CN101462934B - Method for preparing p-hydroxybenzene formaldehyde by diazo salt hydrolysis of p-aminobenzaldehyde - Google Patents
Method for preparing p-hydroxybenzene formaldehyde by diazo salt hydrolysis of p-aminobenzaldehyde Download PDFInfo
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- CN101462934B CN101462934B CN2009100736673A CN200910073667A CN101462934B CN 101462934 B CN101462934 B CN 101462934B CN 2009100736673 A CN2009100736673 A CN 2009100736673A CN 200910073667 A CN200910073667 A CN 200910073667A CN 101462934 B CN101462934 B CN 101462934B
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- hydroxy benzaldehyde
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- 238000000034 method Methods 0.000 title claims abstract description 47
- VATYWCRQDJIRAI-UHFFFAOYSA-N p-aminobenzaldehyde Chemical compound NC1=CC=C(C=O)C=C1 VATYWCRQDJIRAI-UHFFFAOYSA-N 0.000 title claims description 56
- 238000006460 hydrolysis reaction Methods 0.000 title claims description 53
- 230000007062 hydrolysis Effects 0.000 title claims description 44
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 title abstract 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 title 1
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims abstract description 130
- 239000012954 diazonium Substances 0.000 claims abstract description 60
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims abstract description 10
- 238000003860 storage Methods 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 150000001989 diazonium salts Chemical class 0.000 claims description 49
- 239000012452 mother liquor Substances 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 35
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
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- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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Abstract
The invention belongs to the technical field of preparing parahydroxyben-zaldehyde, and more particularly relates to a method for preparing parahydroxyben-zaldehyde by hydrolyzing diazo salt of para aminotenzaldehyde and a device thereof. The invention solves the problems of low efficiency and high energy consumption in the existing method for preparing the parahydroxyben-zaldehyde. The method comprises the steps: reactant is thrown into a rotary packed bed to be heated and then enters a diversion plate type tower, and sent out to be filtered, condensed and filtered again. The device comprises the rotary packed bed and the diversion plate type tower, wherein, a liquid inlet of the rotary packed bed is connected with a liquid storage tank of diazonium, an air inlet is connected with a thermal medium generator, and a liquid outlet is connected with a liquid inlet of the diversion plate type tower; a liquid outlet of the diversion plate type tower is connected with a filter I which is connected with a condenser. The invention has the beneficial effects of easily controlled process, stable operation, uniform product quality, small volume of the device, convenient installation and maintenance and short startup and shutdown time.
Description
Technical field
The invention belongs to the technical field of PARA HYDROXY BENZALDEHYDE preparation, be specifically related to method and device thereof that a kind of diazonium salt hydrolysis by p-Aminobenzaldehyde prepares PARA HYDROXY BENZALDEHYDE.
Background technology
PARA HYDROXY BENZALDEHYDE is called for short PHB, and pure article outward appearance is colourless or faint yellow needle crystal, and aromatic odour is arranged, and 116.4 ℃ of fusing points-118 ℃ (distillation) are soluble in organic solvents such as hot water, methyl alcohol, acetone, ether, are slightly soluble in water, benzene.PARA HYDROXY BENZALDEHYDE is important fine-chemical intermediate, is widely used in fields such as medicine, agricultural chemicals, spices, makeup, liquid crystal, plating.In recent years, along with the fast development of China's agricultural chemicals, medicine and perfume industry, domestic demand to PARA HYDROXY BENZALDEHYDE is continuous rising tendency; But the domestic throughput that exists can not satisfy the demands; Defectives such as production cost is high, and quality product is low, therefore; China's PARA HYDROXY BENZALDEHYDE exploitation has much potentiality, so development research has the necessary property of production technique of high yield, highly selective, economical rationality.
The preparation of PARA HYDROXY BENZALDEHYDE has three kinds of raw material routes: phynol method, p-cresol method and PNT method.The phynol method product separates purification difficult, and yield is low, and cost is high; The p-cresol method is a kind of method of domestic more employing, but there is the product separation difficulty equally in this method, causes product purity low, and yield is low.The PNT route is to use sodium polysulphide that the PNT redox is p-Aminobenzaldehyde, and p-Aminobenzaldehyde carries out diazotization reaction and prepares diazonium salt, and diazonium salt is hydrolyzed to PARA HYDROXY BENZALDEHYDE again.This method compares with the p-cresol method that to have a product easily separated, the product purity advantages of higher.But the hydrolysis process of diazonium salt adopts traditional still formula hydrolysis method; Its process is: the mixed solution with water and acid is warmed up to required hydrolysis temperature earlier, under stirring state, diazonium salt is added drop-wise in the still again, stirs while dripping; The general dropping time is 2.0h～3.5h, and this hydrolytic process is periodical operation.In this process, when hydrolysis reaction generated principal product, principal product also can generate by product with raw material generation coupled reaction.In the reaction later stage,, just more be prone to and raw material generation side reaction especially along with the rising of major product concentration.Therefore, make that the PT is long, by product is many, product yield is low (being merely about 55%), wayward, the unstable product quality of process.
In order to improve the yield of diazonium salt hydrolysis system phenol; Hao Yanxia (fiery explosive journal; 64～66), Zhang Zhenming (prints during chemical industry 2002 (1):; 2004 (18) 6:48～49) etc. all still formula hydrolytic process has been done the research of optimizing technology, main method is to adopt phase transfer method, steam distillation etc., though make the yield of hydrolysate phenol improve through process modification; But having increased operations such as product separation, solvent recuperation, i.e. the production efficiency problem low, that energy consumption is high of still formula method existence is not solved yet.
When the diazotization hydrolysis prepared PARA HYDROXY BENZALDEHYDE, the side reaction of hydrolysis mainly was to generate azo cpd by p-Aminobenzaldehyde, and it is the consecutive side reaction of main reaction, and major and minor reaction equation is following:
Main reaction:
Be abbreviated as: A+B → P
Side reaction:
Be abbreviated as: P+A → S
In above-mentioned reaction, hydrolysis reaction is a nucleophilic substitution reaction, and coupled reaction is an electrophilic substitution reaction, is the reaction product of the adjacency pair position of diazonium positive ion attack phenol.Coupled reaction has lower activation energy than hydrolysis reaction, and this is because hydroxyl is strong power supplying groups, the incidental cause of nucleophilic substitution reaction.Can know from the kinetics mechanism analysis, reduce the generation of side reaction, need emphasis to consider following 2 points:
1, be rapidly heated: in the hydrolytic process of diazonium salt, elevated temperature is favourable to hydrolysis reaction.Need reaction solution be rapidly heated,, so just can effectively suppress the generation of coupled reaction without the intermediate preheating stage.
2, disperse fast: in hydrolytic process, reduce and avoid the back-mixing of principal product and raw material diazonium salt, help suppressing the generation of coupled reaction like this.
Summary of the invention
The problems referred to above that the present invention exists for the preparation method who solves existing PARA HYDROXY BENZALDEHYDE; Provide a kind of diazonium salt hydrolysis to prepare the method and the device of PARA HYDROXY BENZALDEHYDE, with the yield that improves PARA HYDROXY BENZALDEHYDE, shorten the reaction times, cut down the consumption of energy, enhance productivity by p-Aminobenzaldehyde.
The present invention adopts following technical scheme to realize:
A kind ofly prepare the method for PARA HYDROXY BENZALDEHYDE, it is characterized in that step is following by the diazonium salt hydrolysis of p-Aminobenzaldehyde:
1), the diazonium salt solution of p-Aminobenzaldehyde being squeezed into rotating speed is in 600r/min～2000r/min rotary packed bed; Heat rotary packed bed to the required hydrolysis temperature of diazonium salt; Get into the guide plate type tower behind reaction mass rotary packed bed mixing of process and the initial reaction, the total residence time of reaction mass in rotary packed bed and guide plate type tower is 60s～180s;
2), the reacting liquor while hot seen off after will in rotary packed bed and guide plate type tower, reacting filters, condensation then, the crystallization in supersaturated aqueous solution of cooling back PARA HYDROXY BENZALDEHYDE is separated out;
3), again the supersaturated aqueous solution of cooled PARA HYDROXY BENZALDEHYDE is filtered; Obtain filter cake and filtrating; Filter cake is the PARA HYDROXY BENZALDEHYDE that contains certain moisture, filtrates to be the saturated aqueous solution of PARA HYDROXY BENZALDEHYDE, and filtrating is reclaimed; Filter cake gets hydrolysis principal product PARA HYDROXY BENZALDEHYDE through vacuum-drying to constant weight with the frozen water washing for several times.
The required hydrolysis temperature of diazonium salt is 65 ℃～95 ℃.
Realization is prepared the device of the method for PARA HYDROXY BENZALDEHYDE by the diazonium salt hydrolysis of p-Aminobenzaldehyde; Comprise rotary packed bed and the guide plate type tower; Have liquid-inlet, liquid exit, gas feed, pneumatic outlet on rotary packed bed, have fluid inlet and liquid outlet on the guide plate type tower; Rotary packed bed liquid-inlet is connected with diazonium liquid storage tank, and gas feed is connected with the thermal medium producer, and liquid exit is connected with the fluid inlet of guide plate type tower; The liquid outlet of guide plate type tower connects strainer I, and strainer I connects condensing surface, and condensing surface links to each other with strainer II again, and strainer II connects the mother liquor accumulator tank.
Diazonium liquid storage tank is connected with rotary packed bed liquid-inlet through pump, header tank.
Setting can make fluid form baffling mobile several layers traverse baffle and perhaps can make fluid formation eddy flow mobile several layers eddy flow plate in the tower of guide plate type tower.
Rotary packed bed can the efficient hardening mass-and heat-transfer, its mass-and heat-transfer speed improves 1～3 one magnitude than traditional reactor, can be heated to heated air and diazonium liquid short mix temperature required.The guide plate type tower can effectively reduce the material back-mixing, and the nitrogen that is beneficial to reaction simultaneously and is produced discharges, and accomplishes the further hydrolysis reaction of diazonium salt.Based on above characteristics; Rotary packed bed and guide plate type tower combined reactor are applied to the hydrolysis reaction of diazonium salt; Can solve be rapidly heated, problems such as rapid reaction, minimizing back-mixing, thereby effectively suppress the generation of coupled reaction, improve the yield of PARA HYDROXY BENZALDEHYDE.
The present invention has following beneficial effect:
1, the present invention adopt rotary packed bed and the guide plate type tower as the combined hydrolysis reactor drum; This combined reactor has mass-and heat-transfer efficient efficiently; Can effectively reduce the material back-mixing; Diazonium salt and heating medium short mix are conducted heat material are heated up rapidly in rotary packed bed, and reaction mass is disperseed fast, and the guide plate type tower can effectively reduce the material back-mixing; And accomplish further hydrolysis reaction; Meet the kinetics and the thermodynamic condition that promote the hydrolysis main reaction to suppress the coupling side reaction, thereby reduced the generation of side reaction, (hydrolysis time shortens to 2min～6min) by original 2.0h～3.5h to have shortened the reaction times; Improve product yield (the principal product yield brings up to 82% by traditional still formula method 55%), solved the problem that traditional still formula hydrolysis reactor hydrolysis time is long, plant factor is low, by product is many and product yield is low.
2, adopt rotary packed bed and guide plate type tower combined reactor makes this hydrolytic process realize operate continuously by periodical operation, compare with traditional still formula method for hydrolysis have process control easily, stable operation, the equal first-class advantage of quality product.
3, the present invention adopted rotary packed bedly has advantages such as equipment volume is little, installation and maintenance convenient, the start-stop car time is short.
Description of drawings
Fig. 1 is a structural representation of the present invention
Fig. 2 is rotary packed bed structural representation
Fig. 3 is the structural representation of deflector type guide plate type tower
Fig. 4 is the structural representation of whirlwind-type guide plate type tower
Among the figure: 1-diazonium liquid storage tank, 2-pump, 3-valve, 4-header tank; The 5-bleeder valve, 6-under meter, 7-thermal medium producer, 8-HAI Heated Air Intake valve; The 9-motor, 10-thermal medium outlet valve, 11-is rotary packed bed, 12-guide plate type tower; 13-strainer I, 14-condensing surface, 15-strainer II, 16-mother liquor accumulator tank;
2.1-motor, 2.2-rotating shaft, 2.3-pneumatic outlet, 2.4-housing, 2.5-filler, 2.6-rotary drum, 2.7-liquid exit, 2.8-liquid-inlet, 2.9-gas feed, 2.10-liquid distributor, 2.11-oil sealing;
3.1-housing, 3.2-reactive tank, 3.3-liquid outlet, 3.4-fluid inlet, 3.5-traverse baffle, 3.6-eddy flow plate
Embodiment
A kind ofly prepare the method for PARA HYDROXY BENZALDEHYDE, comprise following process step: the diazonium salt solution of raw material p-Aminobenzaldehyde is squeezed into header tank 4 with pump 2 from diazonium liquid storage tank 1, open rotary packed bed 11 by the diazonium salt hydrolysis of p-Aminobenzaldehyde; Regulate rotating speed at 600r/min～2000r/min; Open HAI Heated Air Intake valve 8 and be heated to the required hydrolysis temperature of diazonium salt with rotary packed bed 11, the guide plate type tower 12 that reacted hydrolyzed solution gets into rotary packed bed 11 bottoms continues late phase reaction, and reaction solution filters through strainer I13; To remove oily by product (coupling by product etc.); Get into condensing surface 14 afterwards, hydrolyzed solution is quickly cooled to room temperature, principal product crystallization from water is separated out after cooling; The crystalline principal product filters with strainer II15 from water; Filter cake is the product PARA HYDROXY BENZALDEHYDE that contains certain moisture, filtrates to be the saturated aqueous solution (mother liquor) of PARA HYDROXY BENZALDEHYDE, reclaims mother liquor to mother liquor accumulator tank 16; Wash products obtained therefrom (filter cake) for several times with frozen water, get hydrolysis principal product PARA HYDROXY BENZALDEHYDE through vacuum-drying to constant weight.
Diazonium salt hydrolysis of the present invention is accomplished in the combined reactor of rotary packed bed and guide plate type tower; Rotary packed bed heating medium is warm air or superheated vapour; Hydrolysis temperature is 65 ℃～95 ℃, and the total residence time of reaction mass process rotary packed bed 11 and guide plate type tower 12 is 60s-180s.Hydrolytic process is a continuous operation.
Of the present inventionly prepare the device of PARA HYDROXY BENZALDEHYDE, comprise that the pump 2 of carrying diazonium salt solution links to each other with header tank 4 by the diazonium salt hydrolysis of p-Aminobenzaldehyde; The outlet of header tank 4 links to each other with rotary packed bed 11 liquid-inlet 2.8; Rotary packed bed 11 liquid exit 2.7 links to each other with the fluid inlet 3.4 of guide plate type tower 12, and guide plate type tower 12 links to each other with strainer 13; Strainer I13 links to each other with condensing surface 14, and condensing surface 14 links to each other with strainer II15.Filtration medium in the strainer is gac or glass wool etc.Rotary packed bed material with guide plate type tower and gas-to-liquid contact is a stainless steel.Filler in rotary packed bed can be silk screen or waved plate etc.Condensing surface is a pipe bundle condenser.
Concrete technological process of the present invention:
The diazonium salt solution of the p-Aminobenzaldehyde that makes is squeezed into header tank 4 with pump 2, rotary packed bed 11 rotating speeds is adjusted to 600r/min～2000r/min, regulate the aperture of the bleeder valve 5 of header tank 4, through under meter 6 with 0.5m
3/ h～3.0m
3It is rotary packed bed 11 that the flow velocity of/h gets into, and opens thermal medium intake valve 8 simultaneously, suitably opens thermal medium outlet valve 10; Make diazonium salt solution in rotary packed bed, be heated to 65 ℃～95 ℃ rapidly, equably, and carry out hydrolysis reaction fast, the guide plate type tower 12 that gets into rotary packed bed 11 bottoms then carries out follow-up hydrolysis reaction; The total residence time of reaction mass process rotary packed bed 11 and guide plate type tower 12 is 60s～180s, and reaction solution filters through strainer I13 then, to remove the oily by product; Get into shell-and tube condenser 14 afterwards hydrolyzed solution is quickly cooled to room temperature, principal product crystallization from water is separated out after cooling, filters with strainer II15; Filter cake is the product PARA HYDROXY BENZALDEHYDE that contains certain moisture; Filtrating is the saturated aqueous solution of PARA HYDROXY BENZALDEHYDE (mother liquor), reclaims mother liquor to mother liquor accumulator tank 16, washs products obtained therefrom (filter cake) for several times with frozen water; Get hydrolysis principal product PARA HYDROXY BENZALDEHYDE through vacuum-drying to constant weight, the finished product yield is 65%～83%.
The diazonium salt solution of p-Aminobenzaldehyde is squeezed into header tank 4 with pump 2; Open HAI Heated Air Intake valve 8; Be heated to 65 ℃ with rotary packed bed 11; Simultaneously rotary packed bed 11 rotating speed is adjusted to 600r/min, the bleeder valve 5 of opening header tank 4 is to certain aperture, and regulating the raw material diazonium salt, to get into rotary packed bed 11 flow be 1.0m
3/ h, material rotary packed bed 11 mix with initial reaction after get into guide plate type tower 12 and continue late phase reactions, reaction mass through rotary packed bed 11 with the total residence time of guide plate type tower 12 be 140s.After reaction was accomplished, reaction solution got into the strainer I13 filtered while hot that gac is housed from guide plate type tower 12 liquid outlets and falls the oily by product, gets into pipe bundle condenser 14 again with the rapid cool to room temperature of gained hydrolyzed solution; Principal product crystallization from water is separated out after cooling; With mother liquor and product filtering separation, filter cake is the product PARA HYDROXY BENZALDEHYDE that contains certain moisture with strainer II15, filtrates to be the saturated aqueous solution (mother liquor) of PARA HYDROXY BENZALDEHYDE; Reclaim mother liquor to mother liquor accumulator tank 16; Wash products obtained therefrom (filter cake) for several times with frozen water, get hydrolysis principal product PARA HYDROXY BENZALDEHYDE through vacuum-drying to constant weight, yield is 68%.
With pump 2 diazonium salt solution of raw material p-Aminobenzaldehyde is squeezed in the header tank 4; Open HAI Heated Air Intake valve 8; Be heated to 68 ℃ with rotary packed bed 11; Regulating rotary packed bed 11 rotating speed simultaneously is 600r/min, opens the bleeder valve 5 of header tank 4, and regulating the raw material diazonium salt, to get into rotary packed bed 11 flow be 0.5m
3/ h, material rotary packed bed 11 mix with initial reaction after get into guide plate type tower 12 and continue late phase reactions, reaction mass through rotary packed bed 11 with the total residence time of guide plate type tower 12 be 180s.After reaction was accomplished, reaction solution got liquid outlet from guide plate type tower 12 and gets into the strainer I13 filtered while hot that glass wool is housed, and gets into pipe bundle condenser 14 again with the rapid cool to room temperature of gained hydrolyzed solution; Principal product crystallization from water is separated out after cooling; With mother liquor and product filtering separation, filter cake is the product PARA HYDROXY BENZALDEHYDE that contains certain moisture with strainer II15, filtrates to be the saturated aqueous solution (mother liquor) of PARA HYDROXY BENZALDEHYDE; Reclaim mother liquor to mother liquor accumulator tank 16; Wash products obtained therefrom (filter cake) for several times with frozen water, get hydrolysis principal product PARA HYDROXY BENZALDEHYDE through vacuum-drying to constant weight, yield is 71%.
The diazonium salt solution that will be stored in the raw material p-Aminobenzaldehyde in the diazonium liquid storage tank with pump 2 is with squeezing into header tank 4; Open HAI Heated Air Intake valve 8; Be heated to 72 ℃ with rotary packed bed 11; Rotary packed bed 11 rotating speeds are adjusted to 800r/min, open the bleeder valve 5 of header tank 4, and regulating the raw material diazonium salt, to get into rotary packed bed 11 flow be 0.5m
3/ h, material rotary packed bed 11 mix with initial reaction after get into guide plate type tower 12 and continue late phase reactions, reaction mass through rotary packed bed 11 with the total residence time of guide plate type tower 12 be 180s.After reaction was accomplished, reaction solution got into the strainer I13 filtered while hot that gac is housed from the liquid outlet of guide plate type tower 12, gets into pipe bundle condenser 14 again with the rapid cool to room temperature of gained hydrolyzed solution; Because the reduction of temperature, principal product crystallization from water is separated out, with strainer II15 with mother liquor and product filtering separation; Filter cake is the product PARA HYDROXY BENZALDEHYDE that contains certain moisture; Filtrating is the saturated aqueous solution of PARA HYDROXY BENZALDEHYDE (mother liquor), reclaims mother liquor to mother liquor accumulator tank 16, washs products obtained therefrom (filter cake) for several times with frozen water; Get hydrolysis principal product PARA HYDROXY BENZALDEHYDE through vacuum-drying to constant weight, yield is 73%.
The diazonium salt solution of p-Aminobenzaldehyde is squeezed into header tank 4 with pump 2; Open superheated vapour intake valve 8; Be heated to 85 ℃ with rotary packed bed 11; Simultaneously its rotating speed is adjusted to 1200r/min, opens the bleeder valve 5 of header tank 4, regulating the raw material diazonium salt solution, to get into rotary packed bed 11 flow be 1.2m
3/ h, material rotary packed bed 11 mix with initial reaction after get into guide plate type tower 12 and continue late phase reactions, reaction mass through rotary packed bed 11 with the total residence time of guide plate type tower 12 be 100s.After reaction was accomplished, reaction solution got into the strainer I13 filtered while hot that glass wool is housed from the liquid outlet of guide plate type tower 12, gets into pipe bundle condenser 14 again with the rapid cool to room temperature of gained hydrolyzed solution; Principal product crystallization from water is separated out after cooling; With mother liquor and product filtering separation, filter cake is the product PARA HYDROXY BENZALDEHYDE that contains certain moisture with strainer II15, filtrates to be the saturated aqueous solution (mother liquor) of PARA HYDROXY BENZALDEHYDE; Reclaim mother liquor to mother liquor accumulator tank 16; Wash products obtained therefrom (filter cake) for several times with frozen water, get hydrolysis principal product PARA HYDROXY BENZALDEHYDE through vacuum-drying to constant weight, yield is 80%.
Carry diazonium salt solution to the header tank 4 of p-Aminobenzaldehyde with pump 2; Open HAI Heated Air Intake valve 8; Rotary packed bed reactor drum 11 is heated to 85 ℃; Rotary packed bed 11 rotating speeds are adjusted to 1500r/min, open the bleeder valve 5 of header tank 4, and regulating the raw material diazonium salt solution, to get into rotary packed bed 11 flow be 1.5m
3/ h, material rotary packed bed 11 mix with initial reaction after get into guide plate type tower 12 and continue late phase reactions, reaction mass through rotary packed bed 11 with the total residence time of guide plate type tower 12 be 120s.After reaction was accomplished, reaction solution fell the oily by product from the strainer I13 filtered while hot that gac is equipped with in the liquid outlet entering of guide plate type tower 12, gets into pipe bundle condenser 14 again with the rapid cool to room temperature of gained hydrolyzed solution; PARA HYDROXY BENZALDEHYDE crystallization from water is separated out after cooling; With mother liquor and product filtering separation, filter cake is the product PARA HYDROXY BENZALDEHYDE that contains certain moisture with strainer II15, filtrates to be the saturated aqueous solution (mother liquor) of PARA HYDROXY BENZALDEHYDE; Reclaim mother liquor to mother liquor accumulator tank 16; Wash products obtained therefrom (filter cake) for several times with frozen water, get hydrolysis principal product PARA HYDROXY BENZALDEHYDE through vacuum-drying to constant weight, yield is 81%.
Embodiment 6
The diazonium salt solution of p-Aminobenzaldehyde is squeezed into header tank 4 with pump 2; Open HAI Heated Air Intake valve 8, be heated to 90 ℃ with rotary packed bed 11, rotary packed bed 11 rotating speeds are adjusted to 600r/min; Open the bleeder valve 5 of header tank 4, regulating the raw material diazonium salt, to get into rotary packed bed 11 flow be 2.0m
3/ h, material rotary packed bed 11 mix with initial reaction after get into guide plate type tower 12 and continue late phase reactions, reaction mass through rotary packed bed 11 with the total residence time of guide plate type tower 12 be 90s.After reaction was accomplished, reaction solution got into the strainer I13 filtered while hot that gac is housed from the liquid outlet of guide plate type tower 12, gets into pipe bundle condenser 14 again with the rapid cool to room temperature of gained hydrolyzed solution; Principal product crystallization from water is separated out after cooling; With mother liquor and product filtering separation, filter cake is the product PARA HYDROXY BENZALDEHYDE that contains certain moisture with strainer II15, filtrates to be the saturated aqueous solution (mother liquor) of PARA HYDROXY BENZALDEHYDE; Reclaim mother liquor to mother liquor accumulator tank 16; Wash products obtained therefrom (filter cake) for several times with frozen water, get hydrolysis principal product PARA HYDROXY BENZALDEHYDE through vacuum-drying to constant weight, yield is 83%.
The diazonium salt solution that is stored in the p-Aminobenzaldehyde in the diazonium liquid storage tank is delivered to header tank 4 with pump 2; Open HAI Heated Air Intake valve 8; Be heated to 95 ℃ with rotary packed bed 11; Regulating rotary packed bed 11 rotating speeds simultaneously is 2000r/min, opens the bleeder valve 5 of header tank 4, and regulating the raw material diazonium salt, to get into rotary packed bed 11 flow be 3.0m
3/ h, material rotary packed bed 11 mix with initial reaction after get into guide plate type tower 12 and continue late phase reactions, reaction mass through rotary packed bed 11 with the total residence time of guide plate type tower 12 be 60s.After reaction was accomplished, reaction solution got into the strainer I13 filtered while hot that glass wool is housed from the liquid outlet of guide plate type tower 12, gets into pipe bundle condenser 14 again with the rapid cool to room temperature of gained hydrolyzed solution; Principal product crystallization from water is separated out after cooling; With mother liquor and product filtering separation, filter cake is the product PARA HYDROXY BENZALDEHYDE that contains certain moisture with strainer II15, filtrates to be the saturated aqueous solution (mother liquor) of PARA HYDROXY BENZALDEHYDE; Reclaim mother liquor to mother liquor accumulator tank 16; Wash products obtained therefrom (filter cake) for several times with frozen water, get hydrolysis principal product PARA HYDROXY BENZALDEHYDE through vacuum-drying to constant weight, yield is 82%.
Claims (6)
1. one kind prepares the method for PARA HYDROXY BENZALDEHYDE by the diazonium salt hydrolysis of p-Aminobenzaldehyde, it is characterized in that step is following:
1), the diazonium salt solution of p-Aminobenzaldehyde being squeezed into rotating speed is in 600r/min～2000r/min rotary packed bed; Heat rotary packed bed to the required hydrolysis temperature of diazonium salt; Get into the guide plate type tower behind reaction mass rotary packed bed mixing of process and the initial reaction, the total residence time of reaction mass in rotary packed bed and guide plate type tower is 60s～180s;
2), the reacting liquor while hot seen off after will in rotary packed bed and guide plate type tower, reacting filters, condensation then, the crystallization in supersaturated aqueous solution of cooling back PARA HYDROXY BENZALDEHYDE is separated out;
3), again the supersaturated aqueous solution of cooled PARA HYDROXY BENZALDEHYDE is filtered; Obtain filter cake and filtrating; Filter cake is the PARA HYDROXY BENZALDEHYDE that contains certain moisture, filtrates to be the saturated aqueous solution of PARA HYDROXY BENZALDEHYDE, and filtrating is reclaimed; Filter cake gets hydrolysis principal product PARA HYDROXY BENZALDEHYDE through vacuum-drying to constant weight with the frozen water washing for several times.
2. according to claim 1ly prepare the method for PARA HYDROXY BENZALDEHYDE, it is characterized in that the diazonium salt hydrolysis temperature is 65 ℃～95 ℃ by the diazonium salt hydrolysis of p-Aminobenzaldehyde.
3. realize claim 1 or the 2 described devices that prepare the method for PARA HYDROXY BENZALDEHYDE by the diazonium salt hydrolysis of p-Aminobenzaldehyde for one kind; It is characterized in that comprising rotary packed bed (11) and guide plate type tower (12); Have liquid-inlet (2.8), liquid exit (2.7), gas feed (2.9), pneumatic outlet (2.3) on rotary packed bed (11), have fluid inlet (3.4) and liquid outlet (3.3) on the guide plate type tower (12); Rotary packed bed liquid-inlet (2.8) is connected with diazonium liquid storage tank (1), and gas feed (2.9) is connected with thermal medium producer (7), and liquid exit (2.7) is connected with the fluid inlet (3.4) of guide plate type tower; The liquid outlet of guide plate type tower (3.3) connects strainer I (13), and strainer I (13) connects condensing surface (14).
4. according to claim 3ly prepare the device of PARA HYDROXY BENZALDEHYDE, it is characterized in that diazonium liquid storage tank (1) is connected with rotary packed bed liquid-inlet (2.8) through pump (2), header tank (4) by the diazonium salt hydrolysis of p-Aminobenzaldehyde.
5. according to claim 3ly prepare the device of PARA HYDROXY BENZALDEHYDE, it is characterized in that in the tower of guide plate type tower (12) that setting can make fluid form baffling mobile several layers traverse baffle (3.5) or can make fluid form eddy flow mobile several layers eddy flow plate (3.6) by the diazonium salt hydrolysis of p-Aminobenzaldehyde.
6. according to claim 3ly prepare the device of PARA HYDROXY BENZALDEHYDE by the diazonium salt hydrolysis of p-Aminobenzaldehyde, it is characterized in that condensing surface (14) links to each other with strainer II (15) again, strainer II (15) connects mother liquor accumulator tank (16).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4273941A (en) * | 1977-09-07 | 1981-06-16 | Seitetsu Kagaku Co., Ltd. | Process for producing p-hydroxybenzaldehyde |
| CN1539805A (en) * | 2003-10-24 | 2004-10-27 | 中国科学院广州化学研究所 | Method for synthesizing pterostilbene |
| CN101125800A (en) * | 2007-09-28 | 2008-02-20 | 中北大学 | Technique for preparing m-cresol |
| CN201351148Y (en) * | 2009-01-14 | 2009-11-25 | 中北大学 | Device for preparation of parahydroxyben-zaldehyde by hydrolyzing diazonium salt of para aminotenzaldehyde |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4273941A (en) * | 1977-09-07 | 1981-06-16 | Seitetsu Kagaku Co., Ltd. | Process for producing p-hydroxybenzaldehyde |
| CN1539805A (en) * | 2003-10-24 | 2004-10-27 | 中国科学院广州化学研究所 | Method for synthesizing pterostilbene |
| CN101125800A (en) * | 2007-09-28 | 2008-02-20 | 中北大学 | Technique for preparing m-cresol |
| CN201351148Y (en) * | 2009-01-14 | 2009-11-25 | 中北大学 | Device for preparation of parahydroxyben-zaldehyde by hydrolyzing diazonium salt of para aminotenzaldehyde |
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| 喻华兵等.旋转填料床最新研究进展.《化学工程师》.2005,(第2期),35-37. * |
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