CN117205960A - Method for synthesizing paraxylene by metal modified MCM-22 molecular sieve catalysis - Google Patents
Method for synthesizing paraxylene by metal modified MCM-22 molecular sieve catalysis Download PDFInfo
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- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 title claims abstract description 76
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 85
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000376 reactant Substances 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 19
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 230000035484 reaction time Effects 0.000 claims abstract description 18
- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 239000004570 mortar (masonry) Substances 0.000 claims description 11
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000006071 cream Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 230000002572 peristaltic effect Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 21
- 238000002156 mixing Methods 0.000 abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 48
- XZRHNAFEYMSXRG-UHFFFAOYSA-N 2,5-dimethylbenzoic acid Chemical compound CC1=CC=C(C)C(C(O)=O)=C1 XZRHNAFEYMSXRG-UHFFFAOYSA-N 0.000 description 32
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 17
- 239000006227 byproduct Substances 0.000 description 16
- 239000005457 ice water Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 15
- 238000005342 ion exchange Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011068 loading method Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000006117 Diels-Alder cycloaddition reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- PHTAQVMXYWFMHF-QVPNGJTFSA-N alpha-L-Fucp-(1->2)-beta-D-Galp-(1->4)-beta-D-GlcpNAc Chemical compound O[C@H]1[C@H](O)[C@H](O)[C@H](C)O[C@H]1O[C@H]1[C@H](O[C@@H]2[C@H](O[C@@H](O)[C@H](NC(C)=O)[C@H]2O)CO)O[C@H](CO)[C@H](O)[C@@H]1O PHTAQVMXYWFMHF-QVPNGJTFSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for synthesizing paraxylene by metal modified MCM-22 molecular sieve catalysis, belonging to the technical field of chemical catalysis. The method takes 2, 5-dimethyl furan and acrylic acid as reactants, takes a metal modified MCM-22 molecular sieve as a catalyst, and is carried out in a magnetic stirring kettle, wherein the initial reaction pressure is normal pressure, and the reaction temperature is 150-190 ℃; the reaction time is 3-10 h, and the reaction is carried out under the condition that nitrogen is used as a protective gas. The metal modified MCM-22 molecular sieve has high external specific surface characteristics, realizes the synergistic effect of the L acid site on the metal oxide and the B acid site on the MCM-22 surface by a physical mixing and re-roasting method, balances the catalysis rates of the B acid and the L acid site, and accelerates the total reaction rate. After 10h reaction at 150℃99%2,5-DMF conversion and 98% PX selectivity were obtained.
Description
Technical Field
The invention belongs to the technical field of chemical catalysis, and particularly relates to a method for synthesizing Paraxylene (PX) by using a metal modified MCM-22 molecular sieve as a catalyst to catalyze 2, 5-dimethylfuran (2, 5-DMF) and Acrylic Acid (AA) and application thereof.
Background
Para-xylene (PX) is an important basic raw material in the aromatic industry, and is mainly used for synthesizing refined terephthalic acid by oxidation reaction, thereby producing polyester products (such as synthetic fibers, plastics, etc.).
While the traditional production process of PX relies heavily on fossil energy, fossil energy is now becoming increasingly depleted, and the availability of PX from renewable biomass and its derivatives is of great interest. The biomass-derived 2,5-DMF and dienophile acrylic acid AA undergo Diels-Alder cycloaddition reaction, and then are dehydrated and decarboxylated, so that the method is one of the best ways for synthesizing PX, and the reaction has the advantages of high yield, green sustainable property and the like, and has good industrial application prospect. Numerous scholars have studied to find: the reaction requires co-catalysis of the B acid, the L acid, and typically a bifunctional catalyst. The silicon-aluminum molecular sieve is widely used due to the advantages of high thermal stability, high specific surface and the like. However, although the aluminosilicate molecular sieve has both B acid and L acid sites, the L acid sites are relatively low in content relative to the B acid sites and the acid strength is also relatively weak, resulting in a mismatch in the B acid and L acid catalytic rates and a limited overall reaction rate.
Therefore, the property of the L acid site of the catalyst is urgently required to be modulated, the catalysis rates of B acid and L acid are regulated, and the high-activity molecular sieve catalyst is obtained to be applied to the synthesis of PX by 2, 5-DMF.
Disclosure of Invention
Aiming at the problem of low catalyst activity in the current process of synthesizing PX by using 2,5-DMF and AA, the invention provides a metal modified MCM-22 molecular sieve which is used as a catalyst and has high-efficiency catalytic performance in the process of synthesizing PX by using 2,5-DMF and AA.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for synthesizing PX by catalyzing metal modified MCM-22 molecular sieve is characterized in that reactants are 2,5-DMF and AA, the metal modified MCM-22 molecular sieve is used as a catalyst, wherein the molar ratio of the 2,5-DMF to the AA is 1:2 (the dosage of the 2,5-DMF is 7.5 mmol); the mass of the metal modified MCM-22 molecular sieve catalyst is 5% of the total mass of the reactants; the reaction is carried out in a magnetic stirring kettle; the reaction temperature is 150-190 ℃, the initial reaction pressure is normal pressure, and nitrogen is used as a protective gas.
As the limit of the invention, the preparation method of the metal modified MCM-22 molecular sieve catalyst comprises the following steps:
(1) Placing a metal precursor and MCM-22 (P) without a template agent in a mortar for grinding uniformly, and roasting in a muffle furnace at 550 ℃ for 8 hours to obtain a Na-type modified MCM-22 molecular sieve;
(2) 1.0 mol.L of the Na-modified MCM-22 molecular sieve obtained in the step (1) is used -1 NH 4 And performing ion exchange on the Cl aqueous solution for 3 times, and performing suction filtration, washing and drying, and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain the metal modified MCM-22 molecular sieve.
As a further limitation of the present invention, the metal precursor in step (1) of the present invention is ZrOCl 2 ·8H 2 O、Zn(NO 3 ) 2 ·6H 2 O or SnC 2 O 4 Any one of the metal modified MCM-22 molecular sieves in the step (2) is ZrO 2 /MCM-22、ZnO 2 MCM-22 or SnO 2 Any one of MCM-22.
As a further limitation of the present invention, the non-template MCM-22 (P) of the present invention is prepared as follows:
(1) Dissolving 0.40 g-2.80 g NaOH in deionized water at room temperatureAdding 1.66g NaAlO into the sub-water 2 Stirring for 1h to obtain a clear and transparent solution;
(2) Then slowly dripping 6.94g of Hexamethyleneimine (HMI) into the solution obtained in the step (1), continuously stirring for 0.5h after the dripping is finished, slowly dripping 48.06g of silica sol (25 wt%) by using a peristaltic pump under the condition of intense stirring, adding 0.12g of seed crystal, and aging for 24h in a water bath at 25 ℃ to obtain a pale-cream-yellow precursor, wherein the molar ratio of the pale-cream-yellow precursor is as follows: 0.2SiO 2 ∶0.0067Al 2 O 3 ∶0.01～0.07NaOH∶0.07HMI∶6H 2 O；
(3) Transferring the pale cream yellow precursor obtained in the step (2) into a hydrothermal reaction kettle, and standing and crystallizing for 7 days in a baking oven at 150 ℃;
(4) And (3) carrying out suction filtration, washing and drying on the precursor subjected to standing crystallization in the step (3) to obtain the MCM-22 (P) without the template removal agent.
After the technical scheme is adopted, compared with the prior art method, the method has the following beneficial effects:
the invention provides a simple catalyst modification method, the metal modified MCM-22 molecular sieve obtained by the technical scheme of the invention has high external specific surface characteristics, and the synergistic effect of the L acid site on the metal oxide and the B acid site on the MCM-22 surface is realized by a physical mixing and re-roasting method, so that the catalysis rates of the B acid and the L acid site are balanced, and the total reaction rate is accelerated. After 10 hours of reaction at 150℃and normal pressure, a maximum of 99%2,5-DMF conversion and 98% PX selectivity were obtained.
Drawings
FIG. 1 is an XRD pattern of the metal-modified MCM-22 catalyst prepared in example 3, example 6 and example 9 and the MCM-22 catalyst prepared in comparative example 1, and the characteristic diffraction peaks appearing at about 7.1 DEG, 8.0 DEG, 9.7 DEG, 22.5 DEG, 25.0 DEG and 26.0 DEG of 2θ, which are substantially consistent with the MCM-22 pattern reported in the literature, without other hetero-crystalline phases, can indicate that the loading of metal species does not affect the crystal structure of the MCM-22 molecular sieve.
Catalysts with metal loadings up to 5% do not show metal oxides (ZrO) in the XRD pattern 2 、ZnO 2 、SnO 2 ) This may be due to the high dispersion of metal species on the MCM-22 molecular sieve.
FIG. 2 is a graph of the catalytic activity of MCM-22 and Sn-MCM-22, and it can be seen from the graph that the catalytic activity of the modified MCM-22 is greatly improved.
Detailed Description
The invention will be further illustrated with reference to the following examples, but it should be understood that these examples are for illustrative purposes only and should not be construed as limiting the practice of the invention.
According to the invention, different metal precursors are adopted to prepare the metal modified MCM-22 molecular sieve, and the types and the addition amounts of the metal precursors are regulated in the preparation process, so that different modified MCM-22 molecular sieves can be obtained. Specific examples are as follows:
the preparation method of the precursor MCM-22 (P) comprises the following steps:
first, the precursor MCM-22 (P) is synthesized, 0.40 g-2.80 g NaOH is dissolved in 90.10g deionized water, then 1.66g NaAlO is added 2 Stirring for 1h at room temperature; then 6.94g HMI is added, 48.06g silica sol (25 wt%) is slowly added dropwise under the condition of intense stirring, 0.12g seed crystal is added, and the mixture is aged for 24 hours under the condition of 25 ℃ water bath to obtain a pale-cream yellow precursor, wherein the molar ratio of the pale-cream yellow precursor is as follows: 0.2SiO 2 ∶0.0067Al 2 O 3 ∶0.01～0.07NaOH∶0.07HMI∶6H 2 O。
The precursor is transferred into a hydrothermal reaction kettle, and is kept stand and crystallized in a baking oven at 150 ℃ for 7 days. And (3) carrying out suction filtration, washing and drying on the precursor in the hydrothermal reaction kettle to obtain MCM-22 (P) without template removal.
Example 1
0.0523g ZrOCl 2 ·8H 2 O and 2.0g of MCM-22 (P) are put into a mortar for grinding uniformly, and are roasted for 8 hours at 550 ℃ in a muffle furnace to obtain Na-type 1% ZrO 2 MCM-22. Then go through 1.0 mol.L -1 NH of (C) 4 Ion-exchanging the Cl aqueous solution for 3 times, then drying and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain H-type 1% ZrO 2 /MCM-22。
Example 2
Will be 0.0785g ZrOCl 2 ·8H 2 O and 2.0g of MCM-22 (P) are put into a mortar for grinding uniformly, and are roasted for 8 hours at 550 ℃ in a muffle furnace to obtain Na-type 3% ZrO 2 MCM-22. Then go through 1.0 mol.L -1 NH of (C) 4 Ion-exchanging the Cl aqueous solution for 3 times, then drying and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain H-type 3% ZrO 2 /MCM-22。
Example 3
0.1308g ZrOCl 2 ·8H 2 O and 2.0g of MCM-22 (P) are put into a mortar for grinding uniformly, and are roasted for 8 hours at 550 ℃ in a muffle furnace to obtain Na-type 5% ZrO 2 MCM-22. Then go through 1.0 mol.L -1 NH of (C) 4 Ion-exchanging the Cl aqueous solution for 3 times, then drying and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain H-type 5% ZrO 2 /MCM-22。
Example 4
0.0731g Zn (NO) 3 ) 2 ·6H 2 O and 2.0g of MCM-22 (P) are put into a mortar for grinding uniformly, and are roasted for 8 hours at 550 ℃ in a muffle furnace to obtain Na-type 1% Zr-MCM-22. Then go through 1.0 mol.L -1 NH of (C) 4 Ion-exchanging the Cl aqueous solution for 3 times, then drying and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain H-type 1% ZnO 2 /MCM-22。
Example 5
0.2193g Zn (NO) 3 ) 2 ·6H 2 O and 2.0g of MCM-22 (P) are put into a mortar for grinding uniformly, and are roasted for 8 hours at 550 ℃ in a muffle furnace to obtain 3% ZnO 2 MCM-22. Then go through 1.0 mol.L -1 NH of (C) 4 Ion-exchanging the Cl aqueous solution for 3 times, then drying and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain H-type 3% ZnO 2 /MCM-22。
Example 6
0.3655g Zn (NO) 3 ) 2 ·6H 2 O and 2.0g of MCM-22 (P) are put into a mortar for grinding uniformly, and are roasted for 8 hours at 550 ℃ in a muffle furnace to obtain Na-type 5% ZnO 2 MCM-22. Then go through 1.0 mol.L -1 NH of (C) 4 Ion-exchanging the Cl aqueous solution for 3 times, then drying and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain H-type 5% ZnO 2 /MCM-22。
Example 7
0.0274g of Sn (NO) 3 ) 2 ·6H 2 O and 2.0g of MCM-22 (P) are put into a mortar for grinding uniformly, and are roasted for 8 hours at 550 ℃ in a muffle furnace to obtain Na-type 1% SnO 2 MCM-22. Then go through 1.0 mol.L -1 NH of (C) 4 Ion-exchanging the Cl aqueous solution for 3 times, then drying and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain H-type 1% SnO 2 /MCM-22。
Example 8
0.0823g of Sn (NO) 3 ) 2 ·6H 2 O and 2.0g of MCM-22 (P) are put into a mortar for grinding uniformly, and are roasted for 8 hours at 550 ℃ in a muffle furnace to obtain Na-type 3% SnO 2 MCM-22. Then go through 1.0 mol.L -1 NH of (C) 4 Ion-exchanging the Cl aqueous solution for 3 times, then drying and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain H-type 3% SnO 2 /MCM-22。
Example 9
0.1372g of Sn (NO) 3 ) 2 ·6H 2 O and 2.0g of MCM-22 (P) are put into a mortar for grinding uniformly, and are roasted for 8 hours at 550 ℃ in a muffle furnace to obtain Na-type 5% SnO 2 MCM-22. Then go through 1.0 mol.L -1 NH of (C) 4 Ion-exchanging the Cl aqueous solution for 3 times, then drying and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain H-type 5% SnO 2 /MCM-22。
The catalysts obtained in examples 1 to 9 above were used in the reaction of synthesizing PX from 2,5-DMF and AA, and the specific applications are as follows:
example 10
Mixing 2,5-DMF and AA according to a molar ratio of 1:2, wherein the concentration of the 2,5-DMF is 0.3 mol.L -1 AA concentration of 0.6 mol.L -1 The solvent is n-heptane, the total volume of the reaction solution is 25mL, the mixed solution is transferred into a magnetic stirring kettle, and H-type 1% ZrO which is 5% of the total mass of the reactants is added 2 MCM-22, the gas in the kettle is replaced by high-purity nitrogen for 3 times. The reaction temperature is 150 ℃, the initial pressure is normal pressure, and the reaction time is 3 hours; after the reaction was completed, the reaction vessel was cooled in an ice-water bath. The main products are PX and by-products of 2, 5-hexanedione and 2, 5-dimethylbenzoic acid.
Example 11
Mixing 2,5-DMF and AA according to a molar ratio of 1:2, wherein the concentration of the 2,5-DMF is 0.3 mol.L -1 AA concentration of 0.6 mol.L -1 The solvent is n-heptane, the total volume of the reaction solution is 25mL, the mixed solution is transferred into a magnetic stirring kettle, and H-type 3% ZrO which is 5% of the total mass of the reactants is added 2 MCM-22, the gas in the kettle is replaced by high-purity nitrogen for 3 times. The reaction temperature is 150 ℃, the initial pressure is normal pressure, and the reaction time is 3 hours; after the reaction was completed, the reaction vessel was cooled in an ice-water bath. The main products are PX and by-products of 2, 5-hexanedione and 2, 5-dimethylbenzoic acid.
Example 12
Mixing 2,5-DMF and AA according to a molar ratio of 1:2, wherein the concentration of the 2,5-DMF is 0.3 mol.L -1 AA concentration of 0.6 mol.L -1 The solvent is n-heptane, the total volume of the reaction solution is 25mL, the mixed solution is transferred into a magnetic stirring kettle, and H-type 5% ZrO which is 5% of the total mass of the reactants is added 2 MCM-22, the gas in the kettle is replaced by high-purity nitrogen for 3 times. The reaction temperature is 150 ℃, the initial pressure is normal pressure, and the reaction time is 3 hours; after the reaction was completed, the reaction vessel was cooled in an ice-water bath. The main products are PX and by-products of 2, 5-hexanedione and 2, 5-dimethylbenzoic acid.
Example 13
Mixing 2,5-DMF and AA according to a molar ratio of 1:2, wherein the concentration of the 2,5-DMF is 0.3 mol.L -1 AA concentration of 0.6 mol.L -1 The solvent is n-heptane, the total volume of the reaction solution is 25mL, the mixed solution is transferred into a magnetic stirring kettle, and H-type 1% ZnO which is 5% of the total mass of the reactants is added 2 MCM-22, the gas in the kettle is replaced by high-purity nitrogen for 3 times. The reaction temperature is 150 ℃, the initial pressure is normal pressure, and the reaction time is 3 hours; after the reaction was completed, the reaction vessel was cooled in an ice-water bath. The main products are PX and by-products of 2, 5-hexanedione and 2, 5-dimethylbenzoic acid.
Example 14
Mixing 2,5-DMF and AA according to a molar ratio of 1:2, wherein the concentration of the 2,5-DMF is 0.3 mol.L -1 AA concentration of 0.6 mol.L -1 The solvent was n-heptane and the total reaction volume was 25mL, and the mixture was transferred toAdding H-type 3% ZnO accounting for 5% of the total mass of reactants into a magnetic stirring kettle 2 MCM-22, the gas in the kettle is replaced by high-purity nitrogen for 3 times. The reaction temperature is 150 ℃, the initial pressure is normal pressure, and the reaction time is 3 hours; after the reaction was completed, the reaction vessel was cooled in an ice-water bath. The main products are PX and by-products of 2, 5-hexanedione and 2, 5-dimethylbenzoic acid.
Example 15
Mixing 2,5-DMF and AA according to a molar ratio of 1:2, wherein the concentration of the 2,5-DMF is 0.3 mol.L -1 AA concentration of 0.6 mol.L -1 The solvent is n-heptane, the total volume of the reaction solution is 25mL, the mixed solution is transferred into a magnetic stirring kettle, and H-type 5% ZnO which is 5% of the total mass of the reactants is added 2 MCM-22, the gas in the kettle is replaced by high-purity nitrogen for 3 times. The reaction temperature is 150 ℃, the initial pressure is normal pressure, and the reaction time is 3 hours; after the reaction was completed, the reaction vessel was cooled in an ice-water bath. The main products are PX and by-products of 2, 5-hexanedione and 2, 5-dimethylbenzoic acid.
Example 16
Mixing 2,5-DMF and AA according to a molar ratio of 1:2, wherein the concentration of the 2,5-DMF is 0.3 mol.L -1 AA concentration of 0.6 mol.L -1 The solvent is n-heptane, the total volume of the reaction solution is 25mL, the mixed solution is transferred into a magnetic stirring kettle, and H-type 1% SnO which is 5% of the total mass of the reactants is added 2 MCM-22, the gas in the kettle is replaced by high-purity nitrogen for 3 times. The reaction temperature is 150 ℃, the initial pressure is normal pressure, and the reaction time is 3 hours; after the reaction was completed, the reaction vessel was cooled in an ice-water bath. The main products are PX and by-products of 2, 5-hexanedione and 2, 5-dimethylbenzoic acid.
Example 17
Mixing 2,5-DMF and AA according to a molar ratio of 1:2, wherein the concentration of the 2,5-DMF is 0.3 mol.L -1 AA concentration of 0.6 mol.L -1 The solvent is n-heptane, the total volume of the reaction solution is 25mL, the mixed solution is transferred into a magnetic stirring kettle, and H-type 3% SnO which is 5% of the total mass of the reactants is added 2 MCM-22, the gas in the kettle is replaced by high-purity nitrogen for 3 times. The reaction temperature is 150 ℃, the initial pressure is normal pressure, and the reaction time is 3 hours; reaction junctionAfter bundling, the reaction vessel was placed in an ice-water bath for cooling. The main products are PX and by-products of 2, 5-hexanedione and 2, 5-dimethylbenzoic acid.
Example 18
Mixing 2,5-DMF and AA according to a molar ratio of 1:2, wherein the concentration of the 2,5-DMF is 0.3 mol.L -1 AA concentration of 0.6 mol.L -1 The solvent is n-heptane, the total volume of the reaction solution is 25mL, the mixed solution is transferred into a magnetic stirring kettle, and H-type 5% SnO which is 5% of the total mass of the reactants is added 2 MCM-22, the gas in the kettle is replaced by high-purity nitrogen for 3 times. The reaction temperature is 150 ℃, the initial pressure is normal pressure, and the reaction time is 3 hours; after the reaction was completed, the reaction vessel was cooled in an ice-water bath. The main products are PX and by-products of 2, 5-hexanedione and 2, 5-dimethylbenzoic acid.
Example 19
Mixing 2,5-DMF and AA according to a molar ratio of 1:2, wherein the concentration of the 2,5-DMF is 0.3 mol.L -1 AA concentration of 0.6 mol.L -1 The solvent is n-heptane, the total volume of the reaction solution is 25mL, the mixed solution is transferred into a magnetic stirring kettle, and H-type 3% SnO which is 5% of the total mass of the reactants is added 2 MCM-22, the gas in the kettle is replaced by high-purity nitrogen for 3 times. The reaction temperature is 150 ℃, the initial pressure is normal pressure, and the reaction time is 5 hours; after the reaction was completed, the reaction vessel was cooled in an ice-water bath. The main products are PX and by-products of 2, 5-hexanedione and 2, 5-dimethylbenzoic acid.
Example 20
Mixing 2,5-DMF and AA according to a molar ratio of 1:2, wherein the concentration of the 2,5-DMF is 0.3 mol.L -1 AA concentration of 0.6 mol.L -1 The solvent is n-heptane, the total volume of the reaction solution is 25mL, the mixed solution is transferred into a magnetic stirring kettle, and H-type 3% SnO which is 5% of the total mass of the reactants is added 2 MCM-22, the gas in the kettle is replaced by high-purity nitrogen for 3 times. The reaction temperature is 150 ℃, the initial pressure is normal pressure, and the reaction time is 10 hours; after the reaction was completed, the reaction vessel was cooled in an ice-water bath. The main products are PX and by-products of 2, 5-hexanedione and 2, 5-dimethylbenzoic acid.
Example 21
Will 25-DMF and AA are mixed according to the mol ratio of 1:2, and the concentration of 2,5-DMF is 0.3 mol.L -1 AA concentration of 0.6 mol.L -1 The solvent is n-heptane, the total volume of the reaction solution is 25mL, the mixed solution is transferred into a magnetic stirring kettle, and H-type 3% SnO which is 5% of the total mass of the reactants is added 2 MCM-22, the gas in the kettle is replaced by high-purity nitrogen for 3 times. The reaction temperature is 170 ℃, the initial pressure is normal pressure, and the reaction time is 5 hours; after the reaction was completed, the reaction vessel was cooled in an ice-water bath. The main products are PX and by-products of 2, 5-hexanedione and 2, 5-dimethylbenzoic acid.
Example 22
Mixing 2,5-DMF and AA according to a molar ratio of 1:2, wherein the concentration of the 2,5-DMF is 0.3 mol.L -1 AA concentration of 0.6 mol.L -1 The solvent is n-heptane, the total volume of the reaction solution is 25mL, the mixed solution is transferred into a magnetic stirring kettle, and H-type 3% SnO which is 5% of the total mass of the reactants is added 2 MCM-22, the gas in the kettle is replaced by high-purity nitrogen for 3 times. The reaction temperature is 190 ℃, the initial pressure is normal pressure, and the reaction time is 5 hours; after the reaction was completed, the reaction vessel was cooled in an ice-water bath. The main products are PX and by-products of 2, 5-hexanedione and 2, 5-dimethylbenzoic acid.
The MCM-22 (P) without the template agent is placed in a muffle furnace to be roasted for 8 hours at 550 ℃ to obtain the Na-type MCM-22 molecular sieve. By 1.0 mol.L -1 NH 4 And (3) performing ion exchange on the Cl aqueous solution for 3 times, and performing suction filtration, washing and drying, and roasting in a muffle furnace at 550 ℃ for 4 hours to obtain the H-type MCM-22 molecular sieve.
Comparative example 1
Mixing 2,5-DMF and AA according to a molar ratio of 1:2, wherein the concentration of the 2,5-DMF is 0.3 mol.L -1 AA concentration of 0.6 mol.L -1 The solvent is n-heptane, the total volume of the reaction solution is 25mL, the mixed solution is transferred into a magnetic stirring kettle, H-type MCM-22 which is equivalent to 5% of the total mass of the reactants is added, and high-purity nitrogen is used for replacing the gas in the kettle for 3 times. The reaction temperature is 150 ℃, the initial pressure is normal pressure, and the reaction time is 5 hours; after the reaction was completed, the reaction vessel was cooled in an ice-water bath. The main products are PX and by-products of 2, 5-hexanedione and 2, 5-dimethylbenzoic acid.
Comparative example 2
Mixing 2,5-DMF and AA according to a molar ratio of 1:2, wherein the concentration of the 2,5-DMF is 0.3 mol.L -1 AA concentration of 0.6 mol.L -1 The solvent is n-heptane, the total volume of the reaction solution is 25mL, the mixed solution is transferred into a magnetic stirring kettle, H-type MCM-22 which is equivalent to 5% of the total mass of the reactants is added, and high-purity nitrogen is used for replacing the gas in the kettle for 3 times. The reaction temperature is 170 ℃, the initial pressure is normal pressure, and the reaction time is 5 hours; after the reaction was completed, the reaction vessel was cooled in an ice-water bath. The main products are PX and by-products of 2, 5-hexanedione and 2, 5-dimethylbenzoic acid.
Comparative example 3
Mixing 2,5-DMF and AA according to a molar ratio of 1:2, wherein the concentration of the 2,5-DMF is 0.3 mol.L -1 AA concentration of 0.6 mol.L -1 The solvent is n-heptane, the total volume of the reaction solution is 25mL, the mixed solution is transferred into a magnetic stirring kettle, H-type MCM-22 which is equivalent to 5% of the total mass of the reactants is added, and high-purity nitrogen is used for replacing the gas in the kettle for 3 times. The reaction temperature is 190 ℃, the initial pressure is normal pressure, and the reaction time is 5 hours; after the reaction was completed, the reaction vessel was cooled in an ice-water bath. The main products are PX and by-products of 2, 5-hexanedione and 2, 5-dimethylbenzoic acid.
The specific surface areas and catalytic activities of the catalysts obtained in examples 1 to 9 and the catalysts used in comparative examples 1 to 3 were compared, and the specific surface areas and catalytic activities are shown in the following table 1:
table 1 comparison of catalytic activities of examples 10 to 22 and comparative examples 1 to 3
As can be seen from Table 1, the MCM-22 molecular sieve has a modified molecular sieve, the catalytic activity of which is changed, and the most effective modified metal precursor is SnC 2 O 4 The catalytic activity is best when the metal loading is 3%;when the loading reaches 5%, the catalytic activity is reduced, which is probably that the Sn species cover part of the B acid sites on the outer surface of the molecular sieve. In comparison with comparative example 3, under the same reaction conditions, 3% SnO of H type 2 The 2,5-DMF conversion rate and PX selectivity of the MCM-22 are respectively 15 percent and 19 percent higher than those of the H-type MCM-22, and the former has obvious advantages.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. A method for synthesizing paraxylene by metal modified MCM-22 molecular sieve catalysis is characterized in that 2, 5-dimethylfuran and acrylic acid are used as reactants, the metal modified MCM-22 molecular sieve is used as a catalyst, and the molar ratio of the 2, 5-dimethylfuran to the acrylic acid is 1:2; the mass of the metal modified MCM-22 molecular sieve is 5% of the total mass of the reactants; the reaction is carried out in a magnetic stirring kettle; the reaction temperature is 150-190 ℃, the initial reaction pressure is normal pressure, and the reaction time is 3-10 h; nitrogen was used as a shielding gas.
2. The method for synthesizing paraxylene by metal-modified MCM-22 molecular sieve catalysis according to claim 1, wherein the metal-modified MCM-22 molecular sieve is ZrO 2 /MCM-22、ZnO 2 MCM-22 or SnO 2 Any one of MCM-22.
3. The method for synthesizing paraxylene by catalytic catalysis of a metal modified MCM-22 molecular sieve according to claim 1, wherein the preparation method of the metal modified MCM-22 molecular sieve is as follows:
(1) Placing a metal precursor and MCM-22 (P) without a template agent in a mortar for grinding uniformly, and roasting in a muffle furnace at 550 ℃ for 8 hours to obtain a Na-type modified MCM-22 molecular sieve;
(2) 1.0 mol.L of the Na-modified MCM-22 molecular sieve obtained in the step (1) is used -1 NH 4 Cl aqueous solution was carried out 3 timesIon exchange, suction filtering, washing, drying, roasting in a muffle furnace at 550 ℃ for 4 hours, and obtaining the metal modified MCM-22 molecular sieve.
4. The method for synthesizing paraxylene by metal-modified MCM-22 molecular sieve according to claim 3, wherein the metal precursor in the step (1) is ZrOCl 2 ·8H 2 O、Zn(NO 3 ) 2 ·6H 2 O or SnC 2 O 4 Any one of the following.
5. A process for the molecular sieve catalyzed synthesis of paraxylene of metal modified MCM-22 according to claim 3, characterized in that MCM-22 (P) without template in step (1) is prepared as follows:
(1) Dissolving 0.40 g-2.80 g NaOH in deionized water at room temperature, and adding 1.66g NaAlO 2 Stirring for 1h to obtain a clear and transparent solution;
(2) Then slowly dripping 6.94g of Hexamethyleneimine (HMI) into the solution obtained in the step (1), continuously stirring for 0.5h after the dripping is finished, slowly dripping 48.06g of silica sol (25 wt%) under the condition of intense stirring by using a peristaltic pump, adding 0.12g of seed crystal, and aging in a water bath at 25 ℃ for 24h to obtain a pale-cream yellow precursor, wherein the molar ratio of the pale-cream yellow precursor is as follows: 0.2SiO 2 ∶0.0067Al 2 O 3 ∶0.01～0.07NaOH∶0.07HMI∶6H 2 O；
(3) Transferring the pale cream yellow precursor obtained in the step (2) into a hydrothermal reaction kettle, and standing and crystallizing for 7 days in a baking oven at 150 ℃;
(4) And (3) carrying out suction filtration, washing and drying on the precursor subjected to standing crystallization in the step (3) to obtain the MCM-22 (P) without the template removal agent.
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