CN114163317A - Preparation method of p-hydroxyacetophenone - Google Patents
Preparation method of p-hydroxyacetophenone Download PDFInfo
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- CN114163317A CN114163317A CN202111508947.XA CN202111508947A CN114163317A CN 114163317 A CN114163317 A CN 114163317A CN 202111508947 A CN202111508947 A CN 202111508947A CN 114163317 A CN114163317 A CN 114163317A
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- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 48
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000002156 mixing Methods 0.000 claims abstract description 48
- 229910001868 water Inorganic materials 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 36
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 32
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims abstract description 32
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 31
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 23
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 23
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 16
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000012266 salt solution Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 230000010933 acylation Effects 0.000 claims description 11
- 238000005917 acylation reaction Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 9
- 239000012346 acetyl chloride Substances 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims 3
- 238000012986 modification Methods 0.000 claims 3
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000005618 Fries rearrangement reaction Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of p-hydroxyacetophenone, which is prepared by taking a modified catalyst as a catalyst; the preparation method of the modified catalyst comprises the following steps: uniformly mixing graphene oxide and water, adding n-butylamine, uniformly stirring, adding aluminum isopropoxide and sodium silicate, stirring at 70-85 ℃ for 3-5h, washing, raising to 100-185 ℃, crystallizing for 10-20h, washing, drying and roasting to obtain a material A; exchanging the material A by using an ammonium chloride aqueous solution, and calcining to obtain a material B; mixing citric acid, oxalic acid and water to obtain an acid solution, mixing the material B with the acid solution, heating to 70-80 ℃, stirring for 9-20h, washing with water to neutrality, and drying to obtain a material C; mixing lithium nitrate, ferric nitrate and cerous nitrate with water, mixing with the material C, stirring, standing, filtering, washing, drying, roasting, mixing with phosphotungstic acid, and ball-milling.
Description
Technical Field
The invention relates to the technical field of synthesis, and particularly relates to a preparation method of p-hydroxyacetophenone.
Background
P-hydroxyacetophenone, also known as 4' -hydroxyacetophenone, contains functional groups such as hydroxyl and keto groups attached to the benzene ring, and thus is often used as an intermediate for organic synthesis to participate in reactions with other molecules to synthesize many important compounds. Industrially, the p-hydroxyacetophenone is mainly prepared by taking phenol as a raw material and carrying out acylation and Fries rearrangement. In the traditional synthesis process, the adopted catalyst can shorten the reaction time, but the defects of low catalytic activity, poor product selectivity and the like exist, more byproducts are generated in the reaction process, and the yield and the purity of the p-hydroxyacetophenone are influenced.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of p-hydroxyacetophenone, which has the advantages of simple process, high yield and good purity of the obtained p-hydroxyacetophenone.
The invention provides a preparation method of p-hydroxyacetophenone, which is prepared by taking phenol and acetyl chloride as raw materials and taking a modified catalyst as a catalyst; the preparation method of the modified catalyst comprises the following steps:
s1, mixing graphene oxide with water, adding n-butylamine after uniform dispersion, adding aluminum isopropoxide and sodium silicate after uniform stirring, stirring for 30-60min at 25-30 ℃, heating to 70-85 ℃, stirring for 3-5h, washing with ethanol and deionized water, transferring to a polytetrafluoroethylene-lined high-pressure reaction kettle, heating to 100-130 ℃, crystallizing for 10-20h, heating to 150-185 ℃, crystallizing for 10-30h, washing with ethanol and deionized water, drying, roasting at 400-500 ℃, roasting for 30-60min, and roasting at 550-650 ℃ for 2-5h to obtain a material A;
s2, exchanging the material A by using an ammonium chloride aqueous solution, and then calcining for 2-5h at the temperature of 500-600 ℃ to obtain a material B;
s3, mixing citric acid, oxalic acid and water to obtain an acid solution, mixing the material B with the acid solution, heating to 70-80 ℃, stirring for 9-20 hours, washing with water to be neutral, and drying to obtain a material C;
s4, mixing lithium nitrate, ferric nitrate, cerium nitrate and water to obtain a metal salt solution, mixing the metal salt solution with the material C, stirring at 55-80 ℃ for 5-12h, standing for 1-3h, filtering, washing, drying, roasting at 400-450 ℃ for 1-3h, and roasting at 500-600 ℃ for 3-8h to obtain a material D;
and S5, mixing the material D with phosphotungstic acid, and then carrying out ball milling to obtain the modified catalyst.
Preferably, the preparation method of p-hydroxyacetophenone comprises the following steps: putting phenol and a modified catalyst into an acylation kettle, heating to 45-55 ℃, dropwise adding acetyl chloride under negative pressure, keeping the temperature in the acylation kettle not more than 120 ℃ in the dropwise adding process, preserving the temperature for 7-10 hours after dropwise adding, cooling, hydrolyzing, washing with water, separating a water layer, distilling, freezing, crystallizing and centrifuging to obtain the p-hydroxyacetophenone.
Preferably, the weight ratio of the phenol to the modified catalyst is 100: 0.3-1.5.
Preferably, in the preparation process of the modified catalyst, in S1, the molar ratio of the aluminum isopropoxide to the sodium silicate is 1: 55-65 parts; the mol ratio of the n-butylamine to the aluminum isopropoxide is 9-15: 1; the weight of the graphene oxide is 18-25% of the total weight of the aluminum isopropoxide and the sodium silicate.
Preferably, in the preparation process of the modified catalyst, in S2, the concentration of the ammonium chloride aqueous solution is 0.5-1.5 mol/L; the exchange comprises primary exchange and secondary exchange, and the time of the primary exchange and the time of the secondary exchange are both 6-7 h.
Preferably, in the preparation process of the modified catalyst, in S3, the concentration of citric acid in the acid solution is 0.11-0.15mol/L, and the concentration of oxalic acid in the acid solution is 0.05-0.38 mol/L; the weight volume ratio of the material B to the acid solution is 1g/26-33 ml.
Preferably, in the preparation process of the modified catalyst, in S4, the concentration of lithium nitrate in the metal salt solution is 1.3-2.2mol/L, the concentration of ferric nitrate is 0.7-1.2mol/L, and the concentration of cerium nitrate is 0.1-0.3 mol/L.
Preferably, in the preparation process of the modified catalyst, in S5, the weight ratio of the material D to the phosphotungstic acid is 5-13: 1.
according to the preparation method of the p-hydroxyacetophenone, in the preparation process of the modified catalyst, firstly, graphene oxide, n-butylamine, aluminum isopropoxide and sodium silicate are used as raw materials, reaction conditions are controlled, a graphene material A loaded with a molecular sieve is obtained, the molecular sieve in the material A is uniformly loaded on the surface of graphene, the graphene has an interface induction effect on the formation of the molecular sieve, so that the molecular sieve forms a rich mesoporous structure and an acid catalytic site, and is matched with the graphene for a concerted catalytic reaction; then, a material B obtained after the exchange of an ammonium chloride aqueous solution is treated by using a mixed solution of citric acid, oxalic acid and water, the specific surface area, the pore volume and the pore size of the material B are improved while the molecular sieve framework is maintained, more acid sites are exposed, the obtained material C is used as a carrier and is mixed with a metal salt solution containing lithium nitrate, ferric nitrate and cerium nitrate, more metal active components of lithium, iron and cerium are introduced into the material C, the micropore structure of the material C is changed, and a modified catalyst obtained by ball milling after the material C is mixed with phosphotungstic acid has the effects of graphene, a molecular sieve, metal and phosphotungstic acid, is cooperatively catalyzed, has good selectivity on hydroxyacetophenone, and ensures that the yield of the obtained p-hydroxyacetophenone is high and reaches more than 97.1 percent, and the purity of the p-hydroxyacetophenone reaches more than 99.7 percent.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
The invention provides a preparation method of p-hydroxyacetophenone, which is prepared by taking phenol and acetyl chloride as raw materials and taking a modified catalyst as a catalyst; the weight ratio of the phenol to the modified catalyst is 100: 1.5; the preparation method of the modified catalyst comprises the following steps:
s1, mixing the graphene oxide with water, adding n-butylamine after the graphene oxide is uniformly dispersed, and adding aluminum isopropoxide and sodium silicate after the graphene oxide is uniformly stirred, wherein the molar ratio of the aluminum isopropoxide to the sodium silicate is 1: 55; the mol ratio of n-butylamine to aluminum isopropoxide is 11: 1; the weight of the graphene oxide is 19% of the total weight of aluminum isopropoxide and sodium silicate, the graphene oxide is stirred at 30 ℃ for 30min, then is heated to 85 ℃ and stirred for 3h, is washed by ethanol and deionized water, is transferred to a high-pressure reaction kettle with a polytetrafluoroethylene lining, is heated to 110 ℃ for crystallization for 18h, is heated to 150 ℃ for crystallization for 20h, is washed by ethanol and deionized water, is dried, is roasted at 400 ℃ for 60min, and is roasted at 550 ℃ for 5h to obtain a material A;
s2, exchanging the material A by using 0.5mol/L ammonium chloride aqueous solution, and then calcining for 3 hours at 500 ℃ to obtain a material B; the exchange comprises primary exchange and secondary exchange, and the time of the primary exchange and the time of the secondary exchange are both 7 h;
s3, mixing citric acid, oxalic acid and water to obtain an acid solution, wherein the concentration of the citric acid is 0.11mol/L and the concentration of the oxalic acid is 0.38mol/L, mixing a material B and the acid solution, wherein the weight-volume ratio of the material B to the acid solution is 1g/26ml, heating to 73 ℃, stirring for 9 hours, washing with water to neutrality, and drying to obtain a material C;
s4, mixing lithium nitrate, ferric nitrate, cerium nitrate and water to obtain a metal salt solution, wherein the concentration of the lithium nitrate is 1.3mol/L, the concentration of the ferric nitrate is 1.2mol/L, and the concentration of the cerium nitrate is 0.1 mol/L; mixing the metal salt solution with the material C, stirring for 12h at 55 ℃, standing for 1h, filtering, washing, drying, roasting for 1h at 450 ℃, and then roasting for 3h at 600 ℃ to obtain a material D;
s5, mixing the material D with phosphotungstic acid, and then performing ball milling to obtain the modified catalyst; the weight ratio of the material D to the phosphotungstic acid is 10: 1.
example 2
The invention provides a preparation method of p-hydroxyacetophenone, which is prepared by taking phenol and acetyl chloride as raw materials and taking a modified catalyst as a catalyst; the weight ratio of the phenol to the modified catalyst is 100: 0.3; the preparation method of the modified catalyst comprises the following steps:
s1, mixing the graphene oxide with water, adding n-butylamine after the graphene oxide is uniformly dispersed, adding aluminum isopropoxide and sodium silicate after the graphene oxide is uniformly stirred, wherein the molar ratio of the aluminum isopropoxide to the sodium silicate is 1: 60, adding a solvent to the mixture; the mol ratio of the n-butylamine to the aluminum isopropoxide is 15: 1; the weight of the graphene oxide is 25% of the total weight of aluminum isopropoxide and sodium silicate, the graphene oxide is stirred at 25 ℃ for 60min, then is heated to 70 ℃ and stirred for 5h, is washed by ethanol and deionized water and then is transferred to a polytetrafluoroethylene-lined high-pressure reaction kettle, is heated to 100 ℃ for crystallization for 20h, is heated to 180 ℃ for crystallization for 30h, is washed by ethanol and deionized water and then is dried, is roasted at 500 ℃ for 30min, and is then roasted at 650 ℃ for 2h to obtain a material A;
s2, exchanging the material A by using 1mol/L ammonium chloride aqueous solution, wherein the exchange comprises primary exchange and secondary exchange, the time of the primary exchange and the time of the secondary exchange are both 6h, and then calcining for 2h at 600 ℃ to obtain a material B;
s3, mixing citric acid, oxalic acid and water to obtain an acid solution, wherein the concentration of the citric acid is 0.15mol/L and the concentration of the oxalic acid is 0.05mol/L, mixing a material B and the acid solution, the weight-volume ratio of the material B to the acid solution is 1g/33ml, heating to 80 ℃, stirring for 20 hours, washing with water to be neutral, and drying to obtain a material C;
s4, mixing lithium nitrate, ferric nitrate, cerium nitrate and water to obtain a metal salt solution, wherein the concentration of the lithium nitrate is 2.2mol/L, the concentration of the ferric nitrate is 0.7mol/L and the concentration of the cerium nitrate is 0.18mol/L, mixing the metal salt solution with the material C, stirring for 5 hours at 80 ℃, standing for 3 hours, filtering, washing, drying, roasting for 3 hours at 400 ℃, and then roasting for 8 hours at 500 ℃ to obtain a material D;
s5, mixing the material D with phosphotungstic acid, and then performing ball milling to obtain the modified catalyst; the weight ratio of the material D to the phosphotungstic acid is 13: 1.
example 3
The invention provides a preparation method of p-hydroxyacetophenone, which comprises the following steps: putting phenol and a modified catalyst into an acylation kettle, wherein the weight ratio of the phenol to the modified catalyst is 100: 0.5, heating to 55 ℃, dropwise adding acetyl chloride under negative pressure, keeping the temperature in the acylation kettle at 110 ℃ in the dropwise adding process, preserving the temperature for 7 hours after dropwise adding, cooling, hydrolyzing, washing with water, separating a water layer, distilling, freezing, crystallizing and centrifuging to obtain p-hydroxyacetophenone;
the preparation method of the modified catalyst comprises the following steps:
s1, mixing the graphene oxide with water, adding n-butylamine after the graphene oxide is uniformly dispersed, adding aluminum isopropoxide and sodium silicate after the graphene oxide is uniformly stirred, wherein the molar ratio of the aluminum isopropoxide to the sodium silicate is 1: 65; the mol ratio of the n-butylamine to the aluminum isopropoxide is 9: 1; the weight of the graphene oxide is 18% of the total weight of aluminum isopropoxide and sodium silicate, the graphene oxide is stirred at 28 ℃ for 40min, then is heated to 80 ℃ and stirred for 3h, is washed by ethanol and deionized water and then is transferred to a polytetrafluoroethylene-lined high-pressure reaction kettle, is heated to 130 ℃ for crystallization for 10h, is heated to 185 ℃ for crystallization for 10h, is washed by ethanol and deionized water and then is dried, is roasted at 480 ℃ for 45min, and is then roasted at 600 ℃ for 3h to obtain a material A;
s2, exchanging the material A by using an ammonium chloride aqueous solution with the concentration of 1.2mol/L, and then calcining for 5 hours at 580 ℃ to obtain a material B; the exchange comprises primary exchange and secondary exchange, and the time of the primary exchange and the time of the secondary exchange are both 6 h;
s3, mixing citric acid, oxalic acid and water to obtain an acid solution, wherein the concentration of the citric acid is 0.14mol/L and the concentration of the oxalic acid is 0.1 mol/L; mixing a material B with an acid solution, wherein the weight volume ratio of the material B to the acid solution is 1g/30ml, heating to 70 ℃, stirring for 15h, washing with water to be neutral, and drying to obtain a material C;
s4, mixing lithium nitrate, ferric nitrate, cerium nitrate and water to obtain a metal salt solution, wherein in the metal salt solution, the concentration of the lithium nitrate is 2mol/L, the concentration of the ferric nitrate is 0.8mol/L, and the concentration of the cerium nitrate is 0.3 mol/L; mixing the metal salt solution with the material C, stirring for 10h at 60 ℃, standing for 1h, filtering, washing, drying, roasting for 1h at 440 ℃, and then roasting for 4h at 580 ℃ to obtain a material D;
s5, mixing the material D with phosphotungstic acid, and then performing ball milling to obtain the modified catalyst; the weight ratio of the material D to the phosphotungstic acid is 5: 1.
example 4
The invention provides a preparation method of p-hydroxyacetophenone, which comprises the following steps: putting phenol and a modified catalyst into an acylation kettle, wherein the weight ratio of the phenol to the modified catalyst is 100: 1.3, heating to 45 ℃, dropwise adding acetyl chloride under negative pressure, keeping the temperature in the acylation kettle at 100 ℃ in the dropwise adding process, preserving the temperature for 10 hours after dropwise adding, cooling, hydrolyzing, washing with water, separating a water layer, distilling, freezing, crystallizing and centrifuging to obtain p-hydroxyacetophenone;
the preparation method of the modified catalyst comprises the following steps:
s1, mixing the graphene oxide with water, adding n-butylamine after the graphene oxide is uniformly dispersed, adding aluminum isopropoxide and sodium silicate after the graphene oxide is uniformly stirred, wherein the molar ratio of the aluminum isopropoxide to the sodium silicate is 1: 58; the molar ratio of n-butylamine to aluminum isopropoxide is 13: 1; the weight of the graphene oxide is 22% of the total weight of aluminum isopropoxide and sodium silicate, the graphene oxide is stirred at 26 ℃ for 55min, then heated to 75 ℃ and stirred for 4h, washed by ethanol and deionized water, transferred to a polytetrafluoroethylene-lined high-pressure reaction kettle, heated to 100 ℃ for crystallization for 14h, then heated to 158 ℃ for crystallization for 18h, washed by ethanol and deionized water, dried, roasted at 420 ℃ for 60min, and then roasted at 550 ℃ for 4h to obtain a material A;
s2, exchanging the material A by using an ammonium chloride aqueous solution with the concentration of 0.8mol/L, and then calcining for 3 hours at 550 ℃ to obtain a material B; the exchange comprises primary exchange and secondary exchange, and the time of the primary exchange and the time of the secondary exchange are both 7 h;
s3, mixing citric acid, oxalic acid and water to obtain an acid solution, wherein the concentration of the citric acid is 0.12mol/L and the concentration of the oxalic acid is 0.3 mol/L; mixing a material B with an acid solution, wherein the weight volume ratio of the material B to the acid solution is 1g/28ml, heating to 72 ℃, stirring for 12 hours, washing with water to be neutral, and drying to obtain a material C;
s4, mixing lithium nitrate, ferric nitrate, cerium nitrate and water to obtain a metal salt solution, wherein the concentration of the lithium nitrate is 1.5mol/L, the concentration of the ferric nitrate is 1mol/L, and the concentration of the cerium nitrate is 0.18 mol/L; mixing the metal salt solution with the material C, stirring for 6h at 70 ℃, standing for 2h, filtering, washing, drying, roasting for 3h at 420 ℃, and then roasting for 7h at 500 ℃ to obtain a material D;
s5, mixing the material D with phosphotungstic acid, and then performing ball milling to obtain the modified catalyst; the weight ratio of the material D to the phosphotungstic acid is 8: 1.
example 5
The invention provides a preparation method of p-hydroxyacetophenone, which comprises the following steps: putting phenol and a modified catalyst into an acylation kettle, wherein the weight ratio of the phenol to the modified catalyst is 100: 1, heating to 52 ℃, dropwise adding acetyl chloride under negative pressure, keeping the temperature in an acylation kettle at 115 ℃ in the dropwise adding process, preserving the temperature for 8 hours after dropwise adding, cooling, hydrolyzing, washing, separating a water layer, distilling, freezing, crystallizing and centrifuging to obtain p-hydroxyacetophenone;
the preparation method of the modified catalyst comprises the following steps:
s1, mixing the graphene oxide with water, adding n-butylamine after the graphene oxide is uniformly dispersed, adding aluminum isopropoxide and sodium silicate after the graphene oxide is uniformly stirred, wherein the molar ratio of the aluminum isopropoxide to the sodium silicate is 1: 59; the molar ratio of n-butylamine to aluminum isopropoxide is 13: 1; the weight of the graphene oxide is 22% of the total weight of aluminum isopropoxide and sodium silicate, the graphene oxide is stirred for 50min at 28 ℃, heated to 80 ℃ and stirred for 3h, washed by ethanol and deionized water, transferred to a polytetrafluoroethylene-lined high-pressure reaction kettle, heated to 110 ℃ for crystallization for 11h, then heated to 170 ℃ for crystallization for 18h, washed by ethanol and deionized water, dried, roasted at 430 ℃ for 45min, and then roasted at 600 ℃ for 4h to obtain a material A;
s2, exchanging the material A by using an ammonium chloride aqueous solution with the concentration of 0.9mol/L, and then calcining at 560 ℃ for 2.5h to obtain a material B; the exchange comprises primary exchange and secondary exchange, and the time of the primary exchange and the time of the secondary exchange are both 6.5 h;
s3, mixing citric acid, oxalic acid and water to obtain an acid solution, wherein the concentration of the citric acid is 0.13mol/L and the concentration of the oxalic acid is 0.33 mol/L; mixing a material B with an acid solution, wherein the weight volume ratio of the material B to the acid solution is 1g/29ml, heating to 76 ℃, stirring for 12 hours, washing with water to be neutral, and drying to obtain a material C;
s4, mixing lithium nitrate, ferric nitrate, cerium nitrate and water to obtain a metal salt solution, wherein the concentration of the lithium nitrate is 1.8mol/L, the concentration of the ferric nitrate is 1mol/L, and the concentration of the cerium nitrate is 0.2 mol/L; mixing the metal salt solution with the material C, stirring for 8h at 70 ℃, standing for 2h, filtering, washing, drying, roasting for 1h at 430 ℃, and then roasting for 4h at 570 ℃ to obtain a material D;
s5, mixing the material D and phosphotungstic acid according to the weight ratio of 6: 1, and ball-milling to obtain the modified catalyst.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. The preparation method of p-hydroxyacetophenone is characterized in that phenol and acetyl chloride are used as raw materials, and a modified catalyst is used as a catalyst to prepare the p-hydroxyacetophenone; the preparation method of the modified catalyst comprises the following steps:
s1, mixing graphene oxide with water, adding n-butylamine after uniform dispersion, adding aluminum isopropoxide and sodium silicate after uniform stirring, stirring for 30-60min at 25-30 ℃, heating to 70-85 ℃, stirring for 3-5h, washing with ethanol and deionized water, transferring to a polytetrafluoroethylene-lined high-pressure reaction kettle, heating to 100-130 ℃, crystallizing for 10-20h, heating to 150-185 ℃, crystallizing for 10-30h, washing with ethanol and deionized water, drying, roasting at 400-500 ℃, roasting for 30-60min, and roasting at 550-650 ℃ for 2-5h to obtain a material A;
s2, exchanging the material A by using an ammonium chloride aqueous solution, and then calcining for 2-5h at the temperature of 500-600 ℃ to obtain a material B;
s3, mixing citric acid, oxalic acid and water to obtain an acid solution, mixing the material B with the acid solution, heating to 70-80 ℃, stirring for 9-20 hours, washing with water to be neutral, and drying to obtain a material C;
s4, mixing lithium nitrate, ferric nitrate, cerium nitrate and water to obtain a metal salt solution, mixing the metal salt solution with the material C, stirring at 55-80 ℃ for 5-12h, standing for 1-3h, filtering, washing, drying, roasting at 400-450 ℃ for 1-3h, and roasting at 500-600 ℃ for 3-8h to obtain a material D;
and S5, mixing the material D with phosphotungstic acid, and then carrying out ball milling to obtain the modified catalyst.
2. The method for preparing p-hydroxyacetophenone according to claim 1, characterized by comprising the steps of: putting phenol and a modified catalyst into an acylation kettle, heating to 45-55 ℃, dropwise adding acetyl chloride under negative pressure, keeping the temperature in the acylation kettle not more than 120 ℃ in the dropwise adding process, preserving the temperature for 7-10 hours after dropwise adding, cooling, hydrolyzing, washing with water, separating a water layer, distilling, freezing, crystallizing and centrifuging to obtain the p-hydroxyacetophenone.
3. The method for preparing p-hydroxyacetophenone according to claim 1, wherein the weight ratio of the phenol to the modification catalyst is 100: 0.3-1.5.
4. The method for preparing p-hydroxyacetophenone according to claim 1, wherein in the preparation process of the modified catalyst, the molar ratio of aluminum isopropoxide to sodium silicate in S1 is 1: 55-65 parts; the mol ratio of the n-butylamine to the aluminum isopropoxide is 9-15: 1; the weight of the graphene oxide is 18-25% of the total weight of the aluminum isopropoxide and the sodium silicate.
5. The method for preparing p-hydroxyacetophenone according to claim 1, wherein in the preparation of the modified catalyst, the concentration of the aqueous ammonium chloride solution in S2 is 0.5 to 1.5 mol/L; the exchange comprises primary exchange and secondary exchange, and the time of the primary exchange and the time of the secondary exchange are both 6-7 h.
6. The method for preparing p-hydroxyacetophenone according to claim 1, wherein in the preparation of the modification catalyst, in S3, the concentration of citric acid is 0.11 to 0.15mol/L and the concentration of oxalic acid is 0.05 to 0.38 mol/L; the weight volume ratio of the material B to the acid solution is 1g/26-33 ml.
7. The method for preparing p-hydroxyacetophenone according to claim 1, wherein in the preparation process of the modification catalyst, in S4, the concentration of lithium nitrate is 1.3 to 2.2mol/L, the concentration of ferric nitrate is 0.7 to 1.2mol/L, and the concentration of cerium nitrate is 0.1 to 0.3 mol/L.
8. The process for producing p-hydroxyacetophenone according to any one of claims 1 to 7, characterized in that in the preparation of the modified catalyst, the weight ratio of the material D to the phosphotungstic acid in S5 is 5 to 13: 1.
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