CN104961630A - Preparation method of 2, 5-dichlorophenol - Google Patents
Preparation method of 2, 5-dichlorophenol Download PDFInfo
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- CN104961630A CN104961630A CN201510335204.5A CN201510335204A CN104961630A CN 104961630 A CN104961630 A CN 104961630A CN 201510335204 A CN201510335204 A CN 201510335204A CN 104961630 A CN104961630 A CN 104961630A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
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Abstract
The invention provides a preparation method of 2, 5-dichlorophenol. The preparation method of the 2, 5-dichlorophenol comprises the following steps of pretreatment of catalyst and assistant agents, 1, 4-dichlorobenzene one-step-method product synthesizing, continuous rectification of 2, 5-dichlorophenol and recycling of a substrate and solvent. By the preparation method, the catalyst and the assistant agents are pretreated, the catalytic performance and the catalytic effect of the catalyst can be improved effectively, the efficiency and the yield of synthesis reaction are improved, the use level of the catalyst and the use level of the assistant agents can be reduced obviously, production cost is reduced, heavy components are reduced, and follow-up separation and purification operation is facilitated. Synthetic reaction products are rectified, separated and purified, the purity of the obtained 2, 5-dichlorophenol is greater than 99.5%, the purify of the 1, 4-dichlorobenzene, the solvent and water which are obtained by recycling is greater than 99%, the recycled raw material and the recycled solvent can be directly used for next synthetic reaction, the production cost is reduced, and environmental protection is facilitated.
Description
Technical field
The present invention relates to the preparation method of 2,5-chlorophenesic acid.More particularly, the present invention relates to a kind of with Isosorbide-5-Nitrae-dichlorobenzene for raw material, efficiently synthesize 2,5-chlorophenesic acid by single step reaction, then the method that multistep continuous rectification prepares high purity 2,5-chlorophenesic acid carried out to it.
Background technology
2,5-chlorophenesic acid is the intermediate of a kind of important agricultural chemicals, medicine, dyestuff, nitrogen fertilizer potentiating agent and leather fungicide etc.At present, 2,5-chlorophenesic acid is used for the synthesis of the chloro-O-Anisic Acid of weedicide 3,6-bis-(Dicamba).
The method of current preparation 2,5-chlorophenesic acid, mainly contains 1,2,4-trichlorobenzene hydrolysis method and 2,5-dichlorphenamide bulk powder diazonium hydrolysis method.But 1,2,4-trichlorobenzene hydrolysis method needs to be obtained by high temperature and high pressure hydrolysis, can use a large amount of bronsted lowry acids and bases bronsted lowries in preparation process, produces a large amount of three industrial wastes, and product is the mixture of isomers, and follow-up not easily separating-purifying, industrial cost is high.2,5-dichlorphenamide bulk powder diazonium hydrolysis method can use a large amount of sulfuric acid and nitrite, serious to equipment corrosion, energy consumption is high, is difficult to recycle and process, contaminate environment, substrate 2 in addition, the preparation process of 5-dichlorphenamide bulk powder relates to nitration reaction, and the use of a large amount of sulfuric acid and nitrite is not only had higher requirement to equipment, also exacerbates the harm to environment.
In order to solve this defect, with 1 in prior art, 4-dichlorobenzene is that raw material prepares the method for 2,5-chlorophenesic acid by catalyzed oxidation, adopts heteropolyacid, heteropolyacid salt or its loading type to be catalyzer, its reaction scheme is short, simple to operate, almost environmentally safe, but catalytic effect is undesirable, catalyst recovery difficulty, and its follow-up purification refine technique is not disclosed.
Summary of the invention
As the result of various extensive and careful research and experiment, the present inventor has been found that, with 1,4-dichlorobenzene is raw material, in the technological process by single step reaction catalyzed oxidation synthesis 2,5-chlorophenesic acid, pre-treatment is carried out to auxiliary and catalyzer and can significantly improve catalytic efficiency, improve the yield of 2,5-chlorophenesic acid, and the problems such as the recovery of reaction mixture Raw, solvent etc. and product purity that the present invention is directed to propose a kind of rationally continuous rectification separation method efficiently.
Therefore, an object of the present invention is to solve at least the problems referred to above and/or defect, and the advantage will illustrated at least is below provided.
Another object of the present invention is to provide a kind of synthetic method of 2,5-chlorophenesic acid, its with Isosorbide-5-Nitrae-dichlorobenzene for raw material, by single step reaction can be efficient catalyzed oxidation synthesis 2,5-chlorophenesic acid, product yield is high, low for equipment requirements and environmentally safe.
Another object of the present invention is the mixed composition obtained for described building-up reactions, provides a kind of efficient method for subsequent processing, on the basis that guarantee 2,5-chlorophenesic acid purity is higher, improves organic efficiency and the purity of raw material, solvent etc.
In order to realize according to these objects of the present invention and other advantage, provide a kind of preparation method of 2,5-chlorophenesic acid, it comprises the following steps:
Step one: the auxiliary of the oxide compound of the vanadium of 1/1000 ~ 1/25 weight part and 1/100 ~ 1 weight part is joined in the acetic acid of 1/30 ~ 1/5 weight part, 5 ~ 10min is stirred under 55 ~ 65 DEG C (preferably 60 ~ 62 DEG C), then adding with the oxide mol ratio of described vanadium is the superoxide of 0.5 ~ 1.5, continue stirring 20 ~ 30min, obtain activation solution;
Step 2: the Isosorbide-5-Nitrae-dichlorobenzene of 1 weight part and the acetic acid of 2 ~ 10 weight parts are stirred at not higher than the temperature of 30 DEG C and mix, then add described activation solution, obtain reaction solution;
Step 3: at 35 ~ 75 DEG C of temperature (preferably 40 ~ 50 DEG C), the described superoxide being 0.3 ~ 4 by the mol ratio with described Isosorbide-5-Nitrae-dichlorobenzene drops in described reaction solution, and time for adding is 2 ~ 8h (preferably 4 ~ 6h), after dropwising, continue to stir 0.5h; Add subsequently with described peroxide mole ratio be 0.5 ~ 0.8 sodium bisulfite or S-WAT, stir 5min, filter, obtain filtrate;
Step 4: described filtrate is carried out separating-purifying by least three rectifying tower, described rectifying tower comprises the first rectifying tower, the Second distillation column be connected in parallel by pipeline with described first rectifying tower respectively and the 3rd rectifying tower;
The charging flow velocity of wherein said first rectifying tower is 7500 ~ 9000kg/h, and feeding temperature is 85 ~ 100 DEG C, and feed pressure is 30 ~ 45kPa;
The charging flow velocity of described Second distillation column is 3000 ~ 4500kg/h, and feeding temperature is 80 ~ 90 DEG C, and feed pressure is 30 ~ 40kPa;
The charging flow velocity of described 3rd rectifying tower is 300 ~ 600kg/h, and feeding temperature is 120 ~ 150 DEG C, and feed pressure is 8 ~ 15kPa.
Preferably, wherein, the oxide compound of described vanadium is selected from V
2o
5, V
2o
3in any one, described auxiliary is selected from any one in polyphosphoric acid, tetra-sodium.
Preferably, wherein, described superoxide is selected from H
2o
2, Peracetic Acid, tertbutyl peroxide, peroxyformic acid, any one in Perpropionic Acid, described superoxide is preferably the H that massfraction is 20 ~ 70%
2o
2, preferred, described superoxide to be massfraction be 20 ~ 50% H
2o
2.H
2o
2massfraction be an important influence factor, if its massfraction is too low, too much water can be introduced in organic synthesis system, affect catalytic conversion efficiency and productive rate, work as H
2o
2massfraction when being down to below 20%, the transformation efficiency of Isosorbide-5-Nitrae-dichlorobenzene declines to a great extent; But H
2o
2massfraction can not be too high, the H of high density
2o
2easy decomposition, releases large calorimetric, works as H
2o
2massfraction when being greater than 70%, more by product can be generated, reduce product yield, and the H that massfraction is greater than 70%
2o
2high especially to the equipment requirements of accumulating, and need venting port be reserved, otherwise danger of very easily blasting in transportation.
Preferably, wherein, in step, the add-on of the oxide compound of described vanadium is 1/1000 ~ 1/28 weight part, the add-on of described auxiliary is 1/50 ~ 1/5 weight part, the amount that acetic acid described in step 2 adds is 3 ~ 7 weight parts, and the mol ratio of superoxide described in step 3 and described Isosorbide-5-Nitrae-dichlorobenzene is 0.5 ~ 2.Described catalyzer and auxiliary are after superoxide pre-treatment and activation step, obtain the title complex of three components, the solute effect of catalyzer and auxiliary significantly improves, the catalytic efficiency of catalyzer is also obviously promoted, at substrate 1, when the amount of 4-dichlorobenzene is constant, the add-on of required catalyzer reduces 10 ~ 15 times, and the add-on of required auxiliary reduces 5 ~ 10 times.
Preferably, wherein, described filtrate before entering rectifying tower at least through an evaporating kettle to deviate from heavy component, to prevent heavy component etching apparatus, the charging flow velocity of described evaporating kettle is 6000 ~ 9000kg/h, and feeding temperature is 25 ~ 30 DEG C, and pressure is 300 ~ 500kPa.
Preferably, wherein, stripping tower and Isosorbide-5-Nitrae-dichlorobenzene treating tower between described first rectifying tower and described Second distillation column, is also disposed with, in order to further refine and reclaim Isosorbide-5-Nitrae-dichlorobenzene and the purity improving product.
Preferably, wherein, described first rectifying tower is combination tower, top is 2 sections of packing towers, to be stage number be in the bottom partitioned column of 30 layers, packing tower has higher mass transfer and separation efficiency relative to tray column, tower height can be reduced, but cost is also higher, component for the charging of the present invention first rectifying tower is water, acetic acid, 1, 4-dichlorobenzene and described 2, the practical situation of the mixture of 5-chlorophenesic acid, be designed to top packing tower, the structure of bottom tray column, effectively can increase treatment capacity, on the basis ensureing the certain separation efficiency of batch ingredients, reduce tower height, reduce energy consumption,
Described first rectifying tower bottom is partitioned column mechanism, be divided into two by the main body tower, make three components in tower, carry out mass transfer, heat transfer simultaneously, realize the separation of three components simultaneously, described first rectifying tower tower top deviates from waste water, the mixture extracting acetic acid and water in tower out enters described Second distillation column, tower reactor obtain described 1,4-dichlorobenzene and described 2, the mixture of 5-chlorophenesic acid enters described stripping tower, and this tower structure completes the separation task usually needing two conventional towers just can complete, and greatly reduces energy expenditure.
Preferably, wherein, the stage number of described Second distillation column is 60 layers, it is refined further and obtains the higher acetic acid of purity, in order to recovery in next batch reaction, and Second distillation column tower top is deviate from waste water and flowed to described first tower bottom of rectifying tower with gas phase, waste water condensation releases heat in order to heat the first rectifying tower, saves energy consumption;
Described 3rd rectifying tower is 3 sections of packing towers, and the 3rd rectifying tower obtains product 2,5-chlorophenesic acid in order to be separated, due to higher to the requirement of product purity, and packing tower has higher mass-transfer efficiency compared with tray column, therefore the present invention selects packing tower to reduce tower height, ensures product purity; Packing tower is designed to 3 sections, the purity of product 2, the 5-chlorophenesic acid obtained is greater than 99.5%, and filler disjunction is too many, the column internalss such as required sparger and redistributor also can correspondingly increase, increase cost, but filler segmentation very little, easily occurs wall stream effect, reduce separation efficiency, when filler only has 2 sections, the purity of product 2, the 5-chlorophenesic acid obtained only has 98.9%.
Preferably, wherein, the stage number of described stripping tower is 12 layers, in order to the acetic acid in the mixed solution of Isosorbide-5-Nitrae-dichlorobenzene and 2,5-chlorophenesic acid and water to be separated further; Described Isosorbide-5-Nitrae-dichlorobenzene treating tower is 3 sections of packing towers, makes substrate Isosorbide-5-Nitrae-dichlorobenzene and product 2,5-chlorophenesic acid is effectively separated, wherein, and described 1, the charging flow velocity of 4-dichlorobenzene treating tower is 900 ~ 1500kg/h, and feeding temperature is 130 ~ 150 DEG C, and pressure is 40 ~ 50kPa.
The present invention at least comprises following beneficial effect:
(1) by using a certain amount of oxygenant to carry out pre-treatment to catalyzer and auxiliary, effectively can improve catalytic performance and the catalytic effect of catalyzer, thus improve efficiency and the yield of one-step synthesis reaction;
(2) catalyzer of the present invention and auxiliary are after pretreatment, and when raw material input amount is constant, the amount added needed for catalyzer and auxiliary obviously reduces, and reduces production cost, and heavy component reduces, and is beneficial to later separation purification work;
(3) waste water that Second distillation column tower top is deviate from flows to described first tower bottom of rectifying tower with gas phase, and waste water condensation liberated heat in order to heat the first rectifying tower, can save energy consumption;
(4) first rectifying tower bottoms are partitioned column, be divided into two by the main body tower, make three components in tower, carry out mass transfer, heat transfer simultaneously, realize the separation of three components simultaneously, complete the separation task usually needing two conventional towers just can complete, greatly reduce energy expenditure;
(5) by carrying out rectifying separation purification to synthesis reaction product, obtain product 2, the purity of 5-chlorophenesic acid is greater than 99.5%, reclaim the raw material 1 obtained, 4-dichlorobenzene, solvent and water purity are all greater than 99%, recovery raw material, solvent can be directly used in next batch building-up reactions, reduce production cost, are beneficial to environmental protection;
(6) synthesis step of the present invention only has a step, and route is short, reacts without the need to High Temperature High Pressure, and reaction conditions is gentle, low for equipment requirements, and technological operation is simple, and in product preparation process, almost no waste discharge, environmentally friendly, is beneficial to suitability for industrialized production.
Part is embodied by explanation below by other advantage of the present invention, target and feature, part also will by research and practice of the present invention by those skilled in the art is understood.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, can implement according to this with reference to specification sheets word to make those skilled in the art.
Should be appreciated that used hereinly such as " to have ", other element one or more do not allotted in " comprising " and " comprising " term or the existence of its combination or interpolation.
< example 1>
By the V of 0.001 weight part
2o
5join in the acetic acid of 1/30 weight part with the polyphosphoric acid of 0.01 weight part, at 55 DEG C, stir 8min, then add 2.7 × 10
-4the massfraction of weight part is the H of 20%
2o
2, continue to stir 20min, obtain activation solution;
Isosorbide-5-Nitrae-the dichlorobenzene of 1 weight part and the acetic acid of 2 weight parts are stirred at the temperature of 30 DEG C and mix, then add described activation solution, obtain reaction solution;
At 35 DEG C of temperature, be the H of 20% by the massfraction of 0.20 weight part
2o
2drop in described reaction solution, time for adding is 2h, after dropwising, continues to stir 0.5h; Add the S-WAT of 0.2 weight part subsequently, stir 5min, filter, obtain filtrate;
Join in evaporating kettle by above-mentioned filtrate with the speed of 6000kg/h, its feeding temperature is 25 DEG C, and pressure is 300kPa, to remove the heavy constituent such as phosphoric acid, tar, catalyzer in mother liquor, for the recovery of phosphoric acid, catalyzer.The gas phase that evaporating kettle is deviate from enters the first rectifying tower, and wherein charging flow velocity is 7500kg/h, and feeding temperature is 85 DEG C, and feed pressure is 40kPa; Described first rectifying tower is combination tower, top is 2 sections of packing towers, to be stage number be in the bottom partitioned column of 30 layers, first rectifying tower tower top deviates from waste water with the speed of 500kg/h, the mixture extracting acetic acid and water in tower out enters described Second distillation column, the mixture of described Isosorbide-5-Nitrae-dichlorobenzene that tower reactor obtains and described 2,5-chlorophenesic acid enters described stripping tower.
The stage number of Second distillation column is 60 layers, and its charging flow velocity is 3000kg/h, and feeding temperature is 90 DEG C, and pressure is 35kPa; Second distillation column tower top deviates from waste water with the speed of 200kg/h, tower reactor reclaims with the speed of 3000kg/h and obtains acetic acid, wherein the isolated vapor phase stream of the tower top of Second distillation column is to the left side tower reactor heating of the first partition in tower, self becomes wastewater streams through condensation and goes out, save energy consumption.
The stage number of described stripping tower is 12 layers, and top gaseous phase enters tower reactor on the right side of the first rectifying tower dividing plate, and tower bottoms enters 1 with the flow velocity of 900kg/h, 4-dichlorobenzene treating tower, wherein, described 1,4-dichlorobenzene treating tower is 3 sections of packing towers, and its feeding temperature is 130 DEG C, and pressure is 40kPa; Isosorbide-5-Nitrae-dichlorobenzene treating tower tower top isolates Isosorbide-5-Nitrae-dichlorobenzene with the speed of 900kg/h, and tower bottoms enters the 3rd rectifying tower with 300kg/h, and wherein the 3rd rectifying tower is 3 sections of packing towers, and its feeding temperature is 120 DEG C, and pressure is 8kPa; 3rd rectifying tower ejects light constituent and returns Isosorbide-5-Nitrae-dichlorobenzene treating tower, goes out product 2,5-chlorophenesic acid product, go out component, return evaporating kettle bottom tower reactor in tower with the velocity separation of 210kg/h.
The product 2 that final rectifying obtains, the purity of 5-chlorophenesic acid is 99.8%, the purity reclaiming the acetic acid obtained is 99.4%, and the purity reclaiming the Isosorbide-5-Nitrae-dichlorobenzene obtained is 99.2%, wherein obtain 2 altogether, 5-chlorophenesic acid 0.34 part, reclaims and obtains 0.58 part of raw material Isosorbide-5-Nitrae-dichlorobenzene, the yield (deduction reclaims raw material) of product 2,5-chlorophenesic acid is 73.0%.
< example 2>
By the V of 0.002 weight part
2o
5join in the acetic acid of 1/5 weight part with the polyphosphoric acid of 0.02 weight part, at 65 DEG C, stir 10min, after add 7.4 × 10
-4the massfraction of weight part is the H of 40%
2o
2, after continuing to stir 25min, obtain activation solution;
Isosorbide-5-Nitrae-the dichlorobenzene of 1 weight part and the acetic acid of 5 weight parts are stirred at the temperature of 28 DEG C and mix, then add described activation solution, obtain reaction solution;
At 72 DEG C of temperature, be the H of 40% by the massfraction of 0.92 weight part
2o
2drop in described reaction solution, time for adding is 8h, after dropwising, continues to stir 0.5h; Add the sodium bisulfite of 0.98 weight part subsequently, stir 5min, filter, obtain filtrate;
Join in evaporating kettle by above-mentioned filtrate with the speed of 9000kg/h, its feeding temperature is 30 DEG C, and pressure is 500kPa, to remove the heavy constituent such as phosphoric acid, tar, catalyzer in mother liquor, for the recovery of phosphoric acid, catalyzer.The gas phase that evaporating kettle is deviate from enters the first rectifying tower, and wherein charging flow velocity is 8500kg/h, and feeding temperature is 90 DEG C, and feed pressure is 30kPa; Described first rectifying tower is combination tower, top is 2 sections of packing towers, to be stage number be in the bottom partitioned column of 30 layers, first rectifying tower tower top deviates from waste water with the speed of 600kg/h, the mixture extracting acetic acid and water in tower out enters described Second distillation column, the mixture of described Isosorbide-5-Nitrae-dichlorobenzene that tower reactor obtains and described 2,5-chlorophenesic acid enters described stripping tower.
The stage number of Second distillation column is 60 layers, and its charging flow velocity is 4000kg/h, and feeding temperature is 80 DEG C, and pressure is 30kPa; Second distillation column tower top deviates from waste water with the speed of 220kg/h, tower reactor reclaims with the speed of 4500kg/h and obtains acetic acid, wherein the isolated vapor phase stream of the tower top of Second distillation column is to the left side tower reactor heating of the first partition in tower, self becomes wastewater streams through condensation and goes out, save energy consumption.
The stage number of described stripping tower is 12 layers, and top gaseous phase enters tower reactor on the right side of the first rectifying tower dividing plate, and tower bottoms enters 1 with the flow velocity of 1500kg/h, 4-dichlorobenzene treating tower, wherein, described 1,4-dichlorobenzene treating tower is 3 sections of packing towers, and its feeding temperature is 150 DEG C, and pressure is 50kPa; Isosorbide-5-Nitrae-dichlorobenzene treating tower tower top isolates Isosorbide-5-Nitrae-dichlorobenzene with the speed of 850kg/h, and tower bottoms enters the 3rd rectifying tower with 400kg/h, and wherein the 3rd rectifying tower is 3 sections of packing towers, and its feeding temperature is 130 DEG C, and pressure is 10kPa; 3rd rectifying tower ejects light constituent and returns Isosorbide-5-Nitrae-dichlorobenzene treating tower, goes out product 2,5-chlorophenesic acid product, go out component, return evaporating kettle bottom tower reactor in tower with the velocity separation of 300kg/h.
The product 2 that final rectifying obtains, the purity of 5-chlorophenesic acid is 99.7%, the purity reclaiming the acetic acid obtained is 99.2%, and the purity reclaiming the Isosorbide-5-Nitrae-dichlorobenzene obtained is 99.1%, wherein obtain 2 altogether, 5-chlorophenesic acid 0.39 part, reclaims and obtains 0.54 part of raw material Isosorbide-5-Nitrae-dichlorobenzene, the yield (deduction reclaims raw material) of product 2,5-chlorophenesic acid is 76.5%.
< example 3>
By the V of 0.04 weight part
2o
3join in the acetic acid of 1/20 weight part with the polyphosphoric acid of 1 weight part, at 57 DEG C, stir 9min, the massfraction then adding 0.016 weight part is the H of 70%
2o
2, continue to stir 30min, obtain activation solution;
Isosorbide-5-Nitrae-the dichlorobenzene of 1 weight part and the acetic acid of 10 weight parts are stirred at the temperature of 25 DEG C and mix, then add described activation solution, obtain reaction solution;
At 50 DEG C of temperature, be the H of 70% by the massfraction of 1.32 weight parts
2o
2drop in described reaction solution, time for adding is 5h, after dropwising, continues to stir 0.5h; Add the S-WAT of 1.72 weight parts subsequently, stir 5min, filter, obtain filtrate;
Join in evaporating kettle by above-mentioned filtrate with the speed of 8000kg/h, its feeding temperature is 28 DEG C, and pressure is 400kPa, to remove the heavy constituent such as phosphoric acid, tar, catalyzer in mother liquor, for the recovery of phosphoric acid, catalyzer.The gas phase that evaporating kettle is deviate from enters the first rectifying tower, and wherein charging flow velocity is 9000kg/h, and feeding temperature is 100 DEG C, and feed pressure is 42kPa; Described first rectifying tower is combination tower, top is 2 sections of packing towers, to be stage number be in the bottom partitioned column of 30 layers, first rectifying tower tower top deviates from waste water with the speed of 800kg/h, the mixture extracting acetic acid and water in tower out enters described Second distillation column, the mixture of described Isosorbide-5-Nitrae-dichlorobenzene that tower reactor obtains and described 2,5-chlorophenesic acid enters described stripping tower.
The stage number of Second distillation column is 60 layers, and its charging flow velocity is 4500kg/h, and feeding temperature is 80 DEG C, and pressure is 38kPa; Second distillation column tower top deviates from waste water with the speed of 190kg/h, tower reactor reclaims with the speed of 5500kg/h and obtains acetic acid, wherein the isolated vapor phase stream of the tower top of Second distillation column is to the left side tower reactor heating of the first partition in tower, self becomes wastewater streams through condensation and goes out, save energy consumption.
The stage number of described stripping tower is 12 layers, and top gaseous phase enters tower reactor on the right side of the first rectifying tower dividing plate, and tower bottoms enters 1 with the flow velocity of 1200kg/h, 4-dichlorobenzene treating tower, wherein, described 1,4-dichlorobenzene treating tower is 3 sections of packing towers, and its feeding temperature is 140 DEG C, and pressure is 45kPa; Tower bottoms enters Isosorbide-5-Nitrae-dichlorobenzene treating tower; Isosorbide-5-Nitrae-dichlorobenzene treating tower tower top isolates Isosorbide-5-Nitrae-dichlorobenzene with the speed of 950kg/h, and tower bottoms enters the 3rd rectifying tower with 600kg/h, and wherein the 3rd rectifying tower is 3 sections of packing towers, and its feeding temperature is 150 DEG C, and pressure is 15kPa; 3rd rectifying tower ejects light constituent and returns Isosorbide-5-Nitrae-dichlorobenzene treating tower, goes out product 2,5-chlorophenesic acid product, go out component, return evaporating kettle bottom tower reactor in tower with the velocity separation of 280kg/h.
The product 2 that final rectifying obtains, the purity of 5-chlorophenesic acid is 99.6%, the purity reclaiming the acetic acid obtained is 99.3%, and the purity reclaiming the Isosorbide-5-Nitrae-dichlorobenzene obtained is 99.2%, wherein obtain 2 altogether, 5-chlorophenesic acid 0.39 part, reclaims and obtains 0.55 part of raw material Isosorbide-5-Nitrae-dichlorobenzene, the yield (deduction reclaims raw material) of product 2,5-chlorophenesic acid is 78.2%.
< example 4>
By the V of 0.03 weight part
2o
5join in the acetic acid of 1/15 weight part with the tetra-sodium of 0.05 weight part, at 60 DEG C, stir 6min, after add the Peracetic Acid of 0.013 weight part, continue to stir 28min, obtain activation solution;
Isosorbide-5-Nitrae-the dichlorobenzene of 1 weight part and the acetic acid of 8 weight parts are stirred at the temperature of 27 DEG C and mix, then add described activation solution, obtain reaction solution;
At 38 DEG C of temperature, the Peracetic Acid of 0.91 weight part dropped in described reaction solution, time for adding is 6h, after dropwising, continues to stir 0.5h; Add the sodium bisulfite of 0.63 weight part subsequently, stir 5min, filter, obtain filtrate;
Join in evaporating kettle by above-mentioned filtrate with the speed of 6500kg/h, its feeding temperature is 29 DEG C, and pressure is 450kPa, to remove the heavy constituent such as phosphoric acid, tar, catalyzer in mother liquor, for the recovery of phosphoric acid, catalyzer.The gas phase that evaporating kettle is deviate from enters the first rectifying tower, and wherein charging flow velocity is 7800kg/h, and feeding temperature is 95 DEG C, and feed pressure is 38kPa; Described first rectifying tower is combination tower, top is 2 sections of packing towers, to be stage number be in the bottom partitioned column of 30 layers, first rectifying tower tower top deviates from waste water with the speed of 740kg/h, the mixture extracting acetic acid and water in tower out enters described Second distillation column, the mixture of described Isosorbide-5-Nitrae-dichlorobenzene that tower reactor obtains and described 2,5-chlorophenesic acid enters described stripping tower.
The stage number of Second distillation column is 60 layers, and its charging flow velocity is 3900kg/h, and feeding temperature is 84 DEG C, and pressure is 32kPa; Second distillation column tower top deviates from waste water with the speed of 204kg/h, tower reactor reclaims with the speed of 5200kg/h and obtains acetic acid, wherein the isolated vapor phase stream of the tower top of Second distillation column is to the left side tower reactor heating of the first partition in tower, self becomes wastewater streams through condensation and goes out, save energy consumption.
The stage number of described stripping tower is 12 layers, and top gaseous phase enters tower reactor on the right side of the first rectifying tower dividing plate, and tower bottoms enters 1 with the flow velocity of 1000kg/h, 4-dichlorobenzene treating tower, wherein, described 1,4-dichlorobenzene treating tower is 3 sections of packing towers, and its feeding temperature is 135 DEG C, and pressure is 42kPa; Isosorbide-5-Nitrae-dichlorobenzene treating tower tower top isolates Isosorbide-5-Nitrae-dichlorobenzene with the speed of 980kg/h, and tower bottoms enters the 3rd rectifying tower with 550kg/h, and wherein the 3rd rectifying tower is 3 sections of packing towers, and its feeding temperature is 135 DEG C, and pressure is 12kPa; 3rd rectifying tower ejects light constituent and returns Isosorbide-5-Nitrae-dichlorobenzene treating tower, goes out product 2,5-chlorophenesic acid product, go out component, return evaporating kettle bottom tower reactor in tower with the velocity separation of 280kg/h.
The product 2 that final rectifying obtains, the purity of 5-chlorophenesic acid is 99.7%, the purity reclaiming the acetic acid obtained is 99.2%, and the purity reclaiming the Isosorbide-5-Nitrae-dichlorobenzene obtained is 99.2%, wherein obtain 2 altogether, 5-chlorophenesic acid 0.34 part, reclaims and obtains 0.59 part of raw material Isosorbide-5-Nitrae-dichlorobenzene, the yield (deduction reclaims raw material) of product 2,5-chlorophenesic acid is 74.8%.
< example 5>
By the V of 0.01 weight part
2o
3join in the acetic acid of 1/10 weight part with the polyphosphoric acid of 0.03 weight part, at 62 DEG C, stir 10min, then add the tertbutyl peroxide of 0.006 weight part, continue to stir 22min, obtain activation solution;
Isosorbide-5-Nitrae-the dichlorobenzene of 1 weight part and the acetic acid of 3 weight parts are stirred at the temperature of 25 DEG C and mix, then add described activation solution, obtain reaction solution;
At 65 DEG C of temperature, dropped to by the tertbutyl peroxide of 1.35 weight parts in described reaction solution, time for adding is 3.5h, after dropwising, continues to stir 0.5h; Add the S-WAT of 1.04 weight parts subsequently, stir 5min, filter, obtain filtrate;
Join in evaporating kettle by above-mentioned filtrate with the speed of 8500kg/h, its feeding temperature is 26 DEG C, and pressure is 360kPa, to remove the heavy constituent such as phosphoric acid, tar, catalyzer in mother liquor, for the recovery of phosphoric acid, catalyzer.The gas phase that evaporating kettle is deviate from enters the first rectifying tower, and wherein charging flow velocity is 8300kg/h, and feeding temperature is 88 DEG C, and feed pressure is 37kPa; Described first rectifying tower is combination tower, top is 2 sections of packing towers, to be stage number be in the bottom partitioned column of 30 layers, first rectifying tower tower top deviates from waste water with the speed of 690kg/h, the mixture extracting acetic acid and water in tower out enters described Second distillation column, the mixture of described Isosorbide-5-Nitrae-dichlorobenzene that tower reactor obtains and described 2,5-chlorophenesic acid enters described stripping tower.
The stage number of Second distillation column is 60 layers, and its charging flow velocity is 3700kg/h, and feeding temperature is 83 DEG C, and pressure is 35kPa; Second distillation column tower top deviates from waste water with the speed of 196kg/h, tower reactor reclaims with the speed of 5100kg/h and obtains acetic acid, wherein the isolated vapor phase stream of the tower top of Second distillation column is to the left side tower reactor heating of the first partition in tower, self becomes wastewater streams through condensation and goes out, save energy consumption.
The stage number of described stripping tower is 12 layers, and top gaseous phase enters tower reactor on the right side of the first rectifying tower dividing plate, and tower bottoms enters 1 with the flow velocity of 1400kg/h, 4-dichlorobenzene treating tower, wherein, described 1,4-dichlorobenzene treating tower is 3 sections of packing towers, and its feeding temperature is 145 DEG C, and pressure is 40kPa; Isosorbide-5-Nitrae-dichlorobenzene treating tower tower top isolates Isosorbide-5-Nitrae-dichlorobenzene with the speed of 890kg/h, and tower bottoms enters the 3rd rectifying tower with 340kg/h, and wherein the 3rd rectifying tower is 3 sections of packing towers, and its feeding temperature is 133 DEG C, and pressure is 11kPa; 3rd rectifying tower ejects light constituent and returns Isosorbide-5-Nitrae-dichlorobenzene treating tower, goes out product 2,5-chlorophenesic acid product, go out component, return evaporating kettle bottom tower reactor in tower with the velocity separation of 290kg/h.
The product 2 that final rectifying obtains, the purity of 5-chlorophenesic acid is 99.7%, the purity reclaiming the acetic acid obtained is 99.5%, and the purity reclaiming the Isosorbide-5-Nitrae-dichlorobenzene obtained is 99.3%, wherein obtain 2 altogether, 5-chlorophenesic acid 0.34 part, reclaims and obtains 0.60 part of raw material Isosorbide-5-Nitrae-dichlorobenzene, the yield (deduction reclaims raw material) of product 2,5-chlorophenesic acid is 76.6%.
< example 6>
By the V of 0.005 weight part
2o
5join in the acetic acid of 1/9 weight part with the polyphosphoric acid of 0.9 weight part, at 63 DEG C, stir 6min, after add the peroxyformic acid of 0.002 weight part, continue to stir 21min, obtain activation solution;
Isosorbide-5-Nitrae-the dichlorobenzene of 1 weight part and the acetic acid of 4 weight parts are stirred at the temperature of 27 DEG C and mix, then add described activation solution, obtain reaction solution;
At 58 DEG C of temperature, dropped to by the peroxyformic acid of 0.97 weight part in described reaction solution, time for adding is 6.5h, after dropwising, continues to stir 0.5h; Add the S-WAT of 1.28 weight parts subsequently, stir 5min, filter, obtain filtrate;
Join in evaporating kettle by above-mentioned filtrate with the speed of 7200kg/h, its feeding temperature is 27 DEG C, and pressure is 430kPa, to remove the heavy constituent such as phosphoric acid, tar, catalyzer in mother liquor, for the recovery of phosphoric acid, catalyzer.The gas phase that evaporating kettle is deviate from enters the first rectifying tower, and wherein charging flow velocity is 8800kg/h, and feeding temperature is 97 DEG C, and feed pressure is 32kPa; Described first rectifying tower is combination tower, top is 2 sections of packing towers, to be stage number be in the bottom partitioned column of 30 layers, first rectifying tower tower top deviates from waste water with the speed of 710kg/h, the mixture extracting acetic acid and water in tower out enters described Second distillation column, the mixture of described Isosorbide-5-Nitrae-dichlorobenzene that tower reactor obtains and described 2,5-chlorophenesic acid enters described stripping tower.
The stage number of Second distillation column is 60 layers, and its charging flow velocity is 4100kg/h, and feeding temperature is 88 DEG C, and pressure is 37kPa; Second distillation column tower top deviates from waste water with the speed of 230kg/h, tower reactor reclaims with the speed of 5700kg/h and obtains acetic acid, wherein the isolated vapor phase stream of the tower top of Second distillation column is to the left side tower reactor heating of the first partition in tower, self becomes wastewater streams through condensation and goes out, save energy consumption.
The stage number of described stripping tower is 12 layers, and top gaseous phase enters tower reactor on the right side of the first rectifying tower dividing plate, and tower bottoms enters 1 with the flow velocity of 1100kg/h, 4-dichlorobenzene treating tower, wherein, described 1,4-dichlorobenzene treating tower is 3 sections of packing towers, and its feeding temperature is 138 DEG C, and pressure is 49kPa; Isosorbide-5-Nitrae-dichlorobenzene treating tower tower top isolates Isosorbide-5-Nitrae-dichlorobenzene with the speed of 1000kg/h, and tower bottoms enters the 3rd rectifying tower with 420kg/h, and wherein the 3rd rectifying tower is 3 sections of packing towers, and its feeding temperature is 145 DEG C, and pressure is 13kPa; 3rd rectifying tower ejects light constituent and returns Isosorbide-5-Nitrae-dichlorobenzene treating tower, goes out product 2,5-chlorophenesic acid product, go out component, return evaporating kettle bottom tower reactor in tower with the velocity separation of 250kg/h.
The product 2 that final rectifying obtains, the purity of 5-chlorophenesic acid is 99.7%, the purity reclaiming the acetic acid obtained is 99.3%, and the purity reclaiming the Isosorbide-5-Nitrae-dichlorobenzene obtained is 99.2%, wherein obtain 2 altogether, 5-chlorophenesic acid 0.36 part, reclaims and obtains 0.55 part of raw material Isosorbide-5-Nitrae-dichlorobenzene, the yield (deduction reclaims raw material) of product 2,5-chlorophenesic acid is 72.1%.
< example 7>
By the V of 0.0025 weight part
2o
3join in the acetic acid of 1/27 weight part with the tetra-sodium of 0.17 weight part, at 60 DEG C, stir 9min, then add the peroxyformic acid of 0.0013 weight part, continue to stir 23min, obtain activation solution;
Isosorbide-5-Nitrae-the dichlorobenzene of 1 weight part and the acetic acid of 6 weight parts are stirred at the temperature of 22 DEG C and mix, then add described activation solution, obtain reaction solution;
At 67 DEG C of temperature, dropped to by the peroxyformic acid of 1.26 weight parts in described reaction solution, time for adding is 5h, after dropwising, continues to stir 0.5h; Add the sodium bisulfite of 2.11 weight parts subsequently, stir 5min, filter, obtain filtrate;
Join in evaporating kettle by above-mentioned filtrate with the speed of 8300kg/h, its feeding temperature is 29 DEG C, and pressure is 330kPa, to remove the heavy constituent such as phosphoric acid, tar, catalyzer in mother liquor, for the recovery of phosphoric acid, catalyzer.The gas phase that evaporating kettle is deviate from enters the first rectifying tower, and wherein charging flow velocity is 7800kg/h, and feeding temperature is 86 DEG C, and feed pressure is 38kPa; Described first rectifying tower is combination tower, top is 2 sections of packing towers, to be stage number be in the bottom partitioned column of 30 layers, first rectifying tower tower top deviates from waste water with the speed of 718kg/h, the mixture extracting acetic acid and water in tower out enters described Second distillation column, the mixture of described Isosorbide-5-Nitrae-dichlorobenzene that tower reactor obtains and described 2,5-chlorophenesic acid enters described stripping tower.
The stage number of Second distillation column is 60 layers, and its charging flow velocity is 3200kg/h, and feeding temperature is 84 DEG C, and pressure is 35kPa; Second distillation column tower top deviates from waste water with the speed of 205kg/h, tower reactor reclaims with the speed of 5660kg/h and obtains acetic acid, wherein the isolated vapor phase stream of the tower top of Second distillation column is to the left side tower reactor heating of the first partition in tower, self becomes wastewater streams through condensation and goes out, save energy consumption.
The stage number of described stripping tower is 12 layers, and top gaseous phase enters tower reactor on the right side of the first rectifying tower dividing plate, and tower bottoms enters 1 with the flow velocity of 1300kg/h, 4-dichlorobenzene treating tower, wherein, described 1,4-dichlorobenzene treating tower is 3 sections of packing towers, and its feeding temperature is 143 DEG C, and pressure is 46kPa; Isosorbide-5-Nitrae-dichlorobenzene treating tower tower top isolates Isosorbide-5-Nitrae-dichlorobenzene with the speed of 980kg/h, and tower bottoms enters the 3rd rectifying tower with 550kg/h, and wherein the 3rd rectifying tower is 3 sections of packing towers, and its feeding temperature is 145 DEG C, and pressure is 14kPa; 3rd rectifying tower ejects light constituent and returns Isosorbide-5-Nitrae-dichlorobenzene treating tower, goes out product 2,5-chlorophenesic acid product, go out component, return evaporating kettle bottom tower reactor in tower with the velocity separation of 260kg/h.
The product 2 that final rectifying obtains, the purity of 5-chlorophenesic acid is 99.8%, the purity reclaiming the acetic acid obtained is 99.2%, and the purity reclaiming the Isosorbide-5-Nitrae-dichlorobenzene obtained is 99.2%, wherein obtain 2 altogether, 5-chlorophenesic acid 0.37 part, reclaims and obtains 0.55 part of raw material Isosorbide-5-Nitrae-dichlorobenzene, the yield (deduction reclaims raw material) of product 2,5-chlorophenesic acid is 74.2%.
In order to effect of the present invention is described, contriver provides comparative experiments as follows:
< comparative example 1>
Not to catalyst V
2o
5carry out pre-treatment with auxiliary polyphosphoric acid, directly join in the uniform mixture of Isosorbide-5-Nitrae-dichlorobenzene and acetic acid, identical with example 1 of all the other parameters, technological process is also identical.Finally obtain 2,5-chlorophenesic acid 0.26 part through rectifying, reclaim and obtain 0.57 part of raw material Isosorbide-5-Nitrae-dichlorobenzene, the yield (deduction reclaims raw material) of product 2,5-chlorophenesic acid only has 54.5%.
< comparative example 2>
Not to catalyst V
2o
5pre-treatment is carried out, wherein catalyst V with auxiliary polyphosphoric acid
2o
5for tripolite loading type V
2o
5, catalyzer and auxiliary directly join in the uniform mixture of Isosorbide-5-Nitrae-dichlorobenzene and acetic acid, and identical with example 2 of all the other parameters, technological process is also identical.Finally obtain 2,5-chlorophenesic acid 0.31 part through rectifying, reclaim and obtain 0.56 part of raw material Isosorbide-5-Nitrae-dichlorobenzene, the yield (deduction reclaims raw material) of product 2,5-chlorophenesic acid only has 63.4%.
< comparative example 3>
In this comparative example, the oxide compound of catalyzer vanadium, auxiliary and solvent acetic acid adopt other materials to replace respectively, single factor test simultaneous test (carrying out the replacement simultaneous test of catalyzer, auxiliary and solvent one by one respectively) is carried out with example 3, all the other parameters are identical with example 3, technological process is also identical, and different catalysts, auxiliary and solvent are on synthesizing the impact of reaction yield in table 1.
Table 1 different catalysts, auxiliary and solvent are on the impact of synthesis reaction yield
< comparative example 4>
When Rectification Tower Design, the first rectifying tower bottom does not arrange partitioned column, and identical with example 4 of all the other parameters, technological process is also identical.The product 2 that final rectifying obtains, the purity of 5-chlorophenesic acid is 92.4%, the purity reclaiming the acetic acid obtained is 88.5%, and the purity reclaiming the Isosorbide-5-Nitrae-dichlorobenzene obtained is 91.5%, wherein obtain 2 altogether, 5-chlorophenesic acid 0.28 part, reclaims and obtains 0.51 part of raw material Isosorbide-5-Nitrae-dichlorobenzene, the yield (deduction reclaims raw material) of product 2,5-chlorophenesic acid is 51.5%.
< comparative example 5>
Different feed states can make the amount of liquid of quantity of steam and the decline of rising from feed plate change, thus have influence on separation efficiency, in this comparative example, carry out the first rectifying tower respectively, Second distillation column, 3rd rectifying tower, 1, the charging parameter of 4-dichlorobenzene treating tower and the single factor test simultaneous test of example 5 are (only for the charging flow velocity of one of them rectifying tower, a parameter in feeding temperature and feed pressure changes), identical with example 5 of all the other parameters, technological process is also identical, the concrete charging parameter of rectifying tower and separating effect are in table 2.
The charging parameter of table 2 rectifying tower and separating effect
< comparative example 6>
Different feed states can make the amount of liquid of quantity of steam and the decline of rising from feed plate change, thus have influence on separation efficiency, in this comparative example, carry out the first rectifying tower respectively, Second distillation column, 3rd rectifying tower, 1, the charging parameter of 4-dichlorobenzene treating tower and the single factor test simultaneous test of example 5 are (only for the charging flow velocity of one of them rectifying tower, a parameter in feeding temperature and feed pressure changes), identical with example 6 of all the other parameters, technological process is also identical, the concrete charging parameter of rectifying tower and separating effect are in table 3.
The charging parameter of table 3 rectifying tower and separating effect
Can find out from the various embodiments described above and comparative example, in instances, 2, in the building-up reactions of 5-chlorophenesic acid, owing to having carried out pre-treatment to catalyzer and auxiliary, its Be very effective higher than directly adding not pretreated catalyzer and auxiliary in comparative example, or adds the situation of loaded catalyst and auxiliary; In the rectifying of product, the first rectifying tower bottom is designed to partitioned column, and its rectification and purification successful is better than the structure not arranging partitioned column in comparative example.
Comparative example 1 is compared with example, and comparative example adopts not pretreated catalyzer and auxiliary, and its product yield is 54.5%, significantly lower than in embodiment 1 73.0% product yield.
Comparative example 2 is compared with example, and comparative example adopts not pretreated diatomite support type catalyzer and assists, and its product yield is 63.4%, be starkly lower than the product yield of in embodiment 2 76.5%.
Comparative example 3 is compared with embodiment, and the catalyzer in comparative example, auxiliary and solvent have employed other materials respectively and replace, and its successful declines, and the yield of product is significantly lower than embodiment.
Comparative example 4 is compared with embodiment, first rectifying tower bottom does not arrange partitioned column, the purity of the organic solvent that the product obtained and recovery obtain and raw material all obviously reduces, and due to separating effect decline, portioned product and feedstock portions are taken away by impurity such as solvents, the amount of the product obtained also declines to some extent, and product yield reduces.
Comparative example 5 is compared with embodiment, and the flow velocity of each rectifying tower charging, temperature and pressure are all lower than scope disclosed in this invention, and the flow velocity of rectifying tower charging is too low may cause the phenomenon of leakage, reduces rectification effect; The too low thermal load that can increase evaporating kettle at the bottom of tower of feeding temperature, reduces the refrigeration duty of overhead condenser, affects tower body temperature, changes vapor liquid equilibrium; Feed pressure is too low, and tower top heavy component content can be too high, affects isolate purity, as can be seen from Table 2, the flow velocity of each rectifying tower charging, temperature and pressure, lower than scope disclosed in this invention, can affect rectification effect, cause isolate purity to decline, product yield reduces.
Comparative example 6 is compared with embodiment, the flow velocity of each rectifying tower charging, temperature and pressure are all higher than scope disclosed in this invention, the too high change tower top of flow velocity of rectifying tower charging and the temperature of tower reactor, ring vapor liquid equilibrium in tower, the too high refrigeration duty that can increase overhead condenser of feeding temperature, reduce the thermal load of overhead condenser, affect tower body temperature, change vapor liquid equilibrium; Feed pressure is too high, and at the bottom of tower, Light ends content can be too high, affects isolate purity, as can be seen from Table 3, the flow velocity of each rectifying tower charging, temperature and pressure, higher than scope disclosed in this invention, also can affect rectification effect, cause isolate purity to decline, product yield reduces.
Visible, by using a certain amount of oxygenant to carry out pre-treatment to catalyzer and auxiliary, effectively can improve catalytic performance and the catalytic effect of catalyzer, significantly improving efficiency and the yield of building-up reactions;
In addition, the partitioned column structure of 30 layers that to be stage number be in described first rectifying tower bottom, be divided into two by the main body tower, make three components in tower, carry out mass transfer, heat transfer simultaneously, realize the separation of three components simultaneously, first rectifying tower tower top deviates from waste water, extract the mixture of solvent and water in tower out, tower reactor obtains described Isosorbide-5-Nitrae-dichlorobenzene and described 2, the mixture of 5-chlorophenesic acid, and greatly reduce energy expenditure;
In addition, catalyzer of the present invention and auxiliary after pretreatment, when raw material input amount is constant, due to the raising of catalytic efficiency, the amount added needed for catalyzer and auxiliary all obviously reduces, and reduces production cost, and heavy component reduces, and is beneficial to later separation purification work;
In addition, synthesis step of the present invention only has a step, and route is short, reacts without the need to High Temperature High Pressure, and reaction conditions is gentle, low for equipment requirements, and technological operation is simple, and in product preparation process, almost no waste discharge, environmentally friendly, is beneficial to suitability for industrialized production.
Although embodiment of the present invention are open as above, it is not restricted to listed in specification sheets and embodiment utilization.It can be applied to various applicable the field of the invention completely.For those skilled in the art, can easily realize other amendment.Therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details and illustrates here and the embodiment described.
Claims (10)
1. the preparation method of a chlorophenesic acid, is characterized in that, comprises the following steps:
Step one: the auxiliary of the oxide compound of the vanadium of 1/1000 ~ 1/25 weight part and 1/100 ~ 1 weight part is joined in the acetic acid of 1/30 ~ 1/5 weight part, 5 ~ 10min is stirred at 55 ~ 65 DEG C, then adding with the oxide mol ratio of described vanadium is the superoxide of 0.5 ~ 1.5, continue stirring 20 ~ 30min, obtain activation solution;
Step 2: the Isosorbide-5-Nitrae-dichlorobenzene of 1 weight part and the acetic acid of 2 ~ 10 weight parts are stirred at not higher than the temperature of 30 DEG C and mix, then add described activation solution, obtain reaction solution;
Step 3: at 35 ~ 75 DEG C of temperature, the superoxide being 0.3 ~ 4 by the mol ratio with described Isosorbide-5-Nitrae-dichlorobenzene drops in described reaction solution, and time for adding is 2 ~ 8h, after dropwising, continues to stir 0.5h; Add subsequently with described peroxide mole ratio be 0.5 ~ 0.8 sodium bisulfite or S-WAT, stir 5min, filter, obtain filtrate;
Step 4: described filtrate is carried out separating-purifying by least three rectifying tower, described rectifying tower comprises the first rectifying tower, the Second distillation column be connected in parallel by pipeline with described first rectifying tower respectively and the 3rd rectifying tower;
Wherein, the charging flow velocity of described first rectifying tower is 7500 ~ 9000kg/h, and feeding temperature is 85 ~ 100 DEG C, and feed pressure is 30 ~ 45kPa;
The charging flow velocity of described Second distillation column is 3000 ~ 4500kg/h, and feeding temperature is 80 ~ 90 DEG C, and feed pressure is 30 ~ 40kPa;
The charging flow velocity of described 3rd rectifying tower is 300 ~ 600kg/h, and feeding temperature is 120 ~ 150 DEG C, and feed pressure is 8 ~ 15kPa.
2. the preparation method of 2,5-chlorophenesic acid as claimed in claim 1, is characterized in that, the oxide compound of described vanadium is selected from V
2o
5, V
2o
3in any one, described auxiliary is selected from any one in polyphosphoric acid, tetra-sodium.
3. the preparation method of 2,5-chlorophenesic acid as claimed in claim 1, is characterized in that, described superoxide is selected from H
2o
2, Peracetic Acid, tertbutyl peroxide, peroxyformic acid, any one in Perpropionic Acid, wherein said H
2o
2massfraction be 20 ~ 70%.
4. the preparation method of 2,5-chlorophenesic acid as claimed in claim 3, is characterized in that, described superoxide to be massfraction be 20 ~ 50% H
2o
2.
5. as claimed in claim 12, the preparation method of 5-chlorophenesic acid, it is characterized in that, in step, the add-on of the oxide compound of described vanadium is 1/1000 ~ 1/28 weight part, and the amount that described auxiliary adds is 1/50 ~ 1/5 weight part, and the amount that acetic acid described in step 2 adds is 3 ~ 7 weight parts, the mol ratio of superoxide described in step 3 and described Isosorbide-5-Nitrae-dichlorobenzene is 0.5 ~ 2.
6. as claimed in claim 12, the preparation method of 5-chlorophenesic acid, it is characterized in that, described filtrate before entering rectifying tower at least through an evaporating kettle to deviate from heavy component, the charging flow velocity of described evaporating kettle is 6000 ~ 9000kg/h, feeding temperature is 25 ~ 30 DEG C, and pressure is 300 ~ 500kPa.
7. the preparation method of 2,5-chlorophenesic acid as claimed in claim 1, is characterized in that, stripping tower and 1 is also disposed with between described first rectifying tower and described Second distillation column, 4-dichlorobenzene treating tower, in order to further refine and reclaim Isosorbide-5-Nitrae-dichlorobenzene and the purity improving product.
8. as claimed in claim 72, the preparation method of 5-chlorophenesic acid, it is characterized in that, described first rectifying tower is combination tower, and top is 2 sections of packing towers, to be stage number be in the bottom partitioned column of 30 layers, described first rectifying tower tower top deviates from waste water, and the mixture extracting described acetic acid and water in tower out enters described Second distillation column, tower reactor obtain described 1, the mixed solution of 4-dichlorobenzene and described 2,5-chlorophenesic acid enters described stripping tower.
9. the preparation method of 2,5-chlorophenesic acid as claimed in claim 1, is characterized in that, the stage number of described Second distillation column is 60 layers, and described 3rd rectifying tower is 3 sections of packing towers.
10. as claimed in claim 72, the preparation method of 5-chlorophenesic acid, it is characterized in that, the stage number of described stripping tower is 12 layers, described 1,4-dichlorobenzene treating tower is 3 sections of packing towers, wherein, the charging flow velocity of described Isosorbide-5-Nitrae-dichlorobenzene treating tower is 900 ~ 1500kg/h, feeding temperature is 130 ~ 150 DEG C, and pressure is 40 ~ 50kPa.
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| CN107129426B (en) * | 2016-02-29 | 2021-01-26 | 南京工业大学 | Preparation method of 2, 5-dichlorophenol |
| CN105921161A (en) * | 2016-04-27 | 2016-09-07 | 常州大学 | Catalyst used in p-dichlorobenzene hydroxylate for preparing 2,5-dichlorophenol, and preparation method thereof |
| CN105921161B (en) * | 2016-04-27 | 2018-10-19 | 常州大学 | A kind of catalyst and preparation method thereof preparing 2,5- chlorophenesic acids for paracide hydroxylating |
| CN111825711A (en) * | 2020-07-30 | 2020-10-27 | 四川福思达生物技术开发有限责任公司 | Vanadium pyridine catalyst for preparing 2, 5-dichlorophenol by catalytic oxidation and synthetic method and application thereof |
| CN111825711B (en) * | 2020-07-30 | 2023-08-18 | 四川福思达生物技术开发有限责任公司 | Vanadium pyridine catalyst for preparing 2, 5-dichlorophenol by catalytic oxidation and synthesis method and application thereof |
| CN115385779A (en) * | 2022-08-19 | 2022-11-25 | 湖北泰盛化工有限公司 | 2, 4-dichlorophenol continuous rectification method |
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