to lead to rapid rise of carbon deposition rate, so that the molecular sieve is rapidly deactivated, and the selectivity of target products is rapidly reduced. It is found that the catalyst performance can be improved by creating a multi-stage pore molecular sieve containing both mesopores and micropores, expanding the pore size of the molecular sieve to enhance the diffusion of the substance, or by synthesizing a molecular sieve having a regular morphology in a nanoscale scale, shortening the pore length of the molecular sieve to enhance the diffusion of the substance. Researches show that the multistage pore molecular sieve can be synthesized by dealuminating or desilicating through acid treatment or alkali treatment, but the method is extremely easy to cause pore collapse of the molecular sieve, so that the catalyst performance is poor.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a nano lotus leaf-shaped aluminum-rich mordenite molecular sieve, a preparation method thereof and application thereof in carbonylation reaction.
The molecular sieve is in the shape of a nanometer lotus leaf, the thickness of a sheet layer is 10-100 nm, the eight-membered ring framework is rich in aluminum, and the silicon-aluminum ratio is 7-10.
In order to achieve the above object, the present invention adopts the following scheme:
step 1, adding an aluminum source into an NaOH aqueous solution, and stirring and dissolving the aluminum source in a beaker at constant temperature to obtain a uniform and transparent mixed solution A;
step 2, sequentially adding a template agent, a silicon source, an aluminum-rich agent and a crystal growth inhibitor into the solution A, and stirring vigorously at constant temperature until uniform sol B is formed;
step 3, continuing stirring and aging at constant temperature until sol B forms a dry gel, adding water for dissolution, then loading into a reaction kettle, transferring to a homogeneous phase reactor, crystallizing for a long time under high-temperature oscillation condition, washing, filtering, drying and calcining to obtain a molecular sieve, and marking as Na-MOR;
step 4, adding Na-MOR catalyst into NH 4 And (3) stirring the mixture in a Cl solution at constant temperature, filtering, drying, repeating the steps for 2 to 4 times, and calcining to finally obtain the nano lotus leaf-shaped aluminum-rich mordenite molecular sieve which is named as H-MOR.
Further, in the step 1, the aluminum source is at least one of sodium metaaluminate, aluminum nitrate and aluminum chloride.
Further, in the step 1, the molar ratio of the raw materials in the solution A is that aluminum source, sodium hydroxide, water= (1.0-20): 10-100): 100-1000.
Further, the step 1 and the step 2 are carried out at the temperature of 40-80 ℃ and are vigorously stirred to ensure that the components are fully and uniformly mixed.
Further, in the step 2, the template agent is at least one of sodium hydroxide, tetraethylammonium hydroxide and tetraethylammonium bromide, the silicon source is at least one of water glass, silica sol and white carbon black, the aluminum-rich agent is at least one of 4-methylpiperidine, cyclohexane and homopiperazine, and the crystal growth inhibitor is at least one of polyethylene glycol, urea and ammonium bicarbonate.
Further, in the step 2, the raw material molar ratio of the sol B is silicon source, sodium hydroxide, water, template agent, aluminum-rich agent, crystal growth inhibitor= (1.0-5.0): (0.01-0.2): (0.1-1.0): (1.0-10): (0.1-1.0): (0.01-0.5).
Further, in the step 3, the constant temperature stirring temperature is 40-80 ℃, the aging time is 2-5 h, the mass ratio of the added water to the molecular sieve is (1.0-3.0) (0.1-1.0), the rotating speed of rotating and dissolving in a homogeneous phase reactor is 10-60 rpm, the temperature is 120-200 ℃, and the dissolving time is 60-80 h.
Further, in the step 3, the drying temperature is 100-120 ℃, the drying time is 8-12 h, the calcining temperature is 450-550 ℃ and the calcining time is 3-7 h.
Further, in the step 4, the concentration of ammonium chloride is 1.0-3.0 mol/L, the mass ratio of the added ammonium chloride aqueous solution to the molecular sieve is (1.0-5.0): (0.1-1.0), and the constant temperature stirring temperature is 60-80 ℃.
Further, in the step 4, the drying temperature is 100-120 ℃, the drying time is 2-5 h, the calcining temperature is 450-550 ℃ and the calcining time is 3-7 h.
The invention relates to a method for preparing acetic acid by methanol carbonylation, wherein a nano lotus leaf-shaped aluminum-rich mordenite molecular sieve is used.
Further, the molecular sieve catalyst may be reacted in any conventional manner, preferably using a fixed bed. The carbonylation reaction may be carried out by passing the reaction gas over a catalyst.
Further, the carbonylation reaction temperature is 200-350 ℃, the pressure of the carbonylation reaction is 0.1-10 MPa, and the space velocity of methanol gas feeding is 100-2000 mL.g -1 ·h -1 The molar ratio of carbon monoxide to methanol is 1.0-100.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the eight-membered ring aluminum-enriched MOR molecular sieve is synthesized by introducing the aluminum-enriched agent, the distribution of the acid sites of the molecular sieve is modulated from the synthesis point of view, and the aluminum content of the MOR eight-membered ring skeleton is improved through the size and repulsive force effect of the protonated aluminum-enriched agent.
(2) According to the invention, the crystal growth inhibitor is introduced, the thickness of the molecular sieve sheet layer is 10-100 nm by inhibiting the crystal growth in the MOR synthesis process, and the morphology of the molecular sieve sheet layer is shown to be lotus-like by SEM characterization.
(3) The mordenite molecular sieve catalyst provided by the invention has excellent catalytic performance for preparing acetic acid by methanol carbonylation, the methanol conversion rate is close to 100%, the selectivity of the acetic acid can reach more than 95%, and good stability can be maintained.
(4) The preparation process of the catalyst provided by the invention is simple and controllable, and the catalyst is easy to prepare in a further amplifying way. The catalyst has the advantages of simple preparation method, low cost and good industrial application prospect.
Drawings
FIG. 1 is an XRD spectrum of the MOR molecular sieve of examples 1-7;
FIG. 2 is an XRD spectrum of the MOR molecular sieves of example 1, comparative example 1 and comparative example 2;
FIG. 3 shows the IR spectrum and the peak separation results of the hydroxyl groups of example 1 and comparative example 1;
FIG. 4 is an SEM image of the MOR molecular sieve of example 1;
FIG. 5 is an SEM image of the MOR molecular sieve of comparative example 1;
FIG. 6 is an SEM image of the MOR molecular sieve of comparative example 2;
FIG. 7 is a methanol carbonylation lifetime graph of example 1.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and obvious, the invention is further described in detail below with reference to the accompanying drawings and embodiments.
Example 1
1.0g NaOH powder was weighed and added to 50mL deionized water to be dissolved sufficiently at a constant temperature of 40 ℃. Then accurately weigh 0.8g NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform transparent mixed solution AThe molar ratio of the raw materials in the liquid A is NaAlO 2 :NaOH:H 2 O=1.0:4.5:100, 0.8g NaOH powder, 18g silica sol (30% sio 2 ) 2.0g of 4-methylpiperidine and 0.5g of polyethylene glycol, and stirring vigorously at a constant temperature of 40 ℃ for 4 hours until a uniform sol B is formed, wherein the mol ratio of raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 O4-MPD (tetramethylpiperidine) polyethylene glycol=1.0:0.08:0.36:8.0:0.16:0.01, sol B is stirred continuously at constant temperature of 60 ℃ until dry gel is formed, 30ml of water is added for uniform dissolution, the mixture is put into a 200ml polytetrafluoroethylene reaction kettle and transferred into a homogeneous reactor, and the mixture is rotated at a rotating speed of 30r/min and crystallized at 120 ℃ for 50h. The resulting sample was filtered to neutrality using deionized water. Drying at 115 ℃ for 12 hours, then placing into a muffle furnace and calcining at 550 ℃ for 5 hours to obtain a Na-MOR catalyst, and placing 5.0g of Na-MOR catalyst into 250ml of NH with the concentration of 1.0mol/L 4 Stirring the mixture in Cl solution at 80 ℃ for 2 hours, filtering the mixture by using deionized water, drying the mixture at 115 ℃ for 2 hours, repeating the process for 2 times, and calcining the mixture in a muffle furnace at 550 ℃ for 5 hours to finally obtain the mordenite molecular sieve, wherein the silicon-aluminum ratio is 7.8, the XRD spectrogram is shown in the accompanying drawings 1 and 2, the hydroxyl infrared spectrogram and the peak separation result are shown in the accompanying drawings 3, the SEM is shown in the accompanying drawings 4, the thickness of a molecular sieve sheet is 10-100 nm, and the appearance is similar to a lotus leaf shape.
The reaction conditions of the catalyst for methanol carbonylation are as follows: the reaction temperature is 310 ℃, the reaction pressure is 5.0MPa, and the methanol gas feeding airspeed is 200 mL.g -1 ·h -1 The molar ratio of carbon monoxide to methanol was 45. The reaction raw materials and the products enter gas chromatography for on-line analysis through pipeline heat preservation. The specific catalytic reaction properties are shown in Table 1, and the methanol carbonylation lifetime is shown in FIG. 7.
Example 2
1.0g NaOH powder was weighed and added to 50mL deionized water to be dissolved sufficiently at a constant temperature of 40 ℃. Then accurately weigh 0.4g NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform and transparent mixed solution A, wherein the molar ratio of raw materials in the solution A is NaAlO 2 :NaOH:H 2 O=1.0:9.0:200, 0.8g NaOH powder, 18g silica sol (30% sio 2 ) 2.0g of 4-methylpiperidine and 0.5g of polyethylene glycol, while stirring vigorously at a constant temperature of 40℃for 4h until a homogeneous sol B is formed,the mol ratio of raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 O4-MPD (tetramethylpiperidine) polyethylene glycol=1.0:0.04:0.36:8.0:0.16:0.01, sol B is stirred continuously at constant temperature of 60 ℃ until dry gel is formed, 30ml of water is added for uniform dissolution, the mixture is put into a 200ml polytetrafluoroethylene reaction kettle and transferred into a homogeneous reactor, and the mixture is rotated at a rotating speed of 30r/min and crystallized at 120 ℃ for 50h. The resulting sample was filtered to neutrality using deionized water. Drying at 115 ℃ for 12 hours, then placing into a muffle furnace and calcining at 550 ℃ for 5 hours to obtain a Na-MOR catalyst, and placing 5.0g of Na-MOR catalyst into 250ml of NH with the concentration of 1.0mol/L 4 Stirring in Cl solution at 80deg.C for 2 hr, filtering with deionized water, drying at 115deg.C for 2 hr, repeating the process for 2 times, and calcining in muffle furnace at 550deg.C for 5 hr to obtain mordenite molecular sieve with silicon-aluminum ratio of 8.3, and XRD spectrum shown in figure 1.
The reaction conditions of the catalyst for methanol carbonylation are as follows: the reaction temperature is 310 ℃, the reaction pressure is 5.5MPa, and the space velocity of methanol gas feeding is 300mL g -1 ·h -1 The molar ratio of carbon monoxide to methanol was 38. The reaction raw materials and the products enter gas chromatography for on-line analysis through pipeline heat preservation. The specific catalytic reaction properties are listed in table 1.
Example 3
1.0g NaOH powder was weighed and added to 50mL deionized water to be dissolved sufficiently at a constant temperature of 40 ℃. Then accurately weigh 1.2g NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform and transparent mixed solution A, wherein the molar ratio of raw materials in the solution A is NaAlO 2 :NaOH:H 2 O=1.0:3.0:67, 0.8g NaOH powder, 18g silica sol (30% sio 2 ) 2.0g of 4-methylpiperidine and 0.5g of polyethylene glycol, and stirring vigorously at a constant temperature of 40 ℃ for 4 hours until a uniform sol B is formed, wherein the mol ratio of raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 O4-MPD (tetramethylpiperidine) polyethylene glycol=1.0:0.12:0.36:8.0:0.16:0.01, sol B is stirred continuously at constant temperature of 60 ℃ until dry gel is formed, 30ml of water is added for uniform dissolution, the mixture is put into a 200ml polytetrafluoroethylene reaction kettle and transferred into a homogeneous reactor, and the mixture is rotated at a rotating speed of 30r/min and crystallized at 120 ℃ for 50h. The resulting sample was filtered to neutrality using deionized water.Drying at 115 ℃ for 12 hours, then placing into a muffle furnace and calcining at 550 ℃ for 5 hours to obtain a Na-MOR catalyst, and placing 5.0g of Na-MOR catalyst into 250ml of NH with the concentration of 1.0mol/L 4 Stirring in Cl solution at 80deg.C for 2 hr, filtering with deionized water, drying at 115deg.C for 2 hr, repeating the process for 2 times, and calcining in muffle furnace at 550deg.C for 5 hr to obtain mordenite molecular sieve with silicon-aluminum ratio of 8.6, and XRD spectrum shown in figure 1.
The reaction conditions of the catalyst for methanol carbonylation are as follows: the reaction temperature is 250 ℃, the reaction pressure is 5.0MPa, and the space velocity of methanol gas feeding is 250mL g -1 ·h -1 The molar ratio of carbon monoxide to methanol was 34. The reaction raw materials and the products enter gas chromatography for on-line analysis through pipeline heat preservation. The specific catalytic reaction properties are listed in table 1.
Example 4
0.5g NaOH powder is weighed and added into 50mL deionized water to be fully dissolved at the constant temperature of 40 ℃. Then accurately weigh 0.8g NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform and transparent mixed solution A, wherein the molar ratio of raw materials in the solution A is NaAlO 2 :NaOH:H 2 O=1.0:2.3:100, 0.5g NaOH powder, 18g silica sol (30% sio 2 ) 2.0g of 4-methylpiperidine and 0.5g of polyethylene glycol, and stirring vigorously at a constant temperature of 40 ℃ for 4 hours until a uniform sol B is formed, wherein the mol ratio of raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 O4-MPD (tetramethylpiperidine) polyethylene glycol=1.0:0.08:0.20:8.0:0.16:0.01, sol B is stirred continuously at constant temperature of 60 ℃ until dry gel is formed, 30ml of water is added for uniform dissolution, the mixture is put into a 200ml polytetrafluoroethylene reaction kettle and transferred into a homogeneous reactor, and the mixture is rotated at a rotating speed of 30r/min and crystallized for 50h at 120 ℃. The resulting sample was filtered to neutrality using deionized water. Drying at 115 ℃ for 12 hours, then placing into a muffle furnace and calcining at 550 ℃ for 5 hours to obtain a Na-MOR catalyst, and placing 5.0g of Na-MOR catalyst into 250ml of NH with the concentration of 1.0mol/L 4 Stirring in Cl solution at 80deg.C for 2 hr, filtering with deionized water, drying at 115deg.C for 2 hr, repeating the process for 2 times, and calcining in muffle furnace at 550deg.C for 5 hr to obtain mordenite molecular sieve with silicon-aluminum ratio of 8.5, and XRD spectrum shown in figure 1.
The reaction conditions of the catalyst for methanol carbonylation are as follows: the reaction temperature is 280 ℃, the reaction pressure is 4.5MPa, and the methanol gas feeding airspeed is 300 mL.g -1 ·h -1 The volume ratio of carbon monoxide to methanol was 45. The reaction raw materials and the products enter gas chromatography for on-line analysis through pipeline heat preservation. The specific catalytic reaction properties are listed in table 1.
Example 5
1.5g NaOH powder was weighed and added to 50mL deionized water to be dissolved sufficiently at a constant temperature of 40 ℃. Then accurately weigh 0.8g NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform and transparent mixed solution A, wherein the molar ratio of raw materials in the solution A is NaAlO 2 :NaOH:H 2 O=1.0:4.5:100, 1.1g NaOH powder, 18g silica sol (30% sio 2 ) 2.0g of 4-methylpiperidine and 0.5g of polyethylene glycol, and stirring vigorously at a constant temperature of 40 ℃ for 4 hours until a uniform sol B is formed, wherein the mol ratio of raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 O4-MPD (tetramethylpiperidine) polyethylene glycol=1.0:0.08:0.52:8.0:0.16:0.01, sol B is stirred continuously at constant temperature of 60 ℃ until dry gel is formed, 30ml of water is added for uniform dissolution, the mixture is put into a 200ml polytetrafluoroethylene reaction kettle and transferred into a homogeneous reactor, and the mixture is rotated at a rotating speed of 30r/min and crystallized for 50h at 120 ℃. The resulting sample was filtered to neutrality using deionized water. Drying at 115 ℃ for 12 hours, then placing into a muffle furnace and calcining at 550 ℃ for 5 hours to obtain a Na-MOR catalyst, and placing 5.0g of Na-MOR catalyst into 250ml of NH with the concentration of 1.0mol/L 4 Stirring in Cl solution at 80deg.C for 2 hr, filtering with deionized water, drying at 115deg.C for 2 hr, repeating the process for 2 times, and calcining in muffle furnace at 550deg.C for 5 hr to obtain mordenite molecular sieve with silicon-aluminum ratio of 8.4, and XRD spectrum shown in figure 1.
The reaction conditions of the catalyst for methanol carbonylation are as follows: the reaction temperature is 350 ℃, the reaction pressure is 5.5MPa, and the methanol gas feeding airspeed is 200 mL.g -1 ·h -1 The molar ratio of carbon monoxide to methanol was 68. The reaction raw materials and the products enter gas chromatography for on-line analysis through pipeline heat preservation. The specific catalytic reaction properties are listed in table 1.
Example 6
1.0g NaOH powder was weighed and added to 50mL deionized water to be dissolved sufficiently at a constant temperature of 40 ℃. Then accurately weigh 0.8g NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform and transparent mixed solution A, wherein the molar ratio of raw materials in the solution A is NaAlO 2 :NaOH:H 2 O=1.0:4.5:100, 0.8g NaOH powder, 18g silica sol (30% sio 2 ) 1.5g of 4-methylpiperidine and 0.5g of polyethylene glycol, and stirring vigorously at a constant temperature of 40 ℃ for 4 hours until a uniform sol B is formed, wherein the mol ratio of raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 O4-MPD (tetramethylpiperidine) polyethylene glycol=1.0:0.08:0.36:8.0:0.12:0.01, sol B is stirred continuously at constant temperature of 60 ℃ until dry gel is formed, 30ml of water is added for uniform dissolution, the mixture is put into a 200ml polytetrafluoroethylene reaction kettle and transferred into a homogeneous reactor, and the mixture is rotated at a rotating speed of 30r/min and crystallized at 120 ℃ for 50h. The resulting sample was filtered to neutrality using deionized water. Drying at 115 ℃ for 12 hours, calcining at 550 ℃ for 5 hours in a muffle furnace to obtain a Na-MOR catalyst, placing 5.0g of the Na-MOR catalyst in 250ml of NH4Cl solution with the concentration of 1.0mol/L, stirring at 80 ℃ for 2 hours, filtering with deionized water, drying at 115 ℃ for 2 hours, repeating the process for 2 times, calcining at 550 ℃ for 5 hours in the muffle furnace, and finally obtaining the mordenite molecular sieve, wherein the silicon-aluminum ratio is determined to be 8.2, and the XRD spectrogram is shown in the attached figure 1.
The reaction conditions of the catalyst for methanol carbonylation are as follows: the reaction temperature is 280 ℃, the reaction pressure is 5.5MPa, and the methanol gas feeding airspeed is 300 mL.g -1 ·h -1 The molar ratio of carbon monoxide to methanol was 38. The reaction raw materials and the products enter gas chromatography for on-line analysis through pipeline heat preservation. The specific catalytic reaction properties are listed in table 1.
Example 7
1.0g NaOH powder was weighed and added to 50mL deionized water to be dissolved sufficiently at a constant temperature of 40 ℃. Then accurately weigh 0.8g NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform and transparent mixed solution A, wherein the molar ratio of raw materials in the solution A is NaAlO 2 :NaOH:H 2 O=1.0:4.5:100, 0.8g NaOH powder, 18g silica sol (30% sio 2 ) 2.5g of 4-methylpiperidine and 0.5g of polyethylene glycol, while stirring vigorously at a constant temperature of 40℃for 4h until a homogeneous sol B is formedThe mol ratio of the raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 O4-MPD (tetramethylpiperidine) polyethylene glycol=1.0:0.08:0.36:8.0:0.20:0.01, sol B is stirred continuously at constant temperature of 60 ℃ until dry gel is formed, 30ml of water is added for uniform dissolution, the mixture is put into a 200ml polytetrafluoroethylene reaction kettle and transferred into a homogeneous reactor, and the mixture is rotated at a rotating speed of 30r/min and crystallized at 120 ℃ for 50h. The resulting sample was filtered to neutrality using deionized water. Drying at 115 ℃ for 12 hours, then placing into a muffle furnace and calcining at 550 ℃ for 5 hours to obtain a Na-MOR catalyst, and placing 5.0g of Na-MOR catalyst into 250ml of NH with the concentration of 1.0mol/L 4 Stirring in Cl solution at 80deg.C for 2 hr, filtering with deionized water, drying at 115deg.C for 2 hr, repeating the process for 2 times, and calcining in muffle furnace at 550deg.C for 5 hr to obtain mordenite molecular sieve with silicon-aluminum ratio of 8.3, and XRD spectrum shown in figure 1.
The reaction conditions of the catalyst for methanol carbonylation are as follows: the reaction temperature is 310 ℃, the reaction pressure is 4.5MPa, and the methanol gas feeding airspeed is 230 mL.g -1 ·h -1 The molar ratio of carbon monoxide to methanol was 45. The reaction raw materials and the products enter gas chromatography for on-line analysis through pipeline heat preservation. The specific catalytic reaction properties are listed in table 1.
Comparative example 1
1.0g NaOH powder was weighed and added to 50mL deionized water to be dissolved sufficiently at a constant temperature of 40 ℃. Then accurately weigh 0.8g NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform and transparent mixed solution A, wherein the molar ratio of raw materials in the solution A is NaAlO 2 :NaOH:H 2 O=1.0:4.5:100, 0.8g NaOH powder, 18g silica sol (30% sio 2 ) Simultaneously stirring vigorously at a constant temperature of 40 ℃ for 4 hours to form uniform sol B, wherein the mol ratio of raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 O=1.0:0.08:0.36:8.0 sol B was charged into a 200ml polytetrafluoroethylene reactor and transferred to a homogeneous reactor, rotated at 30r/min and crystallized at 120 ℃ for 50h. The resulting sample was filtered to neutrality using deionized water. Drying at 115 ℃ for 12 hours, then placing into a muffle furnace and calcining at 550 ℃ for 5 hours to obtain a Na-MOR catalyst, and placing 5.0g of Na-MOR catalyst into 250ml of NH with the concentration of 1.0mol/L 4 In Cl solutionStirring at 80deg.C for 2 hr, filtering with deionized water, drying at 115deg.C for 2 hr, repeating the process for 2 times, calcining at 550deg.C for 5 hr in a muffle furnace to obtain mordenite molecular sieve, and measuring to obtain silicon-aluminum ratio of 11.2, wherein XRD spectrum is shown in figure 2, hydroxyl infrared spectrum and peak separation result are shown in figure 3, and SEM is shown in figure 5.
The reaction conditions of the catalyst for methanol carbonylation are as follows: the reaction temperature is 310 ℃, the reaction pressure is 5.0MPa, and the methanol gas feeding airspeed is 200 mL.g -1 ·h -1 The molar ratio of carbon monoxide to methanol was 45. The reaction raw materials and the products enter gas chromatography for on-line analysis through pipeline heat preservation. The specific catalytic reaction properties are listed in table 1.
Comparative example 2
1.0g NaOH powder was weighed and added to 50mL deionized water to be dissolved sufficiently at a constant temperature of 40 ℃. Then accurately weigh 0.8g NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform and transparent mixed solution A, wherein the molar ratio of raw materials in the solution A is NaAlO 2 :NaOH:H 2 O=1.0:4.5:100, 0.8g NaOH powder, 18g silica sol (30% sio 2 ) 2.5g of 4-methylpiperidine are stirred vigorously at a constant temperature of 40 ℃ for 4 hours until a uniform sol B is formed, wherein the molar ratio of the raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 O4-MPD (tetramethylpiperidine) =1.0:0.08:0.36:8.0:0.16 sol B was charged into a 200ml polytetrafluoroethylene reactor and transferred to a homogeneous reactor, rotated at 30r/min and crystallized at 120℃for 50h. The resulting sample was filtered to neutrality using deionized water. Drying at 115 ℃ for 12 hours, then placing into a muffle furnace and calcining at 550 ℃ for 5 hours to obtain a Na-MOR catalyst, and placing 5.0g of Na-MOR catalyst into 250ml of NH with the concentration of 1.0mol/L 4 Stirring in Cl solution at 80deg.C for 2 hr, filtering with deionized water, drying at 115deg.C for 2 hr, repeating the process for 2 times, and calcining in muffle furnace at 550deg.C for 5 hr to obtain mordenite molecular sieve with silicon-aluminum ratio of 9.8, XRD spectrum shown in figure 2, and SEM shown in figure 6.
The reaction conditions of the catalyst for methanol carbonylation are as follows: the reaction temperature is 310 ℃, the reaction pressure is 5.0MPa, and the methanol gas feeding airspeed is 200 mL.g -1 ·h -1 Carbon monoxide and methanolThe molar ratio of (2) was 45. The reaction raw materials and the products enter gas chromatography for on-line analysis through pipeline heat preservation. The specific catalytic reaction properties are listed in table 1.
TABLE 1 evaluation results of catalyst Performance
According to the invention, the eight-membered cyclic aluminum-rich MOR molecular sieve is synthesized by introducing the aluminum-rich agent, the distribution of acid sites of the molecular sieve is modulated from the synthesis point of view, and the aluminum content of the molecular sieve is improved by measuring the silicon-aluminum ratio of the molecular sieve and adding the aluminum-rich agent. And by combining a hydroxyl infrared spectrogram and a peak separation result, the aluminum-rich agent can be known to realize the remarkable improvement of the aluminum content of the eight-membered ring skeleton in the MOR. When the molecular sieve is synthesized, the crystal growth inhibitor is added, so that the crystal growth can be obviously inhibited, the molecular sieve with a certain dimension of nano-scale and another dimension of micro-scale is synthesized, the high crystallinity can be ensured, the channel length of the molecular sieve can be effectively shortened, the diffusion capacity is improved, the catalytic performance is further improved, and the morphology of the molecular sieve is similar to that of lotus leaf. The molecular sieve catalyst of the invention is subjected to methanol carbonylation performance test, and the result shows that the molecular sieve catalyst has excellent catalytic performance for preparing acetic acid by methanol carbonylation and can maintain good stability.
Claims (9)
1. A nano lotus leaf-shaped aluminum-rich mordenite molecular sieve is characterized in that: the morphology of the molecular sieve is in a nano lotus leaf shape, the thickness of a sheet layer is 10-100 nm, the eight-membered ring skeleton is rich in aluminum, and the silicon-aluminum ratio is 7-10;
the preparation method of the nano lotus leaf-shaped aluminum-rich mordenite molecular sieve comprises the following steps:
1) Adding an aluminum source into an NaOH aqueous solution, and stirring and dissolving to obtain a solution A;
2) Sequentially adding a template agent, a silicon source, an aluminum-rich agent and a crystal growth inhibitor into the solution A, and stirring to form sol B; the aluminum-rich agent is at least one of 4-methylpiperidine, cyclohexane and homopiperazine, and the crystal growth inhibitor is at least one of polyethylene glycol, urea and ammonium bicarbonate; the raw material molar ratio of the sol B is a silicon source, a sodium hydroxide, a template agent, an aluminum-rich agent and a crystal growth inhibitor= (1.0-5.0): (0.01-0.2): (0.1-1.0): (1.0-10): (0.1-1.0): (0.01-0.5);
3) Continuously stirring until sol B forms a dry gel, adding water to dissolve, loading into a reaction kettle, transferring to a homogeneous phase reactor, crystallizing and growing under high-temperature oscillation condition, washing, filtering, drying and calcining to obtain a molecular sieve, namely Na-MOR;
4) Adding Na-MOR into ammonium chloride aqueous solution, stirring, filtering, drying, and calcining to obtain the nano lotus leaf-shaped aluminum-rich mordenite molecular sieve.
2. A nano lotus leaf shaped aluminum enriched mordenite molecular sieve as set forth in claim 1, characterized in that: in the step 1), the aluminum source is at least one of sodium metaaluminate, aluminum nitrate and aluminum chloride.
3. A nano lotus leaf shaped aluminum enriched mordenite molecular sieve as set forth in claim 1, characterized in that: in the step 1), the stirring temperature is 40-80 ℃, and the molar ratio of the raw materials in the solution A is aluminum source, sodium hydroxide and water= (1.0-20): (10-100): (100-1000).
4. A nano lotus leaf shaped aluminum enriched mordenite molecular sieve as set forth in claim 1, characterized in that: in the step 2), the template agent is at least one of sodium hydroxide, tetraethylammonium hydroxide and tetraethylammonium bromide, and the silicon source is at least one of water glass, silica sol and white carbon black.
5. A nano lotus leaf shaped aluminum enriched mordenite molecular sieve as set forth in claim 1, characterized in that: in the step 2), the stirring temperature is 40-80 ℃.
6. A nano lotus leaf shaped aluminum enriched mordenite molecular sieve as set forth in claim 1, characterized in that: in the step 3), the stirring temperature is 40-80 ℃, the mass ratio of water to molecular sieve is (1.0-3.0), the rotating speed of rotation in the homogeneous phase reactor is 10-60 rpm, the temperature is 120-200 ℃, and the time is 60-80 h.
7. A nano lotus leaf shaped aluminum enriched mordenite molecular sieve as set forth in claim 1, characterized in that: in the step 4), the concentration of the ammonium chloride aqueous solution is 1.0-3.0 mol/L, the mass ratio of the added ammonium chloride aqueous solution to the molecular sieve is (1.0-5.0), the stirring temperature is 60-80 ℃, the drying temperature is 100-120 ℃, the drying time is 2-5 h, the calcining temperature is 450-550 ℃, and the calcining time is 3-7 h.
8. The application of the nano lotus leaf-shaped aluminum-rich mordenite molecular sieve as set forth in any one of claims 1 to 7, which is characterized in that: is used for preparing acetic acid by methanol carbonylation reaction.
9. Use according to claim 8, characterized in that the conditions of the methanol carbonylation reaction are as follows: the temperature is 200-350 ℃, the pressure is 0.1-10 MPa, and the methanol gas feeding airspeed is 100-2000 mL g -1 ·h -1 The molar ratio of carbon monoxide to methanol is 1.0-100.
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