CN115536040A - Nano lotus leaf-shaped aluminum-rich mordenite molecular sieve, and synthesis method and application thereof - Google Patents
Nano lotus leaf-shaped aluminum-rich mordenite molecular sieve, and synthesis method and application thereof Download PDFInfo
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Abstract
A nano lotus leaf-shaped aluminum-rich mordenite molecular sieve, a synthesis method and an application thereof are disclosed, wherein the preparation method of the zeolite molecular sieve comprises the following steps: adding an aluminum source into a NaOH solution, and uniformly mixing to obtain a solution A; then sequentially adding a template agent, a silicon source, an aluminum-rich agent and a crystal growth inhibitor into the solution A and stirring until uniform sol B is formed; finally, stirring the sol B until the sol B is dry gel-shaped, adding water, transferring the dry gel-shaped to a reaction kettle, and forming uniform and stable gel under the condition of high-temperature oscillation; washing, filtering, drying, roasting, ammonia exchange and roasting to obtain the nano lotus leaf-shaped aluminum-rich MOR molecular sieve with the lamella thickness of 10-100 nm. The catalyst is used for methanol carbonylation reaction, has the characteristic of high acetic acid selectivity, is simple in preparation process and low in cost, and has a good application prospect.
Description
Technical Field
The invention belongs to a zeolite molecular sieve and synthesis and application thereof in the field of catalysis, and particularly relates to a synthesis method of a nano lotus leaf-shaped aluminum-rich mordenite molecular sieve and application thereof in carbonylation reaction.
Background
As an important bulk chemical product, acetic acid is widely applied to the fields of solvents, synthetic coatings, spices, foods, medicines and the like, and downstream products comprise methyl acetate, ethanol, acetic anhydride acetone, polyvinyl acetate and the like. Currently, acetic acid is industrially prepared mainly by a methanol homogeneous carbonylation process (j.cat., 1972,27, 389-396), and the process route contributes 70% of the current production of acetic acid, but the problems that the main catalysts Ir and Rh are expensive, the auxiliary catalyst iodide seriously corrodes equipment, a large amount of water exists in a reaction system, and the product separation is difficult are caused. Therefore, the research on the synthesis of acetic acid by methanol heterogeneous carbonylation has attracted much attention in recent years. Vine et al (angew. Chem. Int.ed.,2006, 45. However, the stability of methanol carbonylation by MOR molecular sieves is still insufficient, the performance is difficult to maintain for over 100 hours, and the desired CO/CH is still present 3 The OH is higher and the performance needs to be further improved.
Research shows that the catalytic active sites of the MOR molecular sieve are mainly distributed on aluminum sites inside a pore channel, so that besides the acidic characteristic, the special pore channel and side pockets formed by the mutual connection among the pore channels of the molecular sieve play a decisive role in the generation of reaction intermediate products and the trend of a reaction path; the long and narrow channels of the molecular sieve are not beneficial to the diffusion of reactant and product molecules, even the length of the channels in the order of several microns can cause the generation of a large amount of aggregation or secondary reaction of the product molecules to cause the rapid increase of the carbon deposition rate, so that the molecular sieve is rapidly inactivated, and the selectivity of a target product is rapidly reduced. Researches show that the diffusion of substances can be enhanced by creating a hierarchical pore molecular sieve containing both mesopores and micropores and enlarging the pore size of the molecular sieve, or the diffusion of substances can be enhanced by synthesizing a nanoscale molecular sieve with a certain regular morphology and shortening the pore length of the molecular sieve, so that the catalytic performance of the catalyst can be improved. Research shows that a hierarchical-level molecular sieve can be synthesized by dealumination or desiliconization through acid treatment or alkali treatment, but the method is easy to collapse the pore channels of the molecular sieve, so that the performance of the catalyst 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 nano lotus leaf-shaped aluminum-rich mordenite molecular sieve disclosed by the invention is in a nano lotus leaf shape, the lamella thickness 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 purpose, the invention adopts the following scheme:
step 3, continuously stirring and aging at constant temperature until the sol B forms a dry gel state, adding water to dissolve the sol B, then putting the sol B into a reaction kettle, transferring the sol B into a homogeneous reactor, crystallizing at high temperature under the condition of oscillation, washing, filtering, drying and calcining to obtain a molecular sieve, and marking the molecular sieve as Na-MOR;
step 4, adding the Na-MOR catalyst into NH 4 And (3) stirring at constant temperature in a Cl solution, filtering, drying, repeating the steps for 2-4 times, and calcining to finally obtain the nano lotus leaf-shaped aluminum-rich mordenite molecular sieve which is marked 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 aluminum source, sodium hydroxide and water = (1.0-20): (10-100): (100-1000).
Further, the step 1 and the step 2 are both carried out at 40-80 ℃, and the components are fully and uniformly mixed by violent stirring.
Further, in the step 2, the template agent is at least one of sodium hydroxide, tetraethyl ammonium hydroxide and tetraethyl ammonium 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, cyclohexylamine and homopiperazine, and the crystal growth inhibitor is at least one of polyethylene glycol, urea and ammonium bicarbonate.
Further, in the step 2, the molar ratio of the raw materials in the sol B is silicon source, aluminum 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), (0.01-1.0) and (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 ratio of the mass of the added water to the mass of the molecular sieve is (1.0-3.0) to (0.1-1.0), the rotating speed of the rotary dissolution in the homogeneous reactor is 10-60 rpm, the temperature is 120-200 ℃, and the dissolution 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 the ammonium chloride is 1.0-3.0 mol/L, the ratio of the mass of the added ammonium chloride aqueous solution to the mass of the molecular sieve is (1.0-5.0): (0.1-1.0), and the 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 the 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 gases over a catalyst.
Further, the temperature of the carbonylation reaction 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) The invention introduces the aluminum-rich agent to synthesize the MOR molecular sieve rich in eight-membered ring aluminum, modulates the distribution of acid sites of the molecular sieve from the synthesis angle, and realizes the improvement of the aluminum content of the MOR eight-membered ring framework through the size and repulsion after the protonation of the aluminum-rich agent.
(2) The invention introduces a crystal growth inhibitor, the thickness of a molecular sieve sheet layer is 10-100 nm by inhibiting the crystal growth in the MOR synthesis process, and the appearance of the molecular sieve sheet layer is shown to be lotus leaf-like by SEM representation.
(3) The mordenite molecular sieve catalyst provided by the invention has excellent catalytic performance for preparing acetic acid by methanol carbonylation, the conversion rate of methanol is close to 100%, the selectivity of 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 further amplify and prepare. 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 sieves 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 hydroxyl group infrared spectra and the peak separation results of example 1 and comparative example 1;
FIG. 4 is an SEM picture of the MOR molecular sieve of example 1;
FIG. 5 is an SEM picture of a MOR molecular sieve of comparative example 1;
FIG. 6 is an SEM picture of a MOR molecular sieve of comparative example 2;
FIG. 7 is a graph of methanol carbonylation lifetime for example 1.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects of the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.
Example 1
1.0g of NaOH powder was weighed and added to 50mL of deionized water and dissolved sufficiently at a constant temperature of 40 ℃. Then accurately weighing 0.8g of NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform and transparent mixed solution A, wherein the molar ratio of the raw materials in the solution A is NaAlO 2 :NaOH:H 2 O =1.0 2 ) 2.0g of 4-methylpiperidine and 0.5g of polyethylene glycol, and stirring vigorously at the constant temperature of 40 ℃ for 4 hours to form uniform sol B, wherein the molar ratio of the raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 4-MPD (tetramethylpiperidine): polyethylene glycol = 1.0. The resulting sample was filtered to neutrality using deionized water. Drying at 115 deg.C for 12h, calcining in muffle furnace at 550 deg.C for 5h to obtain Na-MOR catalyst, adding 5.0g Na-MOR catalyst into 250ml NH with concentration of 1.0mol/L 4 Stirring the Cl solution at 80 ℃ for 2h, filtering the solution by using deionized water, drying the solution at 115 ℃ for 2h, repeating the process for 2 times, calcining the solution in a muffle furnace at 550 ℃ for 5h to finally obtain the mordenite molecular sieve, determining the silicon-aluminum ratio of the mordenite molecular sieve to be 7.8, wherein an XRD (X-ray diffraction) spectrogram is shown in an attached figure 1 and an attached figure 2, a hydroxyl infrared spectrogram and a peak separation result are shown in an attached figure 3, an SEM (scanning electron microscope) is shown in an attached figure 4, the thickness of a molecular sieve sheet layer is 10-100 nm, and the morphology 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 space velocity of methanol gas feeding is 200mL g -1 ·h -1 The molar ratio of carbon monoxide to methanol was 45.The reaction raw materials and products enter a gas chromatography for on-line analysis through pipeline heat preservation. The specific catalytic reaction performance is shown in Table 1, and the methanol carbonylation life is shown in figure 7.
Example 2
1.0g of NaOH powder was weighed and added to 50mL of deionized water and dissolved sufficiently at a constant temperature of 40 ℃. Then accurately weighing 0.4g of NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform and transparent mixed solution A, wherein the molar ratio of the raw materials in the solution A is NaAlO 2 :NaOH:H 2 O =1.0, 9.0, 0.8g of NaOH powder, 18g of silica sol (30% sio) 2 ) 2.0g of 4-methylpiperidine and 0.5g of polyethylene glycol, and stirring vigorously at the constant temperature of 40 ℃ for 4 hours to form uniform sol B, wherein the molar ratio of the raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 4-MPD (tetramethylpiperidine): polyethylene glycol = 1.0. The resulting sample was filtered to neutrality using deionized water. Drying at 115 deg.C for 12h, calcining in muffle furnace at 550 deg.C for 5h to obtain Na-MOR catalyst, adding 5.0g Na-MOR catalyst into 250ml NH with concentration of 1.0mol/L 4 Stirring Cl solution at 80 deg.C for 2h, filtering with deionized water, drying at 115 deg.C for 2h, repeating the process for 2 times, calcining in muffle furnace at 550 deg.C for 5h to obtain mordenite molecular sieve with Si/Al ratio of 8.3, and XRD spectrogram 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 products enter a gas chromatography for on-line analysis through pipeline heat preservation. Specific catalytic reaction properties are listed in table 1.
Example 3
1.0g of NaOH powder was weighed and added to 50mL of deionized water and dissolved sufficiently at a constant temperature of 40 ℃. Then accurately weighing 1.2g of NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform and transparent mixed solutionThe raw material molar ratio of the solution A is NaAlO 2 :NaOH:H 2 O =1.0, 3.0, naOH powder 0.8g, silica sol 18g (30% sio) 2 ) 2.0g of 4-methylpiperidine and 0.5g of polyethylene glycol, and stirring vigorously at the constant temperature of 40 ℃ for 4 hours to form uniform sol B, wherein the molar ratio of the raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 4-MPD (tetramethylpiperidine): polyethylene glycol = 1.0. The resulting sample was filtered to neutrality using deionized water. Drying at 115 deg.C for 12h, calcining in muffle furnace at 550 deg.C for 5h to obtain Na-MOR catalyst, adding 5.0g Na-MOR catalyst into 250ml NH with concentration of 1.0mol/L 4 Stirring Cl solution at 80 deg.C for 2h, filtering with deionized water, drying at 115 deg.C for 2h, repeating the process for 2 times, calcining in muffle furnace at 550 deg.C for 5h to obtain mordenite molecular sieve, determining its Si/Al ratio to be 8.6, and its XRD spectrogram is 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 feeding space velocity of the methanol gas is 250mL g -1 ·h -1 The molar ratio of carbon monoxide to methanol was 34. The reaction raw materials and products enter a gas chromatography for on-line analysis through pipeline heat preservation. Specific catalytic reaction properties are listed in table 1.
Example 4
0.5g of NaOH powder was weighed and added to 50mL of deionized water to be dissolved sufficiently at a constant temperature of 40 ℃. Then accurately weighing 0.8g of NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform and transparent mixed solution A, wherein the molar ratio of the 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 the constant temperature of 40 ℃ for 4 hours to form uniform sol B, wherein the molar ratio of the raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 4-MPD (tetramethylpiperidine): polyethylene glycol =1.0Stirring at constant temperature of 60 deg.C to form dry gel, adding 30ml water, dissolving, placing into 200ml polytetrafluoroethylene reaction kettle, transferring into homogeneous reactor, rotating at 30r/min, and crystallizing at 120 deg.C for 50h. The resulting sample was filtered to neutrality using deionized water. Drying at 115 deg.C for 12h, calcining in muffle furnace at 550 deg.C for 5h to obtain Na-MOR catalyst, adding 5.0g Na-MOR catalyst into 250ml NH with concentration of 1.0mol/L 4 Stirring Cl solution at 80 deg.C for 2h, filtering with deionized water, drying at 115 deg.C for 2h, repeating the process for 2 times, calcining in muffle furnace at 550 deg.C for 5h to obtain mordenite molecular sieve, determining its Si/Al ratio to be 8.5, and its XRD spectrogram is 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 feeding space velocity of the methanol gas is 300mL g -1 ·h -1 The volume ratio of carbon monoxide to methanol was 45. The reaction raw materials and products enter a gas chromatography for on-line analysis through pipeline heat preservation. Specific catalytic reaction properties are listed in table 1.
Example 5
1.5g of NaOH powder is weighed and added into 50mL of deionized water to be fully dissolved at a constant temperature of 40 ℃. Then accurately weighing 0.8g of NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform and transparent mixed solution A, wherein the molar ratio of the raw materials in the solution A is NaAlO 2 :NaOH:H 2 O =1.0 2 ) 2.0g of 4-methylpiperidine and 0.5g of polyethylene glycol, and stirring vigorously at the constant temperature of 40 ℃ for 4 hours to form uniform sol B, wherein the molar ratio of the raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 O:4-MPD (tetramethylpiperidine): polyethylene glycol =1.0: 0.08. The resulting sample was filtered to neutrality using deionized water. Drying at 115 deg.C for 12h, calcining in muffle furnace at 550 deg.C for 5h to obtain Na-MOR catalyst, adding 5.0g Na-MOR catalyst into 250ml NH with concentration of 1.0mol/L 4 Cl solutionStirring at 80 deg.C for 2h, filtering with deionized water, drying at 115 deg.C for 2h, repeating the process for 2 times, calcining in muffle furnace at 550 deg.C for 5h to obtain mordenite molecular sieve with silicon-aluminum ratio of 8.4, and XRD spectrogram 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 feeding space velocity of the methanol gas is 200mL g -1 ·h -1 The molar ratio of carbon monoxide to methanol was 68. The reaction raw materials and products enter a gas chromatography for on-line analysis through pipeline heat preservation. Specific catalytic reaction properties are listed in table 1.
Example 6
1.0g of NaOH powder was weighed and added to 50mL of deionized water and dissolved sufficiently at a constant temperature of 40 ℃. Then accurately weighing 0.8g of NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform and transparent mixed solution A, wherein the molar ratio of the raw materials in the solution A is NaAlO 2 :NaOH:H 2 O =1.0 2 ) 1.5g of 4-methylpiperidine and 0.5g of polyethylene glycol, and stirring vigorously at the constant temperature of 40 ℃ for 4 hours to form uniform sol B, wherein the molar ratio of the raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 4-MPD (tetramethylpiperidine): polyethylene glycol = 1.0. The resulting sample was filtered to neutrality using deionized water. Drying at 115 ℃ for 12h, then placing the dried product into a muffle furnace to calcine the dried product at 550 ℃ for 5h to obtain a Na-MOR catalyst, placing 5.0g of the Na-MOR catalyst into 250ml of NH4Cl solution with the concentration of 1.0mol/L, stirring the solution at 80 ℃ for 2h, filtering the solution by using deionized water, drying the solution at 115 ℃ for 2h, repeating the process for 2 times, then placing the dried product into the muffle furnace to calcine the product at 550 ℃ for 5h to finally obtain the mordenite molecular sieve, and determining the silicon-aluminum ratio of the mordenite molecular sieve to be 8.2, wherein the XRD spectrogram of the mordenite molecular sieve is shown in an 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 feeding space velocity of the methanol gas is 300mL g -1 ·h -1 The molar ratio of carbon monoxide to methanol was 38. The reaction raw materials and products enter a gas chromatography for on-line analysis through pipeline heat preservation. Specific catalytic reaction properties are listed in table 1.
Example 7
1.0g of NaOH powder was weighed and added to 50mL of deionized water and dissolved sufficiently at a constant temperature of 40 ℃. Then accurately weighing 0.8g of NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform and transparent mixed solution A, wherein the molar ratio of the raw materials in the solution A is NaAlO 2 :NaOH:H 2 O =1.0 2 ) 2.5g of 4-methylpiperidine and 0.5g of polyethylene glycol, and stirring vigorously at the constant temperature of 40 ℃ for 4 hours to form uniform sol B, wherein the molar ratio of the raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 4-MPD (tetramethylpiperidine): polyethylene glycol = 1.0. The resulting sample was filtered to neutrality using deionized water. Drying at 115 deg.C for 12h, calcining in muffle furnace at 550 deg.C for 5h to obtain Na-MOR catalyst, adding 5.0g Na-MOR catalyst into 250ml NH with concentration of 1.0mol/L 4 Stirring Cl solution at 80 deg.C for 2h, filtering with deionized water, drying at 115 deg.C for 2h, repeating the process for 2 times, calcining in muffle furnace at 550 deg.C for 5h to obtain mordenite molecular sieve with Si/Al ratio of 8.3, and XRD spectrogram 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 space velocity of methanol gas feeding is 230mL g -1 ·h -1 The molar ratio of carbon monoxide to methanol was 45. The reaction raw materials and products enter a gas chromatography for on-line analysis through pipeline heat preservation. Specific catalytic reaction properties are listed in table 1.
Comparative example 1
1.0g of NaOH powder was weighed and added to 50mL of deionized water and dissolved sufficiently at a constant temperature of 40 ℃. Then accurately weighing 0.8g of NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform and transparent mixtureMixing the solution A, wherein the raw material molar ratio in the solution A is NaAlO 2 :NaOH:H 2 O =1.0 2 ) And at the same time, keeping the temperature at 40 ℃ and violently stirring for 4 hours until uniform sol B is formed, wherein the molar ratio of raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 O =1.0, 0.08. The resulting sample was filtered to neutrality using deionized water. Drying at 115 deg.C for 12h, calcining at 550 deg.C for 5h in muffle furnace to obtain Na-MOR catalyst, adding 5.0g of Na-MOR catalyst into 250ml of NH with concentration of 1.0mol/L 4 Stirring Cl solution at 80 deg.C for 2h, filtering with deionized water, drying at 115 deg.C for 2h, repeating the process for 2 times, calcining in muffle furnace at 550 deg.C for 5h to obtain mordenite molecular sieve with silicon-aluminum ratio of 11.2, XRD (shown in figure 2), hydroxyl infrared spectrum and peak separation result in figure 3, and SEM 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 space velocity of methanol gas feeding is 200mL g -1 ·h -1 The molar ratio of carbon monoxide to methanol was 45. The reaction raw materials and products enter a gas chromatography for on-line analysis through pipeline heat preservation. Specific catalytic reaction properties are listed in table 1.
Comparative example 2
1.0g of NaOH powder was weighed and added to 50mL of deionized water and dissolved sufficiently at a constant temperature of 40 ℃. Then accurately weighing 0.8g of NaAlO 2 Dissolving the powder in NaOH solution to obtain uniform and transparent mixed solution A, wherein the molar ratio of the raw materials in the solution A is NaAlO 2 :NaOH:H 2 O =1.0 2 ) 2.5g of 4-methylpiperidine, and stirring vigorously at the constant temperature of 40 ℃ for 4 hours to form uniform sol B, wherein the molar ratio of the raw materials in the sol B is SiO 2 :NaAlO 2 :NaOH:H 2 O4-MPD (tetramethylpiperidine) = 1.0.08. The sample obtainedThe product was filtered to neutrality using deionized water. Drying at 115 deg.C for 12h, calcining in muffle furnace at 550 deg.C for 5h to obtain Na-MOR catalyst, adding 5.0g Na-MOR catalyst into 250ml NH with concentration of 1.0mol/L 4 Stirring Cl solution at 80 deg.C for 2h, filtering with deionized water, drying at 115 deg.C for 2h, repeating the process for 2 times, calcining in muffle furnace at 550 deg.C for 5h to obtain mordenite molecular sieve with silicon-aluminum ratio of 9.8, and XRD spectrogram and SEM of figure 2 and 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 space velocity of methanol gas feeding is 200 mL/g -1 ·h -1 The molar ratio of carbon monoxide to methanol was 45. The reaction raw materials and products enter a gas chromatography for on-line analysis through pipeline heat preservation. Specific catalytic reaction properties are listed in table 1.
TABLE 1 evaluation results of catalyst Properties
The aluminum-rich agent is introduced to synthesize the eight-membered ring aluminum-rich MOR molecular sieve, from the synthesis angle, the distribution of acid sites of the molecular sieve is modulated, and the silicon-aluminum ratio of the molecular sieve is determined, so that after the aluminum-rich agent is added, the silicon-aluminum ratio of the MOR molecular sieve is obviously reduced, namely, the aluminum content of the molecular sieve is improved. And by combining a hydroxyl infrared spectrogram and a peak separation result, the aluminum-rich agent realizes the remarkable improvement of the aluminum content of the eight-membered ring framework in MOR. The crystal growth inhibitor is added during the synthesis of the molecular sieve, so that the crystal growth can be obviously inhibited, the molecular sieve with one dimension of nanometer and the other dimension of micron can be synthesized, the high crystallinity can be ensured, the length of the pore channel of the molecular sieve can be effectively shortened, the diffusion capability is improved, the catalytic performance is improved, and the appearance of the molecular sieve is exactly like a lotus leaf. The molecular sieve catalyst has excellent catalytic performance for preparing acetic acid by methanol carbonylation and can maintain good stability.
Claims (10)
1. A nano lotus leaf-shaped aluminum-rich mordenite molecular sieve is characterized in that: the molecular sieve is in a nano lotus leaf shape, the thickness of a lamella is 10-100 nm, the eight-membered ring framework is rich in aluminum, and the silicon-aluminum ratio is 7-10.
2. The preparation method of the nano lotus leaf-shaped aluminum-rich mordenite molecular sieve of claim 1, which is characterized by comprising the following steps of:
1) Adding an aluminum source into a 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;
3) Continuously stirring until the sol B forms a dry gel state, adding water to dissolve the sol B, then putting the sol B into a reaction kettle, transferring the sol B into a homogeneous reactor to perform crystallization growth under the condition of high-temperature oscillation, and obtaining a molecular sieve which is marked as Na-MOR after washing, filtering, drying and calcining;
4) Adding Na-MOR into an ammonium chloride aqueous solution, stirring, filtering, drying, and calcining to obtain the nano lotus leaf-shaped aluminum-rich mordenite molecular sieve.
3. The method for preparing the nano lotus leaf-shaped aluminum-rich mordenite molecular sieve as claimed in claim 2, which is characterized in that: in the step 1), the aluminum source is at least one of sodium metaaluminate, aluminum nitrate and aluminum chloride.
4. The method for preparing the nano lotus leaf-shaped aluminum-rich mordenite molecular sieve as claimed in claim 2, which is 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) and (100-1000).
5. The method for preparing the nano lotus leaf-shaped aluminum-rich mordenite molecular sieve as claimed in claim 2, which is characterized in that: 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, cyclohexylamine and homopiperazine, and the crystal growth inhibitor is at least one of polyethylene glycol, urea and ammonium bicarbonate.
6. The method for preparing the nano lotus leaf-shaped aluminum-rich mordenite molecular sieve as claimed in claim 2, which is characterized in that: in the step 2), the stirring temperature is 40-80 ℃, and the molar ratio of the raw materials in the sol B is silicon source, aluminum source, sodium hydroxide, water, template agent, aluminum-rich agent and crystal growth inhibitor = (1.0-5.0), (0.01-0.2), (0.1-1.0), (1.0-10), (0.1-1.0), (0.01-1.0) and (0.01-0.5).
7. The method for preparing the nano lotus leaf-shaped aluminum-rich mordenite molecular sieve as claimed in claim 2, which is characterized in that: in the step 3), the stirring temperature is 40-80 ℃, the ratio of the mass of the added water to the mass of the molecular sieve is (1.0-3.0) to (0.1-1.0), the rotating speed in the homogeneous reactor is 10-60 rpm, the temperature is 120-200 ℃, and the time is 60-80 h.
8. The method for preparing the nano lotus-shaped aluminum-rich mordenite molecular sieve as claimed in claim 2, which is characterized in that: in the step 4), the concentration of the ammonium chloride aqueous solution is 1.0-3.0 mol/L, the ratio of the mass of the added ammonium chloride aqueous solution to the mass of the molecular sieve is (1.0-5.0) to (0.1-1.0), 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.
9. The application of the nano lotus leaf-shaped aluminum-rich mordenite molecular sieve of claim 1 and the nano lotus leaf-shaped aluminum-rich mordenite molecular sieve prepared by the preparation method of any one of claims 2 to 8 is characterized in that: is used for preparing acetic acid by methanol carbonylation reaction.
10. Use according to claim 9, characterized in that the methanol carbonylation reaction conditions are as follows: the temperature is 200-350 ℃, and the pressure is 0.110MPa and the methanol gas feeding airspeed of 100-2000 mL/g -1 ·h -1 The molar ratio of carbon monoxide to methanol is 1.0-100.
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