CN111087002B - Preparation method and application of mordenite molecular sieve - Google Patents
Preparation method and application of mordenite molecular sieve Download PDFInfo
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/26—Mordenite type
- C01B39/265—Mordenite type using at least one organic template directing agent
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
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Abstract
The application discloses a preparation method of a mordenite molecular sieve, wherein a first gel containing an aluminum source, a silicon source, an alkali source M, a mineralizer L, a template agent T and water is obtained; obtaining a second gel containing an aluminum source, a silicon source, an alkali source M, a mineralizer L, a template agent T and water, and performing pre-crystallization on the second gel to obtain pre-crystallization mother liquor; and then adding the first gel into the pre-crystallization mother liquor, mixing to form a mixture, performing hydrothermal crystallization, washing, drying and roasting to obtain the mordenite molecular sieve. The mordenite molecular sieve obtained by the preparation method provided by the application has a needle-shaped stacking structure. The mordenite molecular sieve is used as a dimethyl ether carbonylation catalyst after ammonium ion exchange, and shows better low-temperature activity and higher conversion rate and selectivity.
Description
Technical Field
The invention relates to a preparation method and application of a mordenite molecular sieve, belonging to the field of catalysts.
Background
Methyl acetate is a solvent with low toxicity, biodegradability, active chemical properties and excellent solubility, and can gradually replace conventional solvents such as acetone, butanone, ethyl acetate, cyclopentane and the like to be applied to the fields of coatings, printing ink, resins, adhesives and the like.
The synthesis process of methyl acetate mainly comprises an acetic acid methanol esterification method and a dimethyl ether carbonylation method. With the development and application of the catalyst for synthesizing methyl acetate by dimethyl ether carbonylation, the process of synthesis gas → methanol → dimethyl ether → methyl acetate is realized, good activity and selectivity are expressed at low temperature, the requirements of atomic economy and green chemical industry are met, and the catalyst has great strategic significance in the fields of energy and chemical industry.
CN106032280A discloses a method for synthesizing mordenite with mesopores and micropores, a product and application thereof, wherein the mordenite obtained by preparing initial gel step by step and crystallizing step by step has micropores and mesopores at the same time, and shows excellent performance and stability in the catalysis of dimethyl ether carbonylation reaction. CN108217680A discloses a synthesis method of mordenite molecular sieve with adjustable B acid center placement and distribution, a product and an application thereof, wherein the obtained mordenite has excellent performance and stability in catalyzing dimethyl ether carbonylation reaction by adjusting the position of B acid center on MOR zeolite. CN109092348A discloses a mordenite molecular sieve catalyst, a preparation method thereof and an application thereof in carbonylation synthesis of methyl acetate, the preparation of mordenite H-MOR molecular sieves with different crystal grains is beneficial to reducing diffusion resistance and reducing carbon deposition of the catalyst, and the gas space velocity is 3000H under the condition that DME/Ar/CO is 1/2/47-1The conversion rate of dimethyl ether reaches 88 percent, and the selectivity of methyl acetate reaches 99 percent.
The reported dimethyl ether carbonylation catalysts are mostly spherical or rod-shaped mordenite, the needle-shaped stacking structure MOR molecular sieve catalyst is beneficial to reactant diffusion, and shows better low-temperature activity, higher conversion rate and selectivity in the reaction of preparing methyl acetate by dimethyl ether carbonylation.
Disclosure of Invention
The invention provides an MOR type molecular sieve dimethyl ether carbonylation catalyst, which shortens the radial diffusion distance, is beneficial to the rapid diffusion of reactants and the reduction of carbon deposition while ensuring the number of axial catalytic active sites by synthesizing an acicular mordenite molecular sieve catalyst, and greatly improves the performance and the service life of a reaction catalyst for synthesizing methyl acetate by dimethyl ether carbonylation.
According to one aspect of the present application, there is provided a process for the preparation of a mordenite molecular sieve, characterised in that it comprises at least the steps of:
a) obtaining a first gel containing an aluminum source, a silicon source, an alkali source M, a mineralizer L, a template agent T and water; the components in the first gel have the following molar ratios:
SiO2：Al2O3＝25～55：1
M2O：SiO2＝0.1～2：1
T：Al2O3＝1～5：1
L：SiO2＝0.03～0.1：1
H2O：SiO2＝20～30：1；
b) obtaining a second gel containing an aluminum source, a silicon source, an alkali source M, a mineralizer L, a template agent T and water; the components in the second gel have the following molar ratios:
SiO2：Al2O3＝25～55：1
M2O：SiO2＝0.1～2：1
T：Al2O3＝1～5：1
L：SiO2＝0.03～0.1：1
H2O：SiO2＝9～20：1；
performing pre-crystallization on the second gel to obtain pre-crystallization mother liquor;
c) adding the first gel into the pre-crystallization mother liquor to form a mixture; placing the mixture in a closed reactor, crystallizing and roasting to obtain the mordenite molecular sieve;
wherein the mole number of the silicon source is SiO2Counting; the mole number of the aluminum source is Al2O3Counting; the mole number of the template agent T is calculated by the mole number of the template agent T per se; the number of moles of the alkali source M based on the corresponding alkali metal oxide M2The mole number of O; the moles of mineralizer L are based on the moles of L itself; the mole number of water is H2And (4) measuring O.
Optionally, the components in the first gel in step a) have the following molar ratios:
SiO2：Al2O3＝25～51：1
M2O：SiO2＝0.1～1.2：1
T：Al2O3＝1～2：1
L：SiO2＝0.03～0.09：1
H2O：SiO2＝20～30：1；
the components in the second gel in step b) have the following molar ratios:
SiO2：Al2O3＝25～51：1
M2O：SiO2＝0.1～1.2：1
T：Al2O3＝1～2：1
L：SiO2＝0.03～0.09：1
H2O：SiO2＝9～20：1。
optionally, the SiO2：Al2O3Is selected from 25.81, 30, 30.63, 35, 41.05, 42.05, 45, 50.02, or 55; the lower limit is selected from 25, 25.81, 30, 30.63, 35, 41.05, 42.05, 45 or 50.02.
Optionally, the M2O：SiO2The upper limit of (d) is selected from 0.12, 0.15, 0.5, 1.16, 1.17, 1.2, 1.5 or 2; the lower limit is selected from 0.1, 0.12, 0.15, 0.5, 1.16, 1.17, 1.2 or 1.5.
Optionally, the T: al (Al)2O3The upper limit of (a) is selected from 1.1, 1.2, 1.3, 1.34, 1.41, 1.43, 1.62, 1.65, 2, 3, 4 or 5; the lower limit is selected from 1, 1.1, 1.2, 1.3, 1.34, 1.41, 1.43, 1.62, 1.65, 2, 3 or 4.
Optionally, the L: SiO 22The upper limit of (d) is selected from 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or 0.1; the lower limit is selected from 0.03, 0.04, 0.05, 0.06, 0.07, 0.08 or 0.09.
Optionally, H in the first gel2O：SiO2Is selected from 21, 23, 25, 27, 29 or 30; the lower limit is selected from 20, 21, 23, 25, 27 or 29.
Optionally, H in the second gel2O：SiO2Is selected from the group consisting of 10, 12, 14, 16, 18Or 20; the lower limit is selected from 9, 10, 12, 14, 16 or 18.
Optionally, the mass ratio of the first gel to the second gel is 1-8: 1.
Optionally, the mass ratio of the first gel to the second gel is 1-6: 1.
Optionally, the mass ratio of the first gel to the second gel is 1: 1.
Optionally, the upper limit of the mass ratio of the first gel to the second gel is selected from 2, 3, 4, 5, 6, 7 or 8; the lower limit is selected from 1, 2, 3, 4, 5, 6 or 7.
Optionally, step c) comprises: and adding the first gel into the pre-crystallization mother liquor under the stirring condition to form a mixture.
Optionally, in the step b), the temperature of the pre-crystallization is 100-130 ℃, and the time of the pre-crystallization is 12-48 hours.
Optionally, in step b), the upper limit of the temperature of the pre-crystallization is selected from 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃; the lower limit is selected from 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C, 120 deg.C or 125 deg.C.
Optionally, in step b), the upper limit of the time for the pre-crystallization is selected from 15h, 20h, 25h, 30h, 35h, 40h, 45h or 48 h; the lower limit is selected from 12h, 15h, 20h, 25h, 30h, 35h, 40h or 45 h.
Optionally, in the step c), the crystallization temperature is 150 to 200 ℃, and the crystallization time is 24 to 72 hours.
Optionally, in the step c), the crystallization temperature is 160-190 ℃, and the crystallization time is 24-48 hours.
Optionally, in step c), the upper limit of the temperature of crystallization is selected from 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃ or 200 ℃; the lower limit is selected from 150 deg.C, 155 deg.C, 160 deg.C, 165 deg.C, 170 deg.C, 175 deg.C, 180 deg.C, 185 deg.C, 190 deg.C or 195 deg.C.
Optionally, in step c), the upper limit of the crystallization time is selected from 26h, 30h, 36h, 42h, 48h, 54h, 60h, 66h or 72 h; the lower limit is selected from 24h, 26h, 30h, 36h, 42h, 48h, 54h, 60h, 66h or 70 h.
Optionally, in the step c), the temperature is programmed to the crystallization temperature at a rate of 1-5 ℃/min.
Optionally, in the step c), the roasting temperature is 400-600 ℃, and the roasting time is 2-8 hours.
Optionally, the alkali source M in step a) and step b) is independently selected from at least one of hydroxides of alkali metals.
Optionally, the hydroxide of the alkali metal is selected from at least one of lithium hydroxide, sodium hydroxide and potassium hydroxide.
Optionally, the mineralizer L in step a) and step b) is independently selected from at least one of sodium chloride, sodium bromide, and sodium fluoride.
Alternatively, the templating agent T is independently selected from at least one of cetyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetraethylammonium bromide, isopropylamine, diisopropylamine, triisopropylamine, tetramethylethylenediamine, tetraethylethylenediamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, n-butylamine, cyclohexylamine, caprolactam, tetraethylethylenediamine, tetramethyleneimine, pentamethyleneimine, hexamethyleneimine, heptamethyleneimine, cycloheptaneamine, cyclopentylamine, tetraethylammonium hydroxide, hexadecyltrimethylammonium hydroxide.
Optionally, the silicon source in step a) and step b) is independently selected from at least one of silica, silica sol, sodium silicate and diatomite.
The aluminum sources in step a) and step b) are independently selected from at least one of sodium aluminate, aluminum isopropoxide and aluminum hydroxide.
Optionally, the mordenite molecular sieve is in a needle packing structure.
According to a further aspect of the present application there is provided a dimethyl ether carbonylation catalyst characterised in that a mordenite molecular sieve prepared as described in any preceding method has been ammonium ion exchanged to provide the dimethyl ether carbonylation catalyst.
Optionally, the ammonium ion exchange comprises the steps of:
and (3) placing the mordenite molecular sieve in a solution containing ammonium salt for ion exchange, and washing, drying and roasting to obtain the dimethyl ether carbonylation catalyst.
Optionally, the ammonium salt in the solution containing ammonium salt is selected from at least one of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate, and ammonium carbonate.
Optionally, the concentration of ammonium ions in the solution containing ammonium salt is 0.5-2 mol/L.
Alternatively, the conditions of the ammonium ion exchange are: the exchange time is 1-5 h, the exchange temperature is 50-90 ℃, and the liquid-solid mass ratio is 1-8.
Optionally, the drying temperature is 100-140 ℃, and the drying time is 8-16 h; the roasting temperature is 450-600 ℃, and the roasting time is 3-6 h.
According to another aspect of the application, a method for preparing methyl acetate by carbonylation of dimethyl ether is provided, which is characterized in that raw material gas containing dimethyl ether is led into a reactor filled with a catalyst to react to obtain methyl acetate;
the catalyst is at least one selected from the dimethyl ether carbonylation catalysts.
Alternatively, the reaction conditions are: the reaction temperature is 180-260 ℃, and the reaction pressure is 1-5 MPa; the feed molar ratio of raw material gas dimethyl ether to carbon monoxide is 1: 1-50, wherein the feeding molar ratio of dimethyl ether to nitrogen is 1: 1-60, and the total airspeed of the volume of the mixed gas is 1000h-1～5000h-1。
Alternatively, the reaction conditions are: the reaction temperature is 180-200 ℃, and the reaction pressure is 1-2 MPa; the feed molar ratio of raw material gas dimethyl ether to carbon monoxide is 1: 1-10, wherein the feeding molar ratio of dimethyl ether to nitrogen is 1: 40-60, and the total space velocity of the volume of the mixed gas is 1000h-1～2000h-1。
Optionally, the pre-reaction catalyst is treated with a pretreatment gas;
the pretreatment gas is selected from N2Ar or He gas.
The beneficial effects of the invention include but are not limited to:
the mordenite molecular sieve prepared by the preparation method has a needle-shaped stacking structure, and the dimethyl ether carbonylation catalyst is mostly spherical or rod-shaped mordenite.
Drawings
FIG. 1 is an XRD pattern of Na-MOR synthesized in example 1.
FIG. 2 is an SEM photograph of the Na-MOR synthesized in example 1.
FIG. 3 is an SEM photograph of the synthesized Na-MOR of comparative example 1.
FIG. 4 is an SEM photograph of the synthesized Na-MOR of comparative example 2.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The analysis method in the examples of the present application is as follows:
XRD analysis characterization was performed using X' Pert PRO X-ray diffractometer from PANalytical, netherlands, Cu target, ka radiation source (λ ═ 0.15418nm), voltage 40KV, current 40 mA; the instrument used for SEM test is a Hitachi SU8020 field emission scanning electron microscope, and the accelerating voltage is 2 kV.
Product analysis was performed on a FuliGC 9790 gas chromatograph, HP-PLOT/Q column, FID detector; the dimethyl ether (DME) conversion rate and Methyl Acetate (MA) selectivity data are calculated according to an area normalization method.
Example 1
The method comprises the following steps: sodium aluminate 1.5g, 30% silica sol 155.6g, NaCl 1.2g, NaOH 7.8g, cetyl trimethylammonium bromide (CTMAB) 5.5g and water 41g were mixed to obtain a silica-alumina gel consisting of: n (SiO)2)/n(Al2O3)＝50.02，n(Na2O)/n(SiO2)＝0.15，n(CTMAB)/n(Al2O3)＝1.65，n(NaCl)/n(SiO2)＝0.03，n(H2O)/n(SiO2) 10; the gel was divided equally into two. Adding 65g deionized water into the first component, diluting, and stirring to obtain diluted gel n (H)2O)/n(SiO2) 20; and transferring the component II to a reaction kettle with a polytetrafluoroethylene lining for pre-crystallization for 24 hours at 110 ℃, and cooling to obtain pre-crystallization mother liquor.
Step two: slowly adding the diluted component I into the pre-crystallization mother liquor obtained in the step I, uniformly mixing, and then carrying out temperature programming in a reaction kettle at a speed of 1 ℃/min to 170 ℃ for crystallization for 48 hours; and after crystallization, washing the product with deionized water to be neutral, drying at 120 ℃ for 12h, and roasting at 550 ℃ in a muffle furnace for 4h to obtain Na-MOR.
The XRD spectrum of the product is shown in figure 1, and the characterization result shows mordenite; the SEM image is shown in figure 2, which shows that the mordenite has a needle structure of 10-50X 300-600 nm.
Step three: weighing a certain amount of the Na-MOR molecular sieve, placing the Na-MOR molecular sieve in a beaker, performing ammonia ion exchange on 2mol/L ammonium nitrate solution at the solid-liquid mass ratio of 1:8 for 3H at the temperature of 80 ℃, repeating the ammonia ion exchange for 3 times, drying the mixture for 12H at the temperature of 120 ℃, and then placing the dried mixture in a muffle furnace at the temperature of 550 ℃ for roasting for 4H to prepare the H-MOR molecular sieve catalyst.
Step four: tabletting the catalyst, crushing and screening, weighing 2g of 20-40 mesh catalyst, loading into a fixed bed reactor, and carrying out N treatment at 380 DEG C2In-situ pretreatment is carried out for 3h, the temperature is reduced to 190 ℃, the reaction pressure is adjusted to 1.0MPa for activity evaluation, and the feeding ratio is DME/N21/45/4 at volume space velocity of 1600h-1(ii) a The performance evaluation data of the catalyst carbonylation catalytic reaction are shown in table 1.
Example 2
The method comprises the following steps: weighing 1.5g of sodium aluminate, 75.2g of 30% silica sol, 1.2g of NaF, 1.8g of NaOH, 4.8g of CTMAB and 11g of water, and mixing to obtain the silicon-aluminum gel, wherein the silicon-aluminum gel comprises the following components: n (SiO)2)/n(Al2O3)＝41.05，n(Na2O)/n(SiO2)＝0.12，n(CTMAB)/n(Al2O3)＝1.43，n(NaF)/n(SiO2)＝0.08，n(H2O)/n(SiO2) 9. The gel was divided equally into two. Adding 36g deionized water into the component I, diluting, and stirring to obtain diluted gel n (H)2O)/n(SiO2) 20; and transferring the component II to a reaction kettle with a tetrafluoroethylene lining for pre-crystallization at 110 ℃ for 24 hours, and cooling to obtain pre-crystallization mother liquor.
The operations of the second step, the third step and the fourth step are the same as those of the second step, the third step and the fourth step in the embodiment 1. The XRD pattern and SEM pattern of the Na-MOR sample obtained in step two are similar to those of the Na-MOR sample obtained in example 1, and the characterization result shows that the product is needle-shaped mordenite. The performance evaluation data of the catalyst carbonylation catalytic reaction are shown in table 1.
Example 3
The method comprises the following steps: sodium aluminate 1.5g, 30% silica sol 77.1g, NaCl 0.7g, NaOH 2.5g, Dodecyl Trimethyl Ammonium Bromide (DTAB) 2.8g and water 22g were mixed thoroughly to obtain silica-alumina gel which consisted of: n (SiO)2)/n(Al2O3)＝42.05，n(Na2O)/n(SiO2)＝0.12，n(DTAB)/n(Al2O3)＝1.62，n(NaCl)/n(SiO2)＝0.03，n(H2O)/n(SiO2) 10. The gel was divided equally into two. Adding 35g deionized water into the first component, diluting, and stirring to obtain diluted gel n (H)2O)/n(SiO2) 21; and transferring the component II to a reaction kettle with a tetrafluoroethylene lining for pre-crystallization at 110 ℃ for 24 hours, and cooling to obtain pre-crystallization mother liquor.
The operations of the second step, the third step and the fourth step are the same as those of the second step, the third step and the fourth step in the embodiment 1. The XRD pattern and SEM pattern of the Na-MOR sample obtained in step two are similar to those of the Na-MOR sample obtained in example 1, and the characterization result shows that the product is needle-shaped mordenite. The performance evaluation data of the catalyst carbonylation catalytic reaction are shown in table 1.
Example 4
The method comprises the following steps: 1.5g of sodium aluminate, 79.6g of sodium silicate, 0.5g of NaCl, 3.5g of NaOH, 4.7g of CTMAB and 100.0g of deionized water are mixed to obtain silicon-aluminum gel, and the silicon-aluminum gel comprises the following components: n (SiO)2)/n(Al2O3)＝30.63，n(Na2O)/n(SiO2)＝1.17，n(CTMAB)/n(Al2O3)＝1.41，n(NaCl)/n(SiO2)＝0.03，n(H2O)/n(SiO2) 20. The gel was divided equally into two. Adding 25g deionized water into the first component, diluting, and stirring to obtain diluted gel n (H)2O)/n(SiO2) 30; and transferring the component II to a tetrafluoroethylene lining for precrystallization at 110 ℃ for 24 hours, and cooling to obtain a precrystallized mother liquor.
The operations of the second step, the third step and the fourth step are the same as those of the second step, the third step and the fourth step in the embodiment 1. The XRD pattern and SEM pattern of the Na-MOR sample obtained in step two are similar to those of the Na-MOR sample obtained in example 1, and the characterization result shows that the product is needle-shaped mordenite. The performance evaluation data of the catalyst carbonylation catalytic reaction are shown in table 1.
Example 5
The method comprises the following steps: weighing 1.5g of sodium aluminate, 14g of white carbon black, 1.2g of NaCl, 7.8g of NaOH, 4.7g of CTMAB and 50g of deionized water, and mixing to obtain the silicon-aluminum gel, wherein the silicon-aluminum gel comprises the following components: n (SiO)2)/n(Al2O3)＝25.81，n(Na2O)/n(SiO2)＝1.16，n(CTMAB)/n(Al2O3)＝1.34，n(NaCl)/n(SiO2)＝0.09，n(H2O)/n(SiO2) 12. The gel was divided equally into two. Adding 27g deionized water into the first component, diluting, and stirring to obtain diluted gel n (H)2O)/n(SiO2) 25; and transferring the component II to a tetrafluoroethylene lining for precrystallization at 110 ℃ for 24 hours, and cooling to obtain a precrystallized mother liquor.
The operations of the second step, the third step and the fourth step are the same as those of the second step, the third step and the fourth step in the embodiment 1. The XRD pattern and SEM pattern of the Na-MOR sample obtained in step two are similar to those of the Na-MOR sample obtained in example 1, and the characterization result shows that the product is needle-shaped mordenite. The performance evaluation data of the catalyst carbonylation reaction are shown in table 1.
Example 6
The procedure of step one and step two was similar to example 1, except for the composition of the first gel and the second gel, the pre-crystallization temperature.
Component one is the same as component one of example 1; the second component was the same as the second component of example 5, and the temperature for pre-crystallization of the second component was 120 ℃.
The above synthesized product was characterized by XRD and SEM respectively, the XRD pattern and SEM pattern of the product were similar to those of Na-MOR in example 1, and the characterization result showed that the product was needle-structured mordenite.
The operation of the third step and the fourth step is the same as that of the third step and the fourth step of the example 1. The performance evaluation data of the catalyst carbonylation catalytic reaction are shown in table 1.
Example 7
Step one and step two were operated similarly to example 1, except for the mass ratio of the first gel to the second gel. The mass ratio of the first component to the second component is 1: 3.
The above synthesized product was characterized by XRD and SEM respectively, the XRD pattern and SEM pattern of the product were similar to those of Na-MOR in example 1, and the characterization result showed that the product was needle-structured mordenite.
The operation of the third step and the fourth step is the same as that of the third step and the fourth step of the example 1. The performance evaluation data of the catalyst carbonylation catalytic reaction are shown in table 1.
Example 8
The operations of step one and step two were similar to those of example 1, except for the composition, mass ratio, and crystallization time period of the first gel and the second gel. The mass ratio of the first component to the second component is 1: 6.
Component one is the same as component one of example 1; the second component is that the silicon source in the embodiment 1 is replaced by sodium silicate in equal amount, and the mineralizer is replaced by sodium fluoride; the crystallization time was 36 hours.
The above synthesized product was characterized by XRD and SEM respectively, the XRD pattern and SEM pattern of the product were similar to those of Na-MOR in example 1, and the characterization result showed that the product was needle-structured mordenite.
The operation of the third step and the fourth step is the same as that of the third step and the fourth step of the example 1. The performance evaluation data of the catalyst carbonylation catalytic reaction are shown in table 1.
Comparative example 1
The commercial Na-MOR of a catalyst factory of southern Kai university with a capsule-shaped accumulation structure is used as a raw material to prepare the methyl acetate contrast catalyst for the carbonylation of dimethyl ether. SEM images of the commercial Na-MOR are shown in FIG. 3, showing that the mordenite described above has a capsule-like packing structure. The catalyst preparation method and performance evaluation conditions were the same as in step two, step three, and step four of example 1. The carbonylation catalytic reaction performance evaluation data are shown in table 1.
Comparative example 2
Comparative example the layered packing structure Na-MOR used was prepared according to the published patent for the preparation of a layered nano mordenite molecular sieve (CN102718231A), and SEM images are shown in fig. 4, showing that the mordenite had a layered packing structure. The catalyst preparation method and performance evaluation conditions were the same as in step two, step three, and step four of example 1. The carbonylation catalytic reaction performance evaluation data are shown in table 1.
Comparative example 3
The procedure was similar to example 1, except that KCl was used as the mineralizer. The carbonylation catalytic reaction performance evaluation data are shown in table 1.
Comparative example 4
Operation is similar to example 1, except that NH is selected as mineralizer4And (4) Cl. The carbonylation catalytic reaction performance evaluation data are shown in table 1.
EXAMPLE 9 evaluation of catalyst
Evaluation of MOR type molecular sieve dimethyl ether carbonylation catalyst: product analysis was performed on a FuliGC 9790 gas chromatograph, HP-PLOT/Q column, FID detector; the DME conversion rate and MA selectivity data were calculated by area normalization.
As can be seen from Table 1, the needle-shaped stacked mordenite molecular sieve catalyst provided by the application shows better low-temperature activity, higher conversion rate and selectivity in the reaction of preparing methyl acetate by carbonylation of dimethyl ether.
EXAMPLES 10-12 use of catalysts
The catalyst was applied in the same operation as in step four of example 1, except that the reaction conditions were changed, the product analysis was carried out on a Fuligc 9790 gas chromatograph, HP-PLOT/Q column, FID detector; the DME conversion rate and MA selectivity data were calculated by area normalization. The specific conditions are shown in Table 2. The catalyst used was the catalyst of example 1.
The templating agent of example 1 was exchanged for tetradecyltrimethylammonium bromide, tetraethylammonium bromide, isopropylamine, diisopropylamine, triisopropylamine, tetramethylethylenediamine, tetraethylethylenediamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, n-butylamine, cyclohexylamine, caprolactam, tetraethylethylenediamine, tetramethyleneimine, pentamethyleneimine, hexamethyleneimine, heptamethyleneimine, cycloheptaneamine, cyclopentylamine, tetraethylammonium hydroxide, or hexadecyltrimethylammonium hydroxide, respectively. The XRD spectrogram characterization results of the prepared Na-MOR show that the Na-MOR is mordenite; SEM images show that the mordenite has a needle structure of 10-50 × 300-600 nm. A catalyst was prepared and evaluated in the same manner as in example 1, and its catalytic performance was similar to that of example 1.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (11)
1. A method for preparing a mordenite molecular sieve, which is characterized by at least comprising the following steps:
a) obtaining a first gel containing an aluminum source, a silicon source, an alkali source M, a mineralizer L, a template agent T and water; the components in the first gel have the following molar ratios:
SiO2：Al2O3 = 25~55：1
M2O：SiO2=0.1~2：1
T：Al2O3=1~5：1
L：SiO2=0.03~0.1：1
H2O：SiO2=20~30：1；
b) obtaining a second gel containing an aluminum source, a silicon source, an alkali source M, a mineralizer L, a template agent T and water; the components in the second gel have the following molar ratios:
SiO2：Al2O3 = 25~55：1
M2O：SiO2=0.1~2：1
T：Al2O3=1~5：1
L：SiO2=0.03~0.1：1
H2O：SiO2=9~20：1；
performing pre-crystallization on the second gel to obtain pre-crystallization mother liquor;
c) adding the first gel into the pre-crystallization mother liquor to form a mixture; placing the mixture in a closed reactor, crystallizing and roasting to obtain the mordenite molecular sieve;
wherein the mole number of the silicon source is SiO2Counting; the mole number of the aluminum source is Al2O3Counting; the mole number of the template agent T is calculated by the mole number of the template agent T per se; the number of moles of the alkali source M based on the corresponding alkali metal oxide M2The mole number of O; the moles of mineralizer L are based on the moles of L itself; the number of moles of water is based on the number of moles of water per se;
the mass ratio of the first gel to the second gel is 1-8: 1;
in the step b), the temperature of the pre-crystallization is 100-130 ℃, and the time of the pre-crystallization is 12-48 hours;
in the step c), the crystallization temperature is 150-200 ℃, and the crystallization time is 24-72 hours;
the alkali source M in the step a) and the step b) is independently selected from at least one of hydroxides of alkali metals
The mineralizer L in the step a) and the step b) is independently selected from at least one of sodium chloride, sodium bromide and sodium fluoride;
the mordenite molecular sieve is in a needle-shaped stacking structure.
2. The method according to claim 1, wherein the components of the first gel in step a) have the following molar ratios:
SiO2：Al2O3 = 25~51：1
M2O：SiO2=0.1~1.2：1
T：Al2O3=1~2：1
L：SiO2=0.03~0.09：1
H2O：SiO2=20~30：1；
the components in the second gel in step b) have the following molar ratios:
SiO2：Al2O3 = 25~51：1
M2O：SiO2=0.1~1.2：1
T：Al2O3=1~2：1
L：SiO2=0.03~0.09：1
H2O：SiO2=9~20：1。
3. the method according to claim 1, wherein the mass ratio of the first gel to the second gel is 1-6: 1.
4. The method of claim 1, wherein step c) comprises: and adding the first gel into the pre-crystallization mother liquor under the stirring condition to form a mixture.
5. The method as claimed in claim 1, wherein the temperature of the crystallization in step c) is 160 to 190 ℃ and the time of the crystallization is 24 to 48 hours.
6. The method according to claim 1, wherein in step c), the temperature is programmed to the crystallization temperature at a rate of 1-5 ℃/min.
7. The method according to claim 1, wherein in the step c), the roasting temperature is 400-600 ℃, and the roasting time is 2-8 h.
8. The method according to claim 1, wherein the hydroxide of an alkali metal is selected from at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide.
9. The method of claim 1, wherein the template T is selected from at least one of cetyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetraethylammonium bromide, isopropylamine, diisopropylamine, triisopropylamine, tetramethylethylenediamine, tetraethylethylenediamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, n-butylamine, cyclohexylamine, caprolactam, tetramethyleneimine, pentamethyleneimine, hexamethyleneimine, heptamethyleneimine, cycloheptaneamine, cyclopentylamine, tetraethylammonium hydroxide, and hexadecyltrimethylammonium hydroxide.
10. The method according to claim 1, wherein the silicon source in step a) and step b) is independently selected from at least one of silica white, silica sol, sodium silicate, diatomaceous earth;
the aluminum sources in the step a) and the step b) are independently selected from at least one of sodium aluminate, aluminum isopropoxide and aluminum hydroxide.
11. Use of a mordenite zeolite molecular sieve prepared by a process as claimed in any of claims 1 to 10 as a catalyst for the carbonylation of dimethyl ether by ammonium ion exchange.
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| CN114516640B (en) * | 2020-11-18 | 2024-04-16 | 中国科学院大连化学物理研究所 | Mordenite, preparation method and application thereof |
| CN114572997B (en) * | 2020-11-18 | 2023-11-17 | 中国科学院大连化学物理研究所 | Mordenite molecular sieve, preparation method and application |
| CN114516643B (en) * | 2020-11-18 | 2023-06-30 | 中国科学院大连化学物理研究所 | Mordenite molecular sieve synthesized by pyridine quaternary ammonium salt guided synthesis, preparation method and application |
| WO2022104580A1 (en) * | 2020-11-18 | 2022-05-27 | 中国科学院大连化学物理研究所 | Mordenite molecular sieve, and preparation method and use therefor |
| CN112537778B (en) * | 2020-12-28 | 2022-07-29 | 延长中科（大连）能源科技股份有限公司 | Preparation method and application of mordenite with high silica-alumina ratio |
| CN112645349B (en) * | 2020-12-28 | 2023-10-20 | 延长中科（大连）能源科技股份有限公司 | Preparation method and application of mordenite molecular sieve |
| CN114590818B (en) * | 2022-02-25 | 2023-08-08 | 厦门大学 | Lamellar MOR molecular sieve and preparation method thereof, catalyst for preparing ethanol by using synthesis gas and preparation method thereof |
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