CN102531860A - Method for catalyzing oxosynthesis of parahydroxyben-zaldehyde by using stratified material - Google Patents
Method for catalyzing oxosynthesis of parahydroxyben-zaldehyde by using stratified material Download PDFInfo
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- CN102531860A CN102531860A CN2011104600025A CN201110460002A CN102531860A CN 102531860 A CN102531860 A CN 102531860A CN 2011104600025 A CN2011104600025 A CN 2011104600025A CN 201110460002 A CN201110460002 A CN 201110460002A CN 102531860 A CN102531860 A CN 102531860A
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- Prior art keywords
- cresol
- hydroxy benzaldehyde
- catalyst
- para hydroxy
- catalyzer
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- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 10
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 230000009466 transformation Effects 0.000 claims abstract description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 230000003647 oxidation Effects 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 11
- 239000012498 ultrapure water Substances 0.000 claims description 11
- 230000008929 regeneration Effects 0.000 claims description 10
- 238000011069 regeneration method Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- 239000007790 solid phase Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract 4
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- 230000000887 hydrating effect Effects 0.000 abstract 2
- 230000001172 regenerating effect Effects 0.000 abstract 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 abstract 1
- 229960001545 hydrotalcite Drugs 0.000 abstract 1
- 229910001701 hydrotalcite Inorganic materials 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- VATYWCRQDJIRAI-UHFFFAOYSA-N p-aminobenzaldehyde Chemical compound NC1=CC=C(C=O)C=C1 VATYWCRQDJIRAI-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 229940090668 parachlorophenol Drugs 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000012453 solvate Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- -1 PARA HYDROXY BENZALDEHYDE compound Chemical class 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000007013 Reimer-Tiemann formylation reaction Methods 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000022244 formylation Effects 0.000 description 2
- 238000006170 formylation reaction Methods 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 241001331845 Equus asinus x caballus Species 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-PQMKYFCFSA-N alpha-D-mannose Chemical compound OC[C@H]1O[C@H](O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-PQMKYFCFSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 1
- 238000010850 salt effect Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for catalyzing oxosynthesis of parahydroxyben-zaldehyde by using a stratified material. In the method, parahydroxyben-zaldehyde is synthesized by taking stratified material multi-element hydrotalcite as a catalyst and oxidizing paracresol. The method comprises the following steps in sequence: (1) preparing a catalyst: mixing divalent and trivalent metal salt solutions with a mixed solution of sodium hydrate and sodium carbonate, quickly mixing for preparing a catalyst precursor, baking at a certain temperature, hydrating, filtering and drying; (2) catalytically oxidizing paracresol: adding paracresol, an alkali, a solvent and the catalyst into a four-mouth flask, introducing pure oxygen for oxidizing, and ending a reaction when the paracresol transformation ratio is over 99.0 percent; (3) performing post-treatment on a reaction liquid: rotationally evaporating the reaction liquid for recovering a solvent, adding deionized water, fully mixing, filtering and recovering the catalyst in a hot state, acidifying a filtrate, cooling, crystalizing, filtering and performing vacuum drying to obtain a parahydroxyben-zaldehyde solid; and (4) regenerating the catalyst: fully washing the filtered and recovered catalyst with a solvent, baking, hydrating, filtering and drying. The synthesis method disclosed by the invention for producing parahydroxyben-zaldehyde has the advantages of environmental friendliness, easiness for regenerating the catalyst, high transformation ratio, high selectivity, high yield and the like.
Description
(1) technical field
The present invention relates to a kind of compound method of PARA HYDROXY BENZALDEHYDE, a kind of method with the synthetic PARA HYDROXY BENZALDEHYDE of stratiform material section catalyzed oxidation particularly is provided.
(2) background technology
PARA HYDROXY BENZALDEHYDE is a kind of important fine-chemical intermediate, is widely used in fields such as medicine, agricultural chemicals, spices, petrochemical complex, plating, liquid crystal and photosensitive macromolecular material.In view of the important use of PARA HYDROXY BENZALDEHYDE, further study, optimize its synthetic technology, accelerate its production and application in industry and have great importance.
The compound method of PARA HYDROXY BENZALDEHYDE is a lot of in the industry, and Reimer-Tiemann method, phenol formaldehyde (PF) method, PNT method, para-chlorophenol formylation method, p-Aminobenzaldehyde method, electrochemical synthesis method, microbial method, p-cresol catalytic oxidation etc. are arranged.
The Reimer-Tiemann method: with phenol and chloroform is raw material, under the alkali metal hydroxide effect, obtains two kinds of isomer of PARA HYDROXY BENZALDEHYDE and salicylaldhyde.This method poor selectivity, productive rate are low, and it is many to produce tar content, and chloroform must be difficult for reclaiming product separation and purification difficult by excessive, unreacted phenol.But, receive people's attention deeply because of raw material cheaply is easy to get, simple operation and other advantages always.People have carried out constantly improving to this reaction for many years, obtained many gratifying achievements, but total recovery are still lower, and selectivity is still not enough.
The phenol formaldehyde (PF) method: condensation reaction takes place in its ortho position and the contraposition in phenol and formaldehyde under the alkali effect, generates p-Hydroxybenzylalcohol and diathesin, and oxidation then, acidifying obtain PARA HYDROXY BENZALDEHYDE and salicylaldhyde.Though the selectivity of this method and productive rate are not high, low for equipment requirements, synthetic route is short, in industry, uses to some extent at present.
Para-chlorophenol formylation method: para-chlorophenol can make to be reflected at and carry out under lesser temps and the pressure under the effect of catalyzer such as composite catalyst palladium, tricyclohexyl phosphine and 4-(dimethylamino) pyridine, and productive rate is higher.But this method is high, dangerous big to equipment requirements, and productive rate is unstable.
The PNT method: PNT, ethanol and tensio-active agent mix, with Na
2S
xReaction obtains p-Aminobenzaldehyde, generates PARA HYDROXY BENZALDEHYDE through diazotization, hydrolysis again.This method yield can reach more than 90%, but operational path is complicated, needs a large amount of ethanol of consume, and volume of equipment is huge, and investment cost is high.
The p-Aminobenzaldehyde method: p-Aminobenzaldehyde obtains PARA HYDROXY BENZALDEHYDE through diazotization, hydrolysis, and yield reaches as high as 90%.This method raw material is easy to get, and yield is higher, but the facility investment expense is high.
The electrochemical synthesis method: the hydroxyl with p-cresol carries out etherification reaction earlier, to reduce the big and protection hydroxyl of the dissolving damage of aldehyde in the tens of times of aqueous solution in the indirect electrooxidation reaction process, uses Mn again
3+The indirect electrooxidation methyl is an aldehyde radical, and after oxidizing reaction was accomplished, the reaction with ether bond rupture regeneration hydroxyl made PARA HYDROXY BENZALDEHYDE again.
Microbial method: p-cresol is used for obtaining PARA HYDROXY BENZALDEHYDE through bacterial classification.Use bacterial classification p.putideks-0160 (FERM P-12879), in containing medium such as mannose (seminose) yeast with salt in the presence of, 27 ℃ of controlled temperature, pH are 6.8 times 5d that vibrate.Add the p-cresol of 0.1g, make PARA HYDROXY BENZALDEHYDE through 3d.Microbial method pollutes little, and productive rate is high, and is simple to operate, and reaction conditions is relatively gentleer, but the production cycle is long.
P-cresol catalytic oxidation: under the effect of catalyzer, with the synthetic PARA HYDROXY BENZALDEHYDE of molecular oxygen (oxygen or air) direct oxidation p-cresol.This method has raw material and is easy to get, and reaction conditions relaxes, and product is easy to separate, and product yield is high with purity, two useless advantages such as lack.The key of this synthesis technique be can develop preparation simply, catalyzer efficiently.
From the result of study of existing report, the catalyzer of p-cresol catalyzed oxidation PARA HYDROXY BENZALDEHYDE is divided into the homogeneous catalysis oxidation and heterogeneous catalytic oxidation two mankind.
The homogeneous catalysis oxidation generally uses the salt of transition metal (like Co, Ni, Mn, Cu, Fe, Cr etc.) to be catalyzer, and cobalt salt effect in the process of the synthetic PARA HYDROXY BENZALDEHYDE of p-cresol catalyzed oxidation is obvious.In reaction system, add auxiliary agent (like cupric chloride, nickel salt, cerium salt or molysite etc.), can obviously improve catalytic performance, shorten the reaction times and reduce temperature of reaction.The main drawback of such catalyzer is catalyzer and product separation difficulty, increases difficulty to its recovery and recycling, brings environmental pollution to a certain degree simultaneously.
Heterogeneous catalytic oxidation is mainly through loading on cobalt salt on the specific support; Make it to be applied to the p-cresol catalyzed oxidation; Obtained good result; Employed carrier mainly contains activated carbon, molecular sieve, polymeric adsorbent and some MOXs etc., exists the catalyst activity component to be prone to run off, and causes catalytic activity sharply to descend.In addition, also have some to make the catalyst research of p-cresol oxidizing reaction about using bimetallic oxide or houghite calcining matter, there are shortcomings such as regeneration is difficult for, catalyzer weak point in work-ing life in such catalyzer.
To the technical problem that exists in the prior art, the invention provides a kind of environmental friendliness, catalyst regeneration is simple, and transformation efficiency is high, and selectivity is good, the PARA HYDROXY BENZALDEHYDE compound method that yield is high.
(3) summary of the invention
The purpose of this invention is to provide a kind of environmental friendliness, catalyst regeneration is simple, and transformation efficiency is high, and selectivity is good, the PARA HYDROXY BENZALDEHYDE compound method that yield is high.
The technical scheme that the present invention adopts is:
In four-hole bottle, add p-cresol, alkali, solvent and catalyzer, heat up, aerating oxygen reacts while stirring, follows the tracks of reaction process with gc, when the p-cresol transformation efficiency reaches 99.0% when above, termination reaction; Reaction solution transferred in the single port flask be rotated evaporation, reclaim solvent; In flask, add appropriate amount of deionized water again, thorough mixing, filtered while hot reclaims catalyzer, and filtrating is used the mineral acid acidifying, regulates pH≤5, is cooled to below 10 ℃, and crystallization is filtered, and vacuum-drying gets the PARA HYDROXY BENZALDEHYDE solid; Catalyzer can recycle through simple regeneration.
Said catalyzer is a kind of stratified material, is a kind of polynary houghite, and its chemical constitution is [M
2+ 1-xM
3+ x(OH)
2]
X+(A
N- Xn) mH
2O, M
2+And M
3+Represent divalence and trivalent metal ion respectively, A
N-Represent negatively charged ion, x is M
3+/ (M
2++ M
3+) mol ratio, M
2+Be Ca
2+, Mg
2+, Co
2+, Ni
2+, Mn
2+, Cu
2+, Fe
2+, Cr
2+In two or three, M
3+Be Fe
3+, Al
3+, Cr
3+, Sc
3+In one or both, A
N-Be CO
3 2-, OH
-, NO
3 -, Cl
-, SO
4 2-, PO
4 3-In one or both.
The Preparation of catalysts method is: divalence and trivalent metal salt are mixed with mixed solution I by certain mol proportion, and with the mixed solution I I short mix of sodium hydroxide and yellow soda ash preparation, adjustment pH value 9~10, violent stirring 30min; In 65 ℃ of aging 18h, washing is extremely neutral, drier 12h under 80 ℃; Grind, get catalyst precursor, roasting at a certain temperature then; Join aquation in the ultrapure water behind the naturally cooling, filter, the dry catalyzer that gets.
Said alkali is alkali metal hydroxide or alkaline carbonate, preferably a kind of in sodium hydroxide or the oxygen potassium oxide.
Said solvent is C
1~C
4Alcohols can be a kind of in methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, the trimethyl carbinol, preferably methyl alcohol.
The renovation process of catalyzer is: with the catalyzer of filtered and recycled, and behind organic solvent solvent thorough washing, roasting in retort furnace; Maturing temperature is 300 ℃~600 ℃, preferably 400 ℃~500 ℃, further removes organism; Join aquation in the ultrapure water behind the naturally cooling, filter drying.
It is following that concrete said method goes on foot mule:
1) Preparation of Catalyst
Divalence and trivalent metal salt are mixed with mixed solution I by certain mol proportion, with the mixed solution I I of sodium hydroxide and yellow soda ash preparation, short mix, adjustment pH value is 9~10; Violent stirring 30min, in 65 ℃ of aging 18h, washing is extremely neutral, drier 12h under 80 ℃; Grind, get catalyst precursor, roasting at a certain temperature then joins aquation in the ultrapure water behind the naturally cooling; Filter, drying makes catalyzer.
2) catalyzed oxidation p-cresol
In four-hole boiling flask, add p-cresol, alkali, solvent and catalyzer successively, the consumption of alkali is 1~5 times of amount of p-cresol; Solvent load is 5~30 times of amount of p-cresol, and catalyst levels is 0.1%~5% of a p-cresol quality, heats up; The synthetic PARA HYDROXY BENZALDEHYDE of logical pure oxygen oxidation p-cresol is followed the tracks of reaction process with gc, when the p-cresol transformation efficiency reaches 99.0% when above; Termination reaction, this moment, PARA HYDROXY BENZALDEHYDE chromatogram yield was more than 98.0%.
3) reaction solution aftertreatment
Reaction solution transferred in the single port flask be rotated evaporation, reclaim solvent, in flask, add appropriate amount of deionized water again, thorough mixing; Filtered while hot reclaims catalyzer, and filtrating is used the mineral acid acidifying, regulates pH≤5; Be cooled to below 10 ℃, crystallization is filtered; Vacuum-drying gets the PARA HYDROXY BENZALDEHYDE solid, and yield is more than 85%, and purity is more than 99.0%.
4) catalyst regeneration
With the catalyzer of filtered and recycled, behind the methyl alcohol thorough washing, roasting in retort furnace, maturing temperature is 300 ℃~600 ℃, further removes organism, joins aquation in the ultrapure water behind the naturally cooling, filters drying.
(4) embodiment
Below in conjunction with specific embodiment the present invention is further described, but protection scope of the present invention is not limited in this:
Embodiment 1:
In four-hole bottle, with Co (NO
3)
26H
2O 17.46g, Cu (NO
3)
23H
2O 4.84g, Mn (CH
3COO)
24H
2O 2.45g, Al (NO
3)
39H
2O 7.50g, Fe (NO
3)
39H
2O 4.04g is mixed with mixed solution I, with the mixed solution I I of sodium hydroxide 10g and yellow soda ash 1.7g preparation, and short mix, adjustment pH value 9~10; Violent stirring 30min, in 65 ℃ of aging 18h, washing is extremely neutral, 80 ℃ of following dry 12h; Grind, put into retort furnace in 450 ℃ of following roasting 3h, the cooling back adds in the ultrapure water carries out aquation, filters; Dry 12h under 80 ℃ gets five yuan of houghite stratified material catalyzer 10.53g, kept dry.
In four-hole bottle, add p-cresol 27.00g, sodium hydroxide 30.00g, methyl alcohol 180ml and catalyzer 0.54g successively.Under 65 ℃, logical oxygen reaction 8h after sampling adds the 6mol/L hcl acidifying, adds extracted with diethyl ether, and organic layer is used gas chromatographic analysis, and the p-cresol transformation efficiency is 99.3%, and the PARA HYDROXY BENZALDEHYDE yield is 98.9%.
After logical oxygen reaction finishes, reaction solution transferred to be rotated evaporation in the flask, reclaim methanol solvate, an amount of ultrapure water of adding in the flask again, thorough mixing, filtered while hot obtains the salts solution of PARA HYDROXY BENZALDEHYDE.With 6mol/L hcl acidifying filtrating, regulate pH≤5, be cooled to 10 ℃ of crystallizations, filter after vacuum-drying obtains PARA HYDROXY BENZALDEHYDE 26.14g, yield is 85.7%.
Embodiment 2:
With the catalyzer of filtered and recycled, use earlier the methyl alcohol thorough washing, then in retort furnace in 450 ℃ of roasting 3h, further remove organism; Join aquation in the ultrapure water behind the naturally cooling, filter drying; Subsequent use, get reclaiming catalyzer 0.51g, the recovery is 94.4%.
Embodiment 3:
With the synthetic PARA HYDROXY BENZALDEHYDE of the catalyst oxidation p-cresol of reclaiming.In four-hole bottle, add the catalyzer 0.51g of p-cresol 27.00g, sodium hydroxide 30.00g, methyl alcohol 180ml and reclaiming successively, add live catalyst 0.03g.Under 65 ℃, logical oxygen reaction 8h after sampling adds the 6mol/L hcl acidifying, adds extracted with diethyl ether, and organic layer is used gas chromatographic analysis, and the p-cresol transformation efficiency is 99.2%, PARA HYDROXY BENZALDEHYDE yield 98.6%.
After logical oxygen reaction finishes, reaction solution transferred to be rotated evaporation in the flask, reclaim methanol solvate, an amount of ultrapure water of adding in the flask again, thorough mixing, filtered while hot obtains the salts solution of PARA HYDROXY BENZALDEHYDE.With hcl acidifying filtrating, regulate pH≤5, be cooled to 10 ℃, crystallization is filtered, and vacuum-drying obtains PARA HYDROXY BENZALDEHYDE 26.01g, and yield is 85.2%.The result shows that catalyst recovery regeneration does not influence the transformation efficiency and the selectivity of reaction.
Embodiment 4:
Use the synthetic PARA HYDROXY BENZALDEHYDE of catalyst oxidation p-cresol after the repetition 10 times.In four-hole bottle, add p-cresol 27.00g, sodium hydroxide 30.00g, methyl alcohol 180ml and catalyzer 0.54g successively.Under 65 ℃, logical oxygen reaction 8h after sampling adds the 6mol/L hcl acidifying, adds extracted with diethyl ether, and organic layer is used gas chromatographic analysis, and the p-cresol transformation efficiency is 99.2%, PARA HYDROXY BENZALDEHYDE yield 98.1%.
After logical oxygen reaction finishes, reaction solution transferred to be rotated evaporation in the flask, reclaim methanol solvate, an amount of ultrapure water of adding in the flask again, thorough mixing, filtered while hot obtains the salts solution of PARA HYDROXY BENZALDEHYDE.With hcl acidifying filtrating, regulate pH≤5, be cooled to 10 ℃, crystallization is filtered, and vacuum-drying obtains PARA HYDROXY BENZALDEHYDE 25.9g, and yield is 84.9%.The result shows that the catalyst recirculation use does not influence experimental result.
The above is merely several embodiments of the present invention; Should be pointed out that for the person of ordinary skill of the art, can also make many modification and improvement; For example change the proportioning of two trivalent metal ions; Change the consumption of solvent, change catalyst consumption, all modification or improvement all should be regarded as protection scope of the present invention.
Claims (10)
1. method with the synthetic PARA HYDROXY BENZALDEHYDE of stratified material catalyzed oxidation, it is characterized in that: with the polynary houghite of a kind of stratified material is catalyzer, and the oxidation p-cresol synthesizes PARA HYDROXY BENZALDEHYDE, and concrete said method steps is following:
1) Preparation of Catalyst
Divalence and trivalent metal salt are mixed with mixed solution I by certain mol proportion, with the mixed solution I I of sodium hydroxide and yellow soda ash preparation, short mix, adjustment pH value 9~10; Violent stirring 30min, in 65 ℃ of aging 18h, washing is extremely neutral, drier 12h under 80 ℃; Grind, get catalyst precursor, roasting at a certain temperature then; Join aquation in the ultrapure water behind the naturally cooling, filter, the dry catalyzer that gets;
2) catalyzed oxidation p-cresol
In four-hole boiling flask, add p-cresol, alkali, solvent and catalyzer successively, the consumption of alkali is 1~5 times of amount of p-cresol; Solvent load is 5~30 times of amount of p-cresol, and catalyst levels is 0.1%~5% of a p-cresol quality, heats up; The synthetic PARA HYDROXY BENZALDEHYDE of logical pure oxygen oxidation p-cresol is followed the tracks of reaction process with gc, when the p-cresol transformation efficiency reaches 99.0% when above; Termination reaction, this moment, PARA HYDROXY BENZALDEHYDE chromatogram yield was more than 98.0%;
3) reaction solution aftertreatment
Reaction solution transferred in the single port flask be rotated evaporation, reclaim solvent, in flask, add appropriate amount of deionized water again; Thorough mixing, filtered while hot reclaims catalyzer, and filtrating is with inorganic acid for adjusting pH≤5; Be cooled to below 10 ℃, crystallization is filtered; Vacuum-drying gets the PARA HYDROXY BENZALDEHYDE solid phase prod, and yield is more than 85%;
4) catalyst regeneration
With the catalyzer of filtered and recycled, behind the organic solvent thorough washing, organism is further removed in roasting in retort furnace, joins aquation in the ultrapure water behind the naturally cooling, filters drying.
2. according to the compound method of the said PARA HYDROXY BENZALDEHYDE of claim 1, it is characterized in that: the synthetic catalyst precursor is a kind of polynary houghite in the said step 1), and its chemical constitution is [M
2+ 1-xM
3+ x(OH)
2]
X+(A
N- Xn) mH
2O, M
2+And M
3+Represent divalence and trivalent metal ion respectively, A
N-Represent negatively charged ion, x is M
3+/ (M
2++ M
3+) mol ratio.M
2+Be to wipe Ca
2+, Mg
2+, Co
2+, Ni
2+, Mn
2+, Cu
2+, Fe
2+, Cr
2+In two or three, M
3+Be Fe
3+, Al
3+, Cr
3+, Sc
3+In one or both, A
N-Be CO
3 2-, OH
-, NO
3 -, Cl
-, SO
4 2-, PO
4 3-In one or both.
3. according to the compound method of the said hydroxy benzaldehyde of claim 2, it is characterized in that: in the said step 1), during said catalyst precursor was formed, divalent-metal ion was selected from Co
2+, Mn
2+, Cu
2+, Fe
2+In two or three, trivalent metal ion is selected from Fe
3+, Al
3+In one or both, negatively charged ion is selected from CO
3 2-, OH
-In a kind of.
4. according to the compound method of the said PARA HYDROXY BENZALDEHYDE of claim 1, it is characterized in that: said step 2), used alkali is one or both in alkali metal hydroxide or the alkaline carbonate, and the consumption of alkali is 1~5 times of amount of p-cresol.
5. according to the compound method of the said PARA HYDROXY BENZALDEHYDE of claim 4, it is characterized in that: said step 2), used alkali is a kind of in sodium hydroxide or the Pottasium Hydroxide, and the consumption of alkali is 2~3 times of amount of p-cresol.
6. according to the compound method of the said PARA HYDROXY BENZALDEHYDE of claim 1, it is characterized in that: said step 2), solvent for use is C
1~C
4One or both of alcohol, solvent load are 5~30 times of amount of p-cresol.
7. according to the compound method of the said PARA HYDROXY BENZALDEHYDE of claim 6, it is characterized in that: said step 2), solvent for use is a methyl alcohol, and its consumption is 15~25 times of amount of p-cresol.
8. according to the compound method of the said PARA HYDROXY BENZALDEHYDE of claim 1, it is characterized in that: in the said step 3), mineral acid is hydrochloric acid, sulfuric acid or phosphoric acid, is preferably hydrochloric acid.
9. according to the compound method of the said PARA HYDROXY BENZALDEHYDE of claim 1, it is characterized in that: said step 4) is in the regeneration of catalyzer, and organic solvent is a kind of in methyl alcohol, ethanol, benzene, toluene, the gasoline, preferably methyl alcohol.
10. according to the compound method of the said PARA HYDROXY BENZALDEHYDE of claim 1, it is characterized in that: said step 4) is in the regeneration of catalyzer, and maturing temperature is 300 ℃~600 ℃, preferably 400 ℃~500 ℃.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102992973A (en) * | 2012-12-05 | 2013-03-27 | 嘉兴市安瑞材料科技有限公司 | Industrial method for synthesizing p-hydroxy benzaldehyde in jet flow manner |
CN105562058A (en) * | 2015-12-30 | 2016-05-11 | 衢州学院 | Catalyst for synthesizing 2,3,3,3-tetrafluoropropylene, and preparation method thereof |
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CN109180454A (en) * | 2018-07-16 | 2019-01-11 | 南京雪郎化工科技有限公司 | A kind of preparation method of parahydroxyben-zaldehyde |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1319581A (en) * | 2000-09-06 | 2001-10-31 | 吉林省石油化工设计研究院 | Process for preparation of p-hydroxy-benzaldehyde |
-
2011
- 2011-12-29 CN CN201110460002.5A patent/CN102531860B/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1319581A (en) * | 2000-09-06 | 2001-10-31 | 吉林省石油化工设计研究院 | Process for preparation of p-hydroxy-benzaldehyde |
Non-Patent Citations (3)
Title |
---|
刘玉敏等: "钴铜铝水滑石类化合物的合成及其催化氧化对甲酚", 《应用化学》 * |
李泉等: "多相催化氧化合成对羟基苯甲醛研究", 《化工矿物与加工》 * |
王玉林等: "催化氧化对甲酚合成对羟基苯甲醛的研究进展", 《化工生产与技术》 * |
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