CN116020438A - Solid acid catalyst, preparation method thereof and application of solid acid catalyst in deprotection reaction of p-tert-butoxyphenethyl methyl ether - Google Patents
Solid acid catalyst, preparation method thereof and application of solid acid catalyst in deprotection reaction of p-tert-butoxyphenethyl methyl ether Download PDFInfo
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- 239000011973 solid acid Substances 0.000 title claims abstract description 42
- 238000010511 deprotection reaction Methods 0.000 title claims abstract description 26
- HBOCSQWJBVYGQZ-UHFFFAOYSA-N 1-(2-methoxyethyl)-4-[(2-methylpropan-2-yl)oxy]benzene Chemical compound COCCC1=CC=C(OC(C)(C)C)C=C1 HBOCSQWJBVYGQZ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 24
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- 238000011068 loading method Methods 0.000 claims description 15
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- 238000010438 heat treatment Methods 0.000 claims description 13
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- 150000003839 salts Chemical class 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 8
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- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
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- 238000011156 evaluation Methods 0.000 description 23
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- 239000000047 product Substances 0.000 description 14
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000012847 fine chemical Substances 0.000 description 9
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 8
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- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- -1 fluoride ions Chemical class 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
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- 239000000376 reactant Substances 0.000 description 5
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- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
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- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
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- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
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- 229910052726 zirconium Inorganic materials 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- IUBSYMUCCVWXPE-UHFFFAOYSA-N metoprolol Chemical compound COCCC1=CC=C(OCC(O)CNC(C)C)C=C1 IUBSYMUCCVWXPE-UHFFFAOYSA-N 0.000 description 1
- 229960002237 metoprolol Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a solid acid catalyst, a preparation method thereof and application of the catalyst in deprotection reaction of p-tert-butoxyphenethyl methyl ether. The invention has the advantages of less three-waste discharge, low operation cost and high production efficiency, and is suitable for continuous production of the- (2-methoxy) ethylphenol.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, relates to a solid acid catalyst for deprotection reaction, a preparation method and application thereof, and in particular relates to a solid acid catalyst for producing p- (2-methoxy) ethylphenol, a preparation method thereof and application thereof in a continuous process of deprotection reaction of p-tert-butoxyphenethyl methyl ether.
Background
Protecting agent such as isobutene is used to protect some active functional groups of the reactant, and deprotection reaction is a common method in the synthesis field. At present, liquid acid is mainly used as a catalyst for catalyzing deprotection (tertiary butyl) reaction in the field of fine chemical industry. The liquid acid catalyst has the advantages of high catalytic activity, low price and the like, but the liquid acid catalyst needs neutralization, water washing and other operations after the reaction is finished, and has the defects of more three wastes discharge, complex process and the like. The solid acid catalyst has the advantages of easy separation, less three-waste discharge and the like, and has wide application in the petrochemical industry field. The petrochemical products have smaller reaction molecules, low boiling point and easy gasification, and generally adopt gas-solid phase reaction; the fine chemical products have larger reaction molecules, high boiling point, difficult gasification and liquid phase reaction. Therefore, the conventional solid acid catalyst in the petrochemical field is often not suitable for the fine chemical field.
Patent CN106955687B discloses a catalyst for preparing isoamylene by cracking methyl tertiary amyl ether. The invention takes sulfate radical and fluoride ion modified alumina as catalyst, the reaction temperature is 160 ℃, and the conversion rate and selectivity reach more than 95%. Although the catalyst has higher catalytic activity, sulfate ions and fluoride ions are easy to lose, so the catalyst is only suitable for gas-solid phase reaction. For liquid phase reaction, sulfate ions and fluoride ions are easy to run off, so that the activity of the catalyst is reduced, and equipment such as a reactor and the like are corroded. The molecular weight of the fine chemical products is large, the boiling point is high, the molecular structure is unstable at high temperature, and liquid phase reaction is usually adopted, so that the development of a solid acid catalyst suitable for the liquid phase reaction is required.
Patent CN111530379a discloses a process for preparing isobutene by cracking methyl tert-butyl ether, which adopts sulfonic acid resin as a catalyst. The sulfonic acid resin catalyst has stronger acidity and catalytic activity, but has poor high temperature resistance, and when the reaction temperature exceeds 120 ℃, the active components of the catalyst are easy to decompose and fall off. The high temperature resistance of the sulfonic acid resin is poor, so that the catalytic activity of the sulfonic acid resin catalyst cannot be recovered through high temperature roasting regeneration after the inactivation of the sulfonic acid resin catalyst. The sulfonic acid resin has the defects of poor high temperature resistance, incapability of regeneration after inactivation and the like, and limits the application of the sulfonic acid resin in the field of refinement industry.
Patent CN100482629C discloses a method for synthesizing p- (2-methoxy) ethylphenol, wherein the last step of deprotection reaction of p-tert-butoxyphenethyl methyl ether adopts liquid acid (sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid) as catalyst to catalyze the deprotection reaction. The method has higher reactant conversion rate and product selectivity, but generates a large amount of waste water and waste acid, and a special material reactor is needed to avoid the problem of equipment corrosion.
Patent CN109651094B discloses a process for the preparation of p- (2-methoxy) ethylphenol, wherein the last step p-tert-butoxyphenethyl methyl ether is deprotected under the action of a catalyst thionyl chloride. The method has higher reactant conversion rate and product selectivity, but has higher toxicity of thionyl chloride, generates a large amount of toxic and harmful substances, and is not friendly to the environment.
In summary, in the field of fine chemical industry, the catalyst for the deprotection reaction process is mainly liquid acid to generate a large amount of waste acid, waste water and toxic and harmful substances, and the deprotection reaction in the synthesis of the p- (2-methoxy) ethylphenol is an intermittent process, so that the production period of the product is long, the quality of the product is unstable, and the flexible production is difficult to realize. However, the solid acid catalyst commonly used in the petrochemical industry is not suitable for the production of fine chemical products, so that the development of the solid acid catalyst suitable for the production of fine chemical products and the continuous deprotection reaction production process are urgently needed.
Disclosure of Invention
The invention aims to provide a solid acid catalyst for deprotection reaction, a preparation method and application thereof, so as to solve the problems of environmental protection caused by taking liquid acid as a catalyst in the deprotection reaction and low efficiency caused by a discontinuous process. The invention adopts the solid acid catalyst to replace the liquid acid catalyst to catalyze the deprotection reaction of the p-tert-butoxyphenethyl methyl ether, has the advantages of less three-waste discharge and the like, can realize the continuous production operation of the deprotection reaction of the p-tert-butoxyphenethyl methyl ether by combining with a fixed bed reactor, and is suitable for the continuous production of the p- (2-methoxy) ethylphenol.
The invention provides a solid acid catalyst, which comprises gamma alumina and acidic metal oxide modified on the gamma alumina, wherein the metallic elements contained in the acidic metal oxide comprise: one or two of Nb, V, mo, W, zr or Ti.
Gamma alumina is the most common catalyst support in industry, which is inexpensive and has high mechanical strength, but is generally used as a support for preparing a catalyst due to weak acidity itself. The acidic oxides such as Nb, V, mo, W, zr, ti oxides and the like have stronger acidity, and the gamma alumina is modified by adopting the acidic oxides to prepare the solid acid catalyst, which has stronger acidity than the gamma alumina, high thermal stability and difficult loss of active components, and is suitable for liquid phase reaction.
In the invention, the catalyst carrier is gamma alumina with specific surface area of 100-250 m 2 Per gram, the pore volume is 0.2-1.0 cm 3 And/g, the average pore diameter is 10-20 nm.
Preferably, the loading amount of the metal element (excluding oxygen) on the gamma alumina is 5 to 20wt% based on the mass of the metal.
Preferably, the metal element is a combination of Nb and other metals;
the other metal is V, mo, W, zr or Ti, and the reaction selectivity is high, and preferably, the mass ratio of Nb to the other metal is 1:0.5 to 2.
The invention also provides a preparation method of the solid acid catalyst for the deprotection reaction, which comprises the following steps:
heating an aqueous solution containing Nb, V, mo, W, zr or Ti salts, adding gamma alumina, modifying by an impregnation method, and drying and roasting to obtain the solid acid catalyst.
Preferably, the impregnation method is a primary impregnation method or a secondary impregnation method;
in the secondary impregnation method, after the first impregnation is completed, drying is performed first, and then the second impregnation is performed.
Preferably, when the metal element is a combination of Nb and other metals, the preparation method is as follows:
heating an aqueous solution of Nb-containing salt, then adding gamma alumina, modifying by adopting an impregnation method, and drying and roasting to obtain a Nb-modified gamma alumina catalyst; then heating the water solution containing the salt of V, mo, W, zr or Ti, adding the Nb modified gamma alumina catalyst, adopting an impregnation method for modification, and drying and roasting to obtain the solid acid catalyst.
Preferably, the heating temperature is 45-55 ℃, and the soaking time is 20-40 minutes;
the drying temperature is 110-120 ℃, and the drying time is 10-12 hours;
the roasting temperature is 350-450 ℃, and the roasting time is 4-6 hours.
Preferably, the salt containing Nb, V, mo, W, zr or Ti is niobium oxalate, ammonium metavanadate, ammonium molybdate, ammonium tungstate pentahydrate, zirconium nitrate pentahydrate or n-butyl titanate.
The preparation method of the gamma alumina solid acid catalyst modified by the acid oxide by adopting the one-time impregnation method comprises the following specific steps:
heating an aqueous solution containing Nb, V, mo, W, zr or Ti salts to 50 ℃, immersing gamma alumina in the solution for 30 minutes, drying at 110 ℃ for 12 hours, and then roasting at 350-500 ℃ for 4 hours in air or nitrogen atmosphere to prepare the solid acid catalyst.
The preparation method of the gamma alumina solid acid catalyst modified by the acid oxide by adopting a secondary impregnation method comprises the following specific steps:
heating an aqueous solution of Nb, V, mo, W, zr or Ti-containing salt to 50 ℃, immersing gamma alumina in the solution for 30 minutes, drying at 110 ℃ for 12 hours, immersing the dried catalyst in the same aqueous solution of Nb, V, mo, W, zr or Ti-containing salt for the second time, standing for 30 minutes, drying at 110 ℃ for 12 hours, and roasting at 350-500 ℃ for 4 hours in air or nitrogen atmosphere to obtain the solid acid catalyst.
Two combined type acid oxide modified gamma alumina solid acid catalysts are prepared by adopting an impregnation method, and the specific steps are as follows:
an aqueous solution of a Nb-containing salt was heated to 50 ℃, gamma alumina was immersed in the above solution for 30 minutes, dried at 110 ℃ for 12 hours, and then calcined at high temperature in air or nitrogen atmosphere for 4 hours, to obtain a Nb-modified gamma alumina catalyst. Then the obtained Nb modified gamma alumina catalyst is put into the water solution containing Mo, W or Zr salts of different types, and is stood for 30 minutes, dried for 12 hours at 110 ℃, and then baked for 4 hours at 350-450 ℃ in air or nitrogen atmosphere, thus obtaining the solid acid catalyst.
The p- (2-methoxy) ethylphenol is a key intermediate for synthesizing the medicine metoprolol, the last reaction of the synthesis of the p- (2-methoxy) ethylphenol is performed with deprotection reaction on the p-tert-butoxyphenethyl methyl ether under the acid catalysis condition, and the target product p- (2-methoxy) ethylphenol is obtained. In the reaction of the step, the inventor finds that the solid acid catalyst modified by gamma alumina can be utilized to catalyze the deprotection reaction of the p-tert-butoxyphenethyl methyl ether under normal pressure, the reaction can realize continuous production by using a fixed bed continuous reactor, the reaction temperature is 120-200 ℃, and the liquid space velocity is 0.5-2 h -1 . Therefore, the invention also provides the application of the solid acid catalyst in the deprotection reaction of the p-tert-butoxyphenethyl methyl ether.
The performance of the solid acid catalyst prepared by the above method was evaluated under the condition that a spherical catalyst having a diameter of 2mm was packed into a stainless steel fixed bed reactor having an inner diameter of 15 mm. And starting the heating furnace, starting the plunger pump after the temperature of the catalyst bed reaches the set temperature, and controlling the feeding amount of the reactant p-tert-butoxyphenethyl methyl ether by adopting the plunger pump. The reaction liquid enters a gas-liquid separator after passing through a catalyst bed layer of a fixed bed reactor, liquid products are collected, and the gas products (isobutene) are emptied. The liquid product was quantitatively analyzed using a gas chromatograph, and the conversion and selectivity were calculated.
Compared with the prior art, the invention has the beneficial effects that:
1) The invention adopts the solid acid catalyst to replace the liquid acid catalyst for catalyzing the deprotection reaction, has little three-waste discharge, can realize the continuous production operation of the deprotection reaction by combining with the fixed bed reactor, and is suitable for the production of large-tonnage chemical products.
2) The invention adopts the supported solid acid catalyst and combines a fixed bed continuous reactor to catalyze the deprotection reaction of the p-tert-butoxyphenethyl methyl ether, the highest selectivity can reach 99 percent, and the invention has the advantages of simple operation, continuous production and the like, and also accords with the development direction of green, continuous and intelligent fine chemical industry in the future.
Drawings
FIG. 1 is a result of examining the life of a catalyst according to example 17 of the present invention.
Detailed Description
Evaluation conditions of catalyst performance: spherical catalyst with a diameter of 2mm was packed into a stainless steel fixed bed reactor with an inner diameter of 15 mm. And starting the heating furnace, starting the plunger pump after the temperature of the catalyst bed reaches the set temperature, and controlling the feeding amount of the reactant p-tert-butoxyphenethyl methyl ether by adopting the plunger pump. The reaction liquid enters a gas-liquid separator after passing through a catalyst bed layer of a fixed bed reactor, liquid products are collected, and the gas products (isobutene) are emptied. The liquid product was quantitatively analyzed (normalization) using a gas chromatograph, and the conversion and selectivity were calculated.
Example 1
Adopting Nb modified gamma alumina as catalyst, wherein the Nb loading is 5wt%, and the specific surface area of the gamma alumina is 150m 2 Per g, pore volume of 0.5cm 3 And/g, average pore diameter of 16nm. The preparation method of the catalyst comprises the following steps: 1.73g of niobium oxalate was dissolved in 6g of deionized water, heated to 50 ℃, 6g of gamma alumina was poured into the above solution, left to stand for 30 minutes, dried at 110℃for 12 hours, and calcined at 450℃for 4 hours in an air atmosphere, to prepare a catalyst. The catalyst performance evaluation results are shown in Table 1, the reaction temperature is 140 ℃ and the liquid space velocity is 1h -1 The reaction pressure is normal pressure.
Example 2
Nb modified gamma alumina is used as a catalyst, wherein the Nb loading is 10wtThe specific surface area of the gamma alumina is 210m 2 Per g, pore volume of 0.6cm 3 And/g, average pore diameter of 12nm. The preparation method of the catalyst comprises the following steps: 3.47g of niobium oxalate was dissolved in 6g of deionized water, heated to 50 ℃, 6g of gamma alumina was poured into the above solution, left to stand for 30 minutes, dried at 110 ℃ for 12 hours, and calcined at 450 ℃ for 4 hours in an air atmosphere to prepare a catalyst. The catalyst performance evaluation results are shown in Table 1, the reaction temperature is 170 ℃ and the liquid space velocity is 1h -1 The reaction pressure is normal pressure.
Example 3
Adopting Nb modified gamma alumina as catalyst, wherein the Nb loading is 20wt%, and the specific surface area of the gamma alumina is 250m 2 Per g, pore volume of 0.8cm 3 And/g, the average pore diameter is 10nm. The preparation method of the catalyst comprises the following steps: preparing a catalyst by adopting a secondary impregnation method, dissolving 3.47g of niobium oxalate in 6g of deionized water, heating to 50 ℃, pouring 6g of gamma alumina into the solution, standing for 30 minutes, drying at 110 ℃ for 12 hours, putting the dried catalyst into the same niobium oxalate solution, carrying out secondary impregnation, standing for 30 minutes, drying at 110 ℃ for 12 hours, and roasting at 450 ℃ for 4 hours in an air atmosphere to prepare the catalyst. The catalyst performance evaluation results are shown in Table 1, the reaction temperature is 150 ℃ and the liquid space velocity is 1h -1 The reaction pressure is normal pressure.
Example 4
The catalyst was the same as in example 2 and the liquid space velocity was different from that of example 2. The catalyst performance evaluation results are shown in Table 1, the reaction temperature is 170 ℃ and the liquid space velocity is 0.5h -1 The reaction pressure is normal pressure.
Example 5
The catalyst was the same as in example 2 and the liquid space velocity was different from that of example 2. The catalyst performance evaluation results are shown in Table 1, the reaction temperature is 200 ℃ and the liquid space velocity is 2h -1 The reaction pressure is normal pressure.
Example 6
The catalyst was the same as in example 2, and the reaction temperature was different from that in example 2. The catalyst performance evaluation results are shown in Table 1, the reaction temperature is 120 ℃, and the liquid space velocity is 1h -1 The reaction pressure is normal pressure.
Example 7
Nb modified gamma alumina (specification identical to example 1) was used as catalyst with an Nb loading of 10wt%. The preparation method of the catalyst comprises the following steps: 3.47g of niobium oxalate was dissolved in 6g of deionized water, heated to 50 ℃, 6g of gamma alumina was poured into the above solution, left to stand for 30 minutes, dried at 110 ℃ for 12 hours, and calcined at 350 ℃ for 4 hours in an air atmosphere to prepare a catalyst. The catalyst performance evaluation results are shown in Table 1, the reaction temperature is 170 ℃ and the liquid space velocity is 1h -1 The reaction pressure is normal pressure.
Example 8
Nb modified gamma alumina (specification identical to example 1) was used as catalyst with an Nb loading of 10wt%. The preparation method of the catalyst comprises the following steps: 3.47g of niobium oxalate was dissolved in 6g of deionized water, heated to 50 ℃, 6g of gamma alumina was poured into the above solution, left to stand for 30 minutes, dried at 110 ℃ for 12 hours, and calcined at 350 ℃ for 4 hours in a nitrogen atmosphere, to prepare a catalyst. The catalyst performance evaluation results are shown in Table 1, the reaction temperature is 170 ℃ and the liquid space velocity is 1h -1 The reaction pressure is normal pressure.
Example 9
V-modified gamma alumina is used as a catalyst, wherein the V loading is 10wt%, and the specific surface area of the gamma alumina is 100m 2 Per g, pore volume of 0.2cm 3 And/g, average pore diameter 20nm. The preparation method of the catalyst comprises the following steps: 1.38g of ammonium metavanadate was dissolved in 6g of deionized water, heated to 50 ℃, 6g of gamma alumina was poured into the above solution, left to stand for 30 minutes, dried at 110℃for 12 hours, and calcined at 450℃for 4 hours in an air atmosphere to prepare a catalyst. Catalyst performance evaluation conditions were the same as in example 1, and the results of catalyst performance evaluation are shown in Table 1, with a reaction temperature of 170℃and a liquid space velocity of 1h -1 The reaction pressure is normal pressure.
Example 10
Mo modified gamma alumina is used as a catalyst, wherein the Mo loading amount is 10wt%, and the specific surface area of the gamma alumina is 250m 2 Per g, pore volume of 1.0cm 3 And/g, the average pore diameter is 11nm. The preparation method of the catalyst comprises the following steps: 1.22g of ammonium molybdate was dissolved in 6g of deionized water, heated to 50℃and 6g of gamma alumina was poured into the solutionThe mixture was left to stand for 30 minutes, dried at 110℃for 12 hours, and calcined at 450℃for 4 hours in an air atmosphere to obtain a catalyst. Catalyst performance evaluation conditions were the same as in example 1, and the results of catalyst performance evaluation are shown in Table 1, with a reaction temperature of 190℃and a liquid space velocity of 1h -1 The reaction pressure is normal pressure.
Example 11
Gamma alumina modified with W (specification identical to example 1) was used as catalyst, wherein the W loading was 10wt%. The preparation method of the catalyst comprises the following steps: 1.22g of ammonium tungstate pentahydrate was dissolved in 6g of deionized water, heated to 50 ℃, 6g of gamma alumina was poured into the solution, allowed to stand for 30 minutes, dried at 110 ℃ for 12 hours, and calcined at 450 ℃ for 4 hours in an air atmosphere to prepare a catalyst. Catalyst performance evaluation conditions were the same as in example 1, and the results of catalyst performance evaluation are shown in Table 1, with a reaction temperature of 170℃and a liquid space velocity of 1h -1 The reaction pressure is normal pressure.
Example 12
Zr-modified gamma alumina (specification same as in example 10) was used as catalyst, wherein Zr loading is 10wt%. The preparation method of the catalyst comprises the following steps: 2.83g of zirconium nitrate pentahydrate was dissolved in 6g of deionized water, heated to 50 ℃, 6g of gamma alumina was poured into the above solution, left to stand for 30 minutes, dried at 110 ℃ for 12 hours, and calcined at 450 ℃ for 4 hours in an air atmosphere to prepare a catalyst. Catalyst performance evaluation conditions were the same as in example 1, and the results of catalyst performance evaluation are shown in Table 1, with a reaction temperature of 170℃and a liquid space velocity of 1h -1 The reaction pressure is normal pressure.
Example 13
Ti-modified gamma alumina (specification the same as example 9) was used as the catalyst, with a Ti loading of 10wt%. The preparation method of the catalyst comprises the following steps: 4.25g of n-butyl titanate was dissolved in 6g of ethanol, 6g of gamma alumina was poured into the above solution, allowed to stand for 30 minutes, dried at 110℃for 12 hours, and calcined at 450℃for 4 hours in an air atmosphere to prepare a catalyst. Catalyst performance evaluation conditions were the same as in example 1, and the results of catalyst performance evaluation are shown in Table 1, with a reaction temperature of 160℃and a liquid space velocity of 1h -1 The reaction pressure is normal pressure.
Example 14
Nb+w modified gamma alumina (specification identical to example 1) was used as catalyst, where both Nb and W loadings were 5wt%. The preparation method of the catalyst comprises the following steps: 1.73g of niobium oxalate was dissolved in 6g of deionized water, heated to 50 ℃, 6g of gamma alumina was poured into the above solution, left to stand for 30 minutes, dried at 110 ℃ for 12 hours, and calcined at 450 ℃ for 4 hours in an air atmosphere to obtain a Nb-modified gamma alumina catalyst. 0.61g of ammonium tungstate pentahydrate was dissolved in 6g of deionized water, heated to 50 ℃, and the Nb-modified gamma alumina catalyst was poured into the above solution, left to stand for 30 minutes, dried at 110 ℃ for 12 hours, and calcined at 450 ℃ for 4 hours in an air atmosphere to prepare a catalyst. The catalyst performance evaluation results are shown in Table 1, the reaction temperature is 170 ℃ and the liquid space velocity is 1h -1 The reaction pressure is normal pressure.
Example 15
Gamma alumina modified with Nb + Zr (specification identical to example 1) was used as catalyst, where both Nb and Zr loadings were 5wt%. The preparation method of the catalyst comprises the following steps: 1.73g of niobium oxalate was dissolved in 6g of deionized water, heated to 50 ℃, 6g of gamma alumina was poured into the above solution, left to stand for 30 minutes, dried at 110 ℃ for 12 hours, and calcined at 450 ℃ for 4 hours in an air atmosphere to obtain a Nb-modified gamma alumina catalyst. 1.41g of zirconium nitrate pentahydrate was dissolved in 6g of deionized water, heated to 50 ℃, and the Nb-modified gamma alumina catalyst was poured into the above solution, left to stand for 30 minutes, dried at 110 ℃ for 12 hours, and calcined at 450 ℃ for 4 hours in an air atmosphere to prepare a catalyst. The catalyst performance evaluation results are shown in Table 1, the reaction temperature is 170 ℃ and the liquid space velocity is 1h -1 The reaction pressure is normal pressure.
Example 16
Gamma alumina modified with Nb + Mo (specification identical to example 10) was used as catalyst, where both Nb and Mo loadings were 5wt%. The preparation method of the catalyst comprises the following steps: 1.73g of niobium oxalate was dissolved in 6g of deionized water, heated to 50 ℃, 6g of gamma alumina was poured into the above solution, left to stand for 30 minutes, dried at 110 ℃ for 12 hours, and calcined at 450 ℃ for 4 hours in an air atmosphere to obtain a Nb-modified gamma alumina catalyst. 0.61g of ammonium molybdate was dissolved in 6g of deionized water,heating to 50 ℃, pouring the Nb modified gamma alumina catalyst into the solution, standing for 30 minutes, drying at 110 ℃ for 12 hours, and roasting at 450 ℃ for 4 hours in an air atmosphere to prepare the catalyst. The catalyst performance evaluation results are shown in Table 1, the reaction temperature is 170 ℃ and the liquid space velocity is 1h -1 The reaction pressure is normal pressure.
Example 17
As in example 14, the reaction temperature was 170℃and the liquid space velocity was 1h -1 The reaction pressure was normal pressure and the reaction time was 200 hours, and the life of the catalyst was examined, and the results are shown in FIG. 1.
Table 1 results of evaluation of catalyst properties of examples
In conclusion, the invention can realize the continuous production operation of the deprotection reaction of the p-tert-butoxyphenethyl methyl ether, the selectivity of the p- (2-methoxy) ethylphenol can reach more than 98%, the catalyst has good stability, and the catalyst is not deactivated after continuous reaction for 200 hours. Although the single pass conversion rate does not reach 100%, separation of the product and unreacted raw materials can be realized through rectification, and unreacted raw materials obtained through separation continue to enter a fixed bed reactor.
The above examples will allow a more complete understanding of the present invention to be provided to those skilled in the art, but are not intended to limit the invention in any way.
Claims (10)
1. A solid acid catalyst comprising gamma alumina and an acidic metal oxide modified on the gamma alumina, wherein the acidic metal oxide contains a metal element comprising: one or two of Nb, V, mo, W, zr or Ti.
2. The solid acid catalyst according to claim 1, wherein the gamma alumina has a specific surface area of 100 to 250m 2 Per gram, the pore volume is 0.2-1.0 cm 3 /g, average pore size of10～20nm。
3. The solid acid catalyst according to claim 1, wherein the loading of the metal element on the gamma alumina is 5 to 20wt%.
4. The solid acid catalyst according to claim 1, wherein the metal element is a combination of Nb and other metals;
the other metal is V, mo, W, zr or Ti.
5. A process for preparing a solid acid catalyst as claimed in any one of claims 1 to 4, wherein an aqueous solution of a salt containing Nb, V, mo, W, zr or Ti is heated, then gamma alumina is added, and the resultant is modified by impregnation, dried and calcined to obtain the solid acid catalyst.
6. The method for preparing a solid acid catalyst according to claim 5, wherein the impregnation method is a primary impregnation method or a secondary impregnation method;
in the secondary impregnation method, after the first impregnation is completed, drying is performed first, and then the second impregnation is performed.
7. The method for producing a solid acid catalyst according to claim 5, wherein when the metal element is a combination of Nb and other metal, the method comprises:
heating an aqueous solution of Nb-containing salt, then adding gamma alumina, modifying by adopting an impregnation method, and drying and roasting to obtain a Nb-modified gamma alumina catalyst; then heating the water solution containing the salt of V, mo, W, zr or Ti, adding the Nb modified gamma alumina catalyst, adopting an impregnation method for modification, and drying and roasting to obtain the solid acid catalyst.
8. The method for producing a solid acid catalyst according to any one of claims 5 to 7, wherein the heating temperature is 45 to 55 ℃ and the impregnation time is 20 to 40 minutes;
the drying temperature is 110-120 ℃, and the drying time is 10-12 hours;
the roasting temperature is 350-450 ℃, and the roasting time is 4-6 hours.
9. Use of a solid acid catalyst according to any one of claims 1 to 8 in the deprotection of p-tert-butoxyphenethyl methyl ether.
10. The use according to claim 9, wherein the solid acid catalyst is filled in a fixed bed continuous reactor, and p-tert-butoxyphenethyl methyl ether is led into the fixed bed continuous reactor for deprotection reaction;
the reaction temperature is 120-200 ℃ and the liquid space velocity is 0.5-2 h -1 The reaction pressure is normal pressure.
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