CN1319581A - Process for preparation of p-hydroxy-benzaldehyde - Google Patents
Process for preparation of p-hydroxy-benzaldehyde Download PDFInfo
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- CN1319581A CN1319581A CN 00118977 CN00118977A CN1319581A CN 1319581 A CN1319581 A CN 1319581A CN 00118977 CN00118977 CN 00118977 CN 00118977 A CN00118977 A CN 00118977A CN 1319581 A CN1319581 A CN 1319581A
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Abstract
The present invention belongs to the synthesis method of p-hydroxybenzaldehyde. In said method cresol is used as raw material, cobalt chelate is used as catalyst, after having been carried said catalyst can be repeatedly used, and features high activity and good selectivity. The oxidizing agent selects and uses oxygen gas or hydrogen gas, said reaction is implemented in the alkaline solution of anhydrous monobasic alcohol, and one kind selected from inorganic salts of copper (II), cerium (IV) and nickel (II) can be used as catalyst promoter. The cresol conversion rate is greater than 97.0%, and its product yield is 80%-87%, and p-hydroxybenzaldehyde selectivity is greater than 82%, the crude product is recrystallized so as to can obtain p-hydroxybenzaldehyde whose purity is greater than 98%.
Description
The invention belongs to the preparation method of p-Hydroxybenzaldehyde.
P-Hydroxybenzaldehyde is a kind of crucial fine-chemical intermediate.Because have a hydroxyl and an aldehyde radical on its phenyl ring, character is very active, can synthesize many kinds of materials by it, is widely used in the industries such as agricultural chemicals, spices, medicine, liquid crystal and plating.The method of industrial synthetic p-Hydroxybenzaldehyde is a lot, past is raw material mostly with phenol, as the Reimer-Tieman method (U.S.Pat.3365500) that the Dow Chemical Company of the U.S. adopts, the Gatterman-Adlams method (China's " Guangdong chemical industry " fourth phase nineteen ninety) that Japanese fine chemistry company etc. adopts.Adopt the yield of these method p-Hydroxybenzaldehydes to have only 50%～70%, and have problems such as isomer separation difficulty and prussiate toxicity.After the eighties, it is the method for the synthetic p-Hydroxybenzaldehyde of raw material with the p-cresol that some countries have developed, and this method technical process is short, pollution is little.The emphasis of technological development is an oxide catalyst.Catalyzer mainly uses the organism and the inorganic salt of cobalt, nickel, iron etc., the yield 40%～80% of p-Hydroxybenzaldehyde, but catalyzer is difficult to reclaim repeated use.Nineteen ninety, United States Patent (USP) 4978802, having reported a kind of is raw material with p-cresol and p-cresol derivative, through the method for catalyzed oxidation synthetic aroma aldehyde.The catalyzer that this method is used is the complex compound of cobalt, can reclaim repeated use, the thick product yield 31.1%～85.8% of aromatic aldehyde.But this patent does not provide a complete catalyst cupport, recovery, reusable method, and containing by product in the product p-Hydroxybenzaldehyde does not have separated.
The preparation method who the purpose of this invention is to provide a kind of p-Hydroxybenzaldehyde, this method is raw material with the p-cresol, make p-Hydroxybenzaldehyde through catalyzed oxidation, Primary Catalysts is selected binuclear phthalocyanine cobalt (II), binuclear phthalocyanine cobalt (II) sulfonate, phthalocyanine cobalt (II), phthalocyanine cobalt (II) sulfonate respectively for use.Catalyzer is through immobilized, recyclable repeated use, and have active high, the life-span is long, selectivity is good characteristics.Oxygenant is selected oxygen or air for use, is reflected in the alkaline medium of anhydrous monohydroxy-alcohol to carry out, and adds a certain amount of promotor, improves the yield of p-Hydroxybenzaldehyde.
The present invention attempts to find a kind of catalyzer, in the oxidizing reaction of p-cresol, has Stability Analysis of Structures, and active high, selectivity is good, can reclaim reusable characteristics.Catalyzer selects cobaltous inner complex to combine with oxygen than its cobalt salt is easier, and the structure quite stable, and catalytic activity is higher.Phthalocyanine cobalt (II), binuclear phthalocyanine cobalt (II), phthalocyanine cobalt (II) sulfonate, binuclear phthalocyanine cobalt (II) sulfonate are class cobalt chelates, in the present invention, because it is insoluble in the dielectric solvent that oxidizing reaction is used, thereby can reclaim by fairly simple method and reuse, and have quite high catalytic activity and selectivity.In order further to improve activity of such catalysts, in reaction system, add the inorganic salt of a certain amount of copper (II), cerium (IV), nickel (II), as promotor.
The present invention is raw material with the p-cresol, and it is dissolved in the causticity alkali alcosol, and the weight ratio that feeds intake is a p-cresol: alkali: solvent: catalyzer=10.8: 6～24: 32～86.4: 0.0216～0.55.The cobalt chelates that catalyzer is selected is wherein a kind of of phthalocyanine cobalt (II), binuclear phthalocyanine cobalt (II), phthalocyanine cobalt (II) sulfonate, binuclear phthalocyanine cobalt (II) sulfonate, in oxidizing reaction, the amount that cobalt chelates adds is 0.2%～5.1% of raw material p-cresol; Catalyzer is fixed on the carrier, carrier is selected gac, gac is immersed in the alkaline aqueous solution of cobalt chelates, the weight ratio that feeds intake is a water: cobalt chelates: gac: sodium hydroxide=100: 0.25～5.0: 10～50: 0.5～2.0, mixed solution is heated to 60～105 ℃, stirred 0.5～3 hour, be cooled to room temperature and filter, filter cake was 105～180 ℃ of dryings 3～10 hours, and is standby.Solvent is selected anhydrous monohydroxy-alcohol, is specially in methyl alcohol, ethanol, the Virahol any, preferably methyl alcohol.Alkali is selected alkali metal hydroxide, is sodium hydroxide or potassium hydroxide, preferably sodium hydroxide.The promotor weight ratio that feeds intake is a p-cresol: promotor=10.8: 0.00108～0.54, promotor is selected the inorganic salt of transition metal and rare earth metal, is specially a kind of in the inorganic salt of copper (II), cerium (IV), nickel (II).The oxidizing reaction of p-cresol is carried out under the condition that oxygen exists, and oxidizing gas is selected the mixture of pure oxygen, air or air and oxygen.The under agitation logical oxygen reaction of reaction solution 8～15 hours, temperature of reaction is between 55～80 ℃, and the absolute pressure of reaction system is 0.005～0.401MPa.Reaction process is as follows:
After reaction finished, with reacting liquid filtering, filter cake was washed 2-5 time with methyl alcohol, colourless to washing lotion, it is colourless to be washed till washing lotion with 0.5%～10% caustic-alkali aqueous solution again, filters and drain filter cake, the catalyzer of filter cake for reclaiming, 105～180 ℃ of dryings 3～10 hours, standby; The filtrate thin up, be heated to 55～60 ℃ of underpressure distillation, vacuum tightness 0.07～0.095MPa reclaims solvent methanol, and raffinate is cooled to≤10 ℃ of crystallizations, filter out crystallization, use water dissolution, with 3.5N dilute hydrochloric acid solution is neutralized to pH=3～5 again, be cooled to≤10 ℃ of filtrations, filtration cakes torrefaction obtains the thick product of p-Hydroxybenzaldehyde.P-cresol transformation efficiency＞97.0% calculates product yield 80%～87% with the raw material p-cresol.P-Hydroxybenzaldehyde selectivity＞82%, thick product is surveyed its purity by potentiometric titration, purity＞98% through recrystallization.With nuclear magnetic resonance method and infrared spectroscopy testing product, and survey the product fusing point.
The present invention is Primary Catalysts with the cobalt chelates, and transistion metal compound and rare earth compound are promotor, is the synthetic p-Hydroxybenzaldehyde of raw material with the p-cresol.This catalyst structure stable, active high, selectivity is good, recyclable repeated use after immobilized.Reaction solvent is selected anhydrous monohydroxy-alcohol for use, and oxygenant is selected the mixture of oxygen, air or air and oxygen.This synthetic method that possesses above-mentioned feature, the transformation efficiency height of p-cresol, the yield height of p-Hydroxybenzaldehyde, the selectivity that generates p-Hydroxybenzaldehyde is good.Therefore it is good in economic efficiency to adopt this synthetic method to produce.
Embodiment provided by the invention is as follows:
Embodiment 1:
In 150 milliliters of reaction flasks that agitator, prolong, oxygen catheter are housed, add 10.8 gram p-cresol, 14.0 gram sodium hydroxide, 48.0 gram anhydrous methanols, 0.32 gram binuclear phthalocyanine cobalt (II), stir, 65 ℃ of constant temperature, logical oxygen reaction is 13 hours under the absolute pressure 0.005MPa, and the transformation efficiency that reaction process is followed the tracks of p-cresol with gas-chromatography is 97.9%.After reaction finished, with reacting liquid filtering, filter cake reclaimed catalyzer after treatment with small amount of methanol washing 3 times, filter residue.The filtrate thin up is heated to 55 ℃ of underpressure distillation, and vacuum tightness 0.07MPa reclaims methyl alcohol.Raffinate is cooled to 10 ℃, has the p-Hydroxybenzaldehyde crystals of sodium salt to produce.The crystal that filtration obtains is dissolved in water, and is neutralized to pH=3 with 3.5N dilute hydrochloric acid, is cooled to filtration, filtration cakes torrefaction below 10 ℃, obtains pale yellow powder 11.6 grams.It is 85.6% that potentiometric titration is surveyed its p-Hydroxybenzaldehyde content, and the p-Hydroxybenzaldehyde yield is 81.4% as calculated, and the selectivity of p-Hydroxybenzaldehyde is 83.1%.
Thick product obtains white crystal through recrystallization, and surveying its molten point is 115.4 ℃, and it is 98.1% that potentiometric titration is surveyed its purity.
Embodiment 2:
In 150 milliliters of reaction flasks, add 10.8 gram p-cresol, 24 gram potassium hydroxide, 86.4 gram dehydrated alcohols, 0.55 gram binuclear phthalocyanine cobalt (II) sulfonate respectively, stir, 80 ℃ of constant temperature, the aerating oxygen reaction is 8 hours under the absolute pressure 0.401MPa.After reaction finished, with reacting liquid filtering, filter cake reclaimed catalyzer after treatment with small amount of methanol washing 2 times, filter residue.The filtrate thin up is heated to 60 ℃ of underpressure distillation, and vacuum tightness 0.09MPa reclaims methyl alcohol.Raffinate is cooled to 7 ℃, has the p-Hydroxybenzaldehyde crystals of sodium salt to produce.The crystal that filtration obtains, be dissolved in water, be neutralized to pH=4, cool off 7 ℃ of filtrations, filtration cakes torrefaction with 3.5N dilute hydrochloric acid, obtain thick product, through recrystallization, obtain white crystal, the product fusing point is 117 ℃, purity is 98.2%, the transformation efficiency of p-cresol is 98.1%, and the yield of p-Hydroxybenzaldehyde is 83.7%, and the selectivity of p-Hydroxybenzaldehyde is 85.3%.
Embodiment 3:
In 150 milliliters of reaction flasks, add 10.8 gram p-cresol, 14.0 gram sodium hydroxide, 32 gram anhydrous methanols, 0.0216 gram phthalocyanine cobalt (II) sulfonate, 0.00108 gram Copper dichloride dihydrate respectively, stir, 55 ℃ of constant temperature, the aerating oxygen reaction is 15 hours under the absolute pressure 0.105MPa.After reaction finished, with reacting liquid filtering, filter cake reclaimed catalyzer after treatment with small amount of methanol washing 5 times, filter residue.The filtrate thin up is heated to 60 ℃ of underpressure distillation, and vacuum tightness 0.095MPa reclaims methyl alcohol.Raffinate is cooled to 3 ℃, has the p-Hydroxybenzaldehyde crystals of sodium salt to produce.The crystal that filtration obtains, be dissolved in water, be neutralized to pH=5 with 3.5N dilute hydrochloric acid, cool off 3 ℃ of filtrations, filtration cakes torrefaction, 116 ℃ of the product fusing points that obtains, purity are 98.1%, and the transformation efficiency of p-cresol is 98.9%, the yield of p-Hydroxybenzaldehyde is 82.8%, and the selectivity of p-Hydroxybenzaldehyde is 83.7%.
Embodiment 4:
In 150 milliliters of reaction flasks, add 10.8 gram p-cresol, 14.0 gram sodium hydroxide, 48 gram anhydrous isopropyl alcohols, 0.128 gram phthalocyanine cobalt (II), 0.54 gram single nickel salt respectively, stir, 65 ℃ of constant temperature, the aerating oxygen reaction is 11 hours under the absolute pressure 0.105MPa.Reaction finishes the back to be handled according to the method for embodiment 1, and the product fusing point is 114.6 ℃, and purity is 98.2%, and the transformation efficiency of p-cresol is 97.2%, and the yield of p-Hydroxybenzaldehyde is 80.2%, and the selectivity of p-Hydroxybenzaldehyde is 82.5%.
Embodiment 5:
In 200 milliliters of reaction flasks, with water, binuclear phthalocyanine cobalt (II) sulfonate, gac, sodium hydroxide by weight 100: 2.65: 30: 0.5 ratio is mixed with mixed solution, be warming up to 105 ℃ then, stirred 0.5 hour, be cooled to room temperature, filter, filter cake is following dry 3 hours at 180 ℃, make loaded catalyst, the activated carbon supported binuclear phthalocyanine cobalt of every gram (II) sulfonate 0.088 gram.
Embodiment 6:
In 200 milliliters of reaction flasks, with water, binuclear phthalocyanine cobalt (II) sulfonate, gac, sodium hydroxide by weight 100: 0.25: 10: 1.5 ratio is mixed with mixed solution, be warming up to 80 ℃ then, stirred 2 hours, be cooled to room temperature, filter, filter cake is following dry 5 hours at 130 ℃, make loaded catalyst, the activated carbon supported binuclear phthalocyanine cobalt of every gram (II) sulfonate 0.025 gram.
Embodiment 7:
In 200 milliliters of reaction flasks, with water, binuclear phthalocyanine cobalt (II) sulfonate, gac, sodium hydroxide by weight 100: 5: 50: 2.0 ratio is mixed with mixed solution, be warming up to 60 ℃ then, stirred 3 hours, be cooled to room temperature, filter, filter cake is following dry 10 hours at 105 ℃, make loaded catalyst, the activated carbon supported binuclear phthalocyanine cobalt of every gram (II) sulfonate 0.100 gram.
Embodiment 8:
In 150 milliliters of reaction flasks, add 10.8 gram p-cresol, 14.0 gram sodium hydroxide, 56 gram anhydrous methanols, the loaded catalyst of 3.69 gram embodiment, 5 preparations, 0.0137 gram cerous ammonium nitrate respectively, stir, 70 ℃ of constant temperature, the aerating oxygen reaction is 13 hours under the absolute pressure 0.25MPa.Reaction finishes the method processing reaction liquid of back according to embodiment 1, filter residue is washed 3 times with a small amount of 5% sodium hydroxide solution, colourless to washing lotion, treated filter residue descended dry 10 hours at 105 ℃, reclaimed catalyzer 3.51 grams, and the product fusing point is 115～116 ℃, purity is 98.5%, the transformation efficiency of p-cresol is 99.1%, and the yield of p-Hydroxybenzaldehyde is 86.4%, the selectivity 87.2% of p-Hydroxybenzaldehyde.
Embodiment 9:
Prescription is except that the loaded catalyst that adds 5.17 gram embodiment, 6 preparations, other is with embodiment 8, reaction finishes the method processing reaction liquid of back according to embodiment 1, filter residue is colourless to washing lotion with a small amount of 0.5% aqueous sodium hydroxide washes 3 times, treated filter residue descended dry 6 hours at 130 ℃, reclaimed catalyzer 4.96 grams.The transformation efficiency of p-cresol is 98.5%, and the yield of p-Hydroxybenzaldehyde is 82.6%, the selectivity 83.9% of p-Hydroxybenzaldehyde.
Embodiment 10:
Prescription is except that the loaded catalyst that adds 3.17 gram embodiment, 7 preparations, other is with embodiment 8, reaction finishes the method processing reaction liquid of back according to embodiment 1, filter residue is colourless to washing lotion with a small amount of 10% aqueous sodium hydroxide washes 3 times, treated filter residue descended dry 3 hours at 180 ℃, reclaimed catalyzer 3.05 grams.The transformation efficiency of p-cresol is 98.9%, and the yield of p-Hydroxybenzaldehyde is 83.1%, the selectivity 84.0% of p-Hydroxybenzaldehyde.
Embodiment 11:
Catalyzer 3.51 grams that catalyzer uses embodiment 8 to reclaim are added the loaded catalyst that 0.18 gram embodiment 5 prepares.Other component is with embodiment 8 in the prescription, the reaction conditions treatment process is with example 8, reaction finishes the back and reclaims catalyzer 3.53 grams, the product fusing point is 116.5 ℃, purity is 98.7%, the transformation efficiency of p-cresol is 99.0%, and the yield of p-Hydroxybenzaldehyde is 85.8%, the selectivity 86.7% of p-Hydroxybenzaldehyde.
Embodiment 12:
Prescription stirs with embodiment 8,75 ℃ of temperature of reaction, and the bubbling air reaction is 15 hours under the absolute pressure 0.105MPa.Reaction finishes the back to be handled according to the method for example 8, and the product fusing point is 114.6 ℃, and purity is 98.1%, and the transformation efficiency of p-cresol is 97.5%, and the yield of p-Hydroxybenzaldehyde is 82.8%, and the selectivity of p-Hydroxybenzaldehyde is 84.9%.
Claims (10)
1. the preparation method of a p-Hydroxybenzaldehyde, it is characterized in that with the p-cresol being raw material, it is dissolved in the causticity alkali alcosol, the weight ratio that feeds intake is a p-cresol: alkali: solvent: catalyzer=10.8: 6～24: 32～86.4: 0.0216～0.55, the cobalt chelates that catalyzer is selected is wherein a kind of of phthalocyanine cobalt (II), binuclear phthalocyanine cobalt (II), phthalocyanine cobalt (II) sulfonate, binuclear phthalocyanine cobalt (II) sulfonate, in oxidizing reaction, the amount that cobalt chelates adds is 0.2%～5.1% of raw material p-cresol; Catalyzer is fixed on the carrier, carrier is selected gac, gac is immersed in the alkaline aqueous solution of cobalt chelates, the weight ratio that feeds intake is a water: cobalt chelates: gac: sodium hydroxide=100: 0.25～5.0: 10～50: 0.5～2.0, mixed solution is heated to 60～105 ℃, stirred 0.5～3 hour, be cooled to room temperature and filter, filter cake was 105～180 ℃ of dryings 3～10 hours, and is standby; Solvent is selected anhydrous monohydroxy-alcohol, is specially in methyl alcohol, ethanol, the Virahol any, methyl alcohol preferably, and alkali is selected alkali metal hydroxide, is sodium hydroxide or potassium hydroxide, preferably sodium hydroxide; The promotor weight ratio that feeds intake is a p-cresol: promotor=10.8: 0.00108～0.54, and promotor is selected the inorganic salt of transition metal and rare earth metal, is specially a kind of in the inorganic salt of copper (II), cerium (IV), nickel (II); The oxidizing reaction of p-cresol is carried out under the condition that oxygen exists, and oxidizing gas is selected the mixture of pure oxygen, air or air and oxygen; The under agitation logical oxygen reaction of reaction solution 8～15 hours, temperature of reaction is between 55～80 ℃, and the absolute pressure of reaction system is 0.005～0.401Mpa; Reaction process is as follows:
After reaction finished, with reacting liquid filtering, filter cake was washed 2-5 time with methyl alcohol, colourless to washing lotion, it is colourless to be washed till washing lotion with 0.5%～10% caustic-alkali aqueous solution again, filters and drain filter cake, the catalyzer of filter cake for reclaiming, 105～180 ℃ of dryings 3～10 hours, standby; The filtrate thin up, be heated to 55～60 ℃ of underpressure distillation, vacuum tightness 0.07～0.095MPa, reclaim solvent methanol, raffinate is cooled to≤10 ℃ of crystallizations, filters out crystallization, uses water dissolution, with 3.5N dilute hydrochloric acid solution is neutralized to pH=3～5 again, be cooled to≤10 ℃ of filtrations, filtration cakes torrefaction obtains the thick product of p-Hydroxybenzaldehyde, p-cresol transformation efficiency＞97.0%, calculate product yield 80%～87%, p-Hydroxybenzaldehyde selectivity＞82% with the raw material p-cresol, thick product gets purity＞98% p-Hydroxybenzaldehyde through recrystallization.
2. synthetic method as claimed in claim 1 is characterized in that the cobalt chelates that catalyzer is selected is phthalocyanine cobalt (II).
3. synthetic method as claimed in claim 1 is characterized in that the cobalt chelates that catalyzer is selected is binuclear phthalocyanine cobalt (II).
4. synthetic method as claimed in claim 1 is characterized in that the cobalt chelates that catalyzer is selected is phthalocyanine cobalt (II) sulfonate.
5. synthetic method as claimed in claim 1 is characterized in that the cobalt chelates that catalyzer is selected is binuclear phthalocyanine cobalt (II) sulfonate.
6. synthetic method as claimed in claim 1 is characterized in that solvent selection anhydrous methanol.
7. synthetic method as claimed in claim 1 is characterized in that alkali selection sodium hydroxide.
8. synthetic method as claimed in claim 1 is characterized in that promotor selection copper (II).
9. synthetic method as claimed in claim 1 is characterized in that promotor selection cerium (IV).
10. synthetic method as claimed in claim 1 is characterized in that promotor selection nickel (II).
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101947471A (en) * | 2010-09-19 | 2011-01-19 | 陈晓洲 | Preparation method of noble metal catalyst for propylene oxidation |
| CN101417929B (en) * | 2008-11-26 | 2011-06-08 | 合肥工业大学 | Synthetic method of hydroxybenzaldehyde |
| CN102531860A (en) * | 2011-12-29 | 2012-07-04 | 衢州学院 | Method for catalyzing oxosynthesis of parahydroxyben-zaldehyde by using stratified material |
| US20150182949A1 (en) * | 2004-01-22 | 2015-07-02 | Arkema France | Activated carbon with improved mechanical resistance, and the uses thereof, especially as a catalyst carrier |
| CN107935834A (en) * | 2017-11-17 | 2018-04-20 | 西北化工研究院 | A kind of synthetic method of parahydroxyben-zaldehyde |
| CN115385783A (en) * | 2022-09-09 | 2022-11-25 | 上海应用技术大学 | Method for synthesizing p-hydroxybenzaldehyde by catalytic oxidation of p-cresol with metal phthalocyanine |
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| CN101187654B (en) * | 2007-12-13 | 2012-09-05 | 中国石油兰州石油化工公司 | Analysis method for oxidized liquid and product from paracresol catalytic oxidized synthesis for p-hydroxybenzaldehyde |
| CN101270037B (en) * | 2008-03-31 | 2011-05-25 | 浙江工业大学 | Method for preparing p-hydroxybenzene methanal with Reimer-Tiemann reaction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20150182949A1 (en) * | 2004-01-22 | 2015-07-02 | Arkema France | Activated carbon with improved mechanical resistance, and the uses thereof, especially as a catalyst carrier |
| CN101417929B (en) * | 2008-11-26 | 2011-06-08 | 合肥工业大学 | Synthetic method of hydroxybenzaldehyde |
| CN101947471A (en) * | 2010-09-19 | 2011-01-19 | 陈晓洲 | Preparation method of noble metal catalyst for propylene oxidation |
| CN101947471B (en) * | 2010-09-19 | 2012-06-27 | 薛华 | Preparation method of noble metal catalyst for propylene oxidation |
| CN102531860A (en) * | 2011-12-29 | 2012-07-04 | 衢州学院 | Method for catalyzing oxosynthesis of parahydroxyben-zaldehyde by using stratified material |
| CN102531860B (en) * | 2011-12-29 | 2015-05-20 | 衢州学院 | Method for catalyzing oxosynthesis of parahydroxyben-zaldehyde by using stratified material |
| CN107935834A (en) * | 2017-11-17 | 2018-04-20 | 西北化工研究院 | A kind of synthetic method of parahydroxyben-zaldehyde |
| CN107935834B (en) * | 2017-11-17 | 2021-07-13 | 西北化工研究院 | Synthetic method of p-hydroxybenzaldehyde |
| CN115385783A (en) * | 2022-09-09 | 2022-11-25 | 上海应用技术大学 | Method for synthesizing p-hydroxybenzaldehyde by catalytic oxidation of p-cresol with metal phthalocyanine |
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