CN104151152B - A kind of three circulating methods preparing phenoxy acetic acid without waste water - Google Patents
A kind of three circulating methods preparing phenoxy acetic acid without waste water Download PDFInfo
- Publication number
- CN104151152B CN104151152B CN201410337292.8A CN201410337292A CN104151152B CN 104151152 B CN104151152 B CN 104151152B CN 201410337292 A CN201410337292 A CN 201410337292A CN 104151152 B CN104151152 B CN 104151152B
- Authority
- CN
- China
- Prior art keywords
- sodium
- acetic acid
- mother liquor
- solution
- phenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The problem that the productive rate existed in production process for existing phenoxy acetic acid is not high, produce a large amount of contaminated wastewater environment, the invention provides one " three circulations " formula and prepares the method for phenoxy acetic acid without waste water.It is characterized in that using iron protochloride-EDTA-sodium iodide as catalyzer and adopt the production technique of " three circulation ".In water-organic biphasic, sodium phenylate and sodium chloroacetate condensation generate sodiumphenoxyacetate, and wherein sodium phenylate is excessive, and excessive phenol dissolves recycled in a solvent, is " Recycling Mother Solution "; Use solvent wash sodiumphenoxyacetate, reclaim the phenol carried secretly, be " washings circulation "; Sodiumphenoxyacetate generates phenoxy acetic acid by four phase reactions, decrease temperature crystalline, realizes " salification cycles ".The present invention realizes sodium-chlor and is separated with the effective of phenoxy acetic acid, and overall process emits no waste water, and in working cycle, productive rate can up to more than 98%.
Description
Technical field
The invention belongs to chemical field, have and relate to one " three circulation " formula and prepare the method for phenoxy acetic acid without waste water.
Background technology
Phenoxy acetic acid is a kind of very important chemical, itself and derived product thereof are widely used agricultural chemicals, pharmaceutical prod, have longer use history, verified its of use for many years has the advantages that low toxicity is efficient, security is good, extensively accept by people.But the production process of these chemical still comparatively backwardness, most production technique state being still in its exploitation at first, has the shortcomings such as productive rate is low, waste discharge is high, wastewater flow rate is large.
The synthetic method of phenoxy acetic acid mainly adopts Williamson synthesis, also develops various new synthetic method in recent years as [Northwest Normal College's journal (natural science edition), 1984,2:31-34 such as phase transfer catalysis process; Northwest Normal College's journal (natural science edition), 1984,4:84-86].[Chenzhou Journal of Teachers College (general news column) such as Wu little Wei, 1998,1:43-44] once reported employing Moist chemical synthesis, synthesize phenoxy acetic acid by microwave method, yield is 84.2%, survey fusing point is 97-98 DEG C, king deposited [chemical reagent, 1996,18 (6): 355-356] such as morals and expanded afterwards, the serial aryloxyacetic acid with microwave Fast back-projection algorithm, yield can reach 86.8%-94.1%.Lee's note waits very much [University Of Hebei's journal (natural science edition), 1986,3:59-62] to report a kind of two-phase synthesis method, and in benzene-aqueous sodium hydroxide solution, produce phenoxy acetic acid by phenol and Mono Chloro Acetic Acid condensation, the product yield obtained is 96.4%.Compare with classical way, the temperature of reaction of the method is lower, and operate comparatively easy, product yield is high, and favorable reproducibility.It is catalyst aryl phenol and chloroacetic condensation reaction that Huang Xiaoling etc. [agricultural chemicals, 1989,28 (6): 21] there was reported with 2-fluoro-4-methyl-benzyl trimethylammonium bromide (fluorine quaternary ammonium), and productive rate is 75%.Product fusing point conforms to literature value.With fluorine quaternary ammonium catalysis method synthesis phenoxy acetic acid, be than by liquid-liquid, advantage that is liquid-solid and three-phase catalytic method: without organic solvent, the reaction times is short, productive rate is higher and easy and simple to handle.
Li Yingjun etc. [Northwest Normal College's journal (natural science edition), 1986,2:47-49] once reported with solid-liquid phase transfer catalysis synthesis of aryloxy acetic acid.Reaction is carried out under solid-liquid phase transfer catalysis agent polyoxyethylene glycol (PEG-400) catalysis.Minister in ancient times phoenix tail feathers etc. [chemical reagent, 1989,11 (4): 250] report the polyoxyethylene glycol with homemade polymer catalyst-polystyrene-supported, synthesis of aryloxy acetic acid under three-phase catalytic condition.Huang Shiwei [chemical reagent, 1992,14 (5): 313] etc. there was reported the method for Fast back-projection algorithm aryloxy acetic acid, and with the water of minute quantity, productive rate is up to 98%.
It is phenol that Liang Ying etc. [application chemical industry, 2001,30 (4): 31-32] filter out optimum process condition by orthogonal experiment: Mono Chloro Acetic Acid: sodium hydroxide=0.9:1.1:2.4, and at 102 DEG C of reaction 5h, yield is 69%.
All methods are all adopt the excessive mode of Mono Chloro Acetic Acid to react above.Because chloroacetic hydrolysis is inevitable, therefore in order to improve the transformation efficiency of phenol, Mono Chloro Acetic Acid at least wants excessive more than 20% can obtain higher yield.It is as follows that this method is applied to flow process in industrial production:
This technical process two-step reaction is all carry out in the aqueous solution, simple to operate, and equipment is simple, and solvent cost is also low.But greatest drawback is exactly Mono Chloro Acetic Acid, and hydrolysis is serious, excessive Mono Chloro Acetic Acid cannot re-use, and phenol cannot transform completely, and the Mono Chloro Acetic Acid of hydrolysis and the phenol do not reacted all are drained with waste water, cause raw materials cost to run off in a large number, and bring serious burden to environment.
Summary of the invention
The problem that the productive rate existed in production process for existing phenoxy acetic acid is not high, produce a large amount of contaminated wastewater environment, the present invention improves from three aspects, and one is use catalyzer, improves the efficiency of reaction; Two is the modes adopting condensed mother liquor circulation and wash phenol solvent cycle, achieves the high conversion of phenol; Three is the modes adopting condensed mother liquor water cycle, hydrogen chloride gas acidifying+acidified mother liquor circulation, solves the wastewater problem in production.The application of comprehensive above-mentioned new technology, the invention provides one " three circulations " formula and prepare the method for phenoxy acetic acid without waste water, overall process emits no waste water, and productive rate is up to 98%.
For achieving the above object, technical scheme of the present invention is:
A kind of " three circulations " formula prepares the method for phenoxy acetic acid without waste water, comprises the steps:
(1) sodium phenylate and sodium chloroacetate condensation generate sodiumphenoxyacetate
Get Mono Chloro Acetic Acid and sodium carbonate reacts in water, pH value of solution is adjusted to 6, generate the sodium chloroacetate aqueous solution;
In condensed mother liquor, add phenol and 32-50wt% aqueous sodium hydroxide solution reacts, pH value of solution is adjusted to 12, generate sodium phenylate solution;
With iron protochloride-EDTA-sodium iodide for catalyzer, under the condition of backflow, by above-mentioned sodium phenylate solution and sodium chloroacetate aqueous solution, react, keep temperature of reaction 90 ~ 95 DEG C, reaction soln pH=11.0 ~ 12, reacted after 1 ~ 2 hour, be cooled to less than 40 DEG C, then adjust solution ph to 5 ~ 7 with concentrated hydrochloric acid;
By reacting liquid filtering, obtain solid and mother liquor, mother liquor is divided into two-layer; Wherein, organic phase is condensed mother liquor, recycles in this step; Aqueous phase is condensed mother liquor water, and reuse prepares the reaction solvent of sodium chloroacetate as Mono Chloro Acetic Acid and sodium carbonate, and preparation sodium hydroxide solution; Solid is sodiumphenoxyacetate and sodium chloride mixture;
The main chemical reactions of this process is:
Described condensed mother liquor is chlorine benzene,toluene,xylene, dichlorobenzene, ethylene dichloride or zellon; In described catalyzer, the mol ratio of iron protochloride, EDTA, sodium iodide is 1:1:1; Described catalyst charge is, catalyzer: sodium phenylate is 1g:(3 ~ 3.3) mol; Described concentrated hydrochloric acid is hydrochloric acid or the HCl gas of mass concentration >=30%;
(2) sodiumphenoxyacetate washing is except phenol
The sodiumphenoxyacetate obtain step (1) and sodium chloride mixture, with washing mother liquor making beating process 15 ~ 30 minutes, be dissolved in washing mother liquor by phenol remaining in mixture; After filtration, solid phase is sodiumphenoxyacetate and sodium chloride mixture, and liquid phase is mother liquor; By liquid phase 32-50wt% sodium hydroxide solution process, extract the phenol reclaimed wherein, obtain washing mother liquor after separation respectively and contain phenol sodium hydroxide solution;
Washing mother liquor obtains regenerating and recycles in this step, returns step (1) for preparing sodium phenylate with phenol reactant in condensation reaction containing phenol sodium hydroxide solution;
Described washing mother liquor is chlorine benzene,toluene,xylene, dichlorobenzene, ethylene dichloride or zellon;
(3) sodiumphenoxyacetate acidifying generates phenoxy acetic acid
The solid phase sodiumphenoxyacetate obtain step (2) and sodium chloride mixture join in the acidified mother liquor and water mixed liquid that volume is solid phase 3 ~ 4 times, the volume ratio of acidified mother liquor and water is 4 ~ 6:1, mixed solution dispersed with stirring is heated to 50 ~ 70 DEG C, pass into hydrogen chloride gas again, 1 ~ 2 is reached to acidified mother liquor pH value, the phenoxy acetic acid generated is dissolved in acidified mother liquor, simultaneously precipitated sodium chloride;
After filtered while hot removing sodium-chlor, solution is cooled to less than 20 DEG C crystallizations, and after filtration, drying obtains phenoxy acetic acid solid; Liquid phase is acidified mother liquor and water, recycles in this step;
The main chemical reactions of this process is:
Described acidified mother liquor is chlorine benzene,toluene,xylene, dichlorobenzene, ethylene dichloride or zellon;
The above-mentioned method preparing phenoxy acetic acid, initial feed ratio ratio, phenol: Mono Chloro Acetic Acid: sodium carbonate: sodium hydroxide: hydrogen chloride gas=(1.15 ~ 1.25): (1 ~ 1.05): (0.5 ~ 0.525): (1.15 ~ 1.25): (1.15 ~ 1.25);
Whole process feed ratio is calculated in molar ratio as, phenol: Mono Chloro Acetic Acid: sodium carbonate: sodium hydroxide: hydrogen chloride gas=1:(1 ~ 1.05): (0.5 ~ 0.525): (1.15 ~ 1.25): (1.15 ~ 1.25);
Whole process yield, counts 98% with phenol, counts 94 ~ 95% with Mono Chloro Acetic Acid.
The invention has the advantages that:
1, present invention employs " three circulations " formula synthetic method and prepare phenoxy acetic acid.Generate in sodiumphenoxyacetate step at circulation 1 i.e. sodium phenylate and sodium chloroacetate condensation, in water-organic biphasic, sodium phenylate and sodium chloroacetate condensation generate sodiumphenoxyacetate, and wherein sodium phenylate is excessive, excessive phenol dissolves recycled in a solvent, is " Recycling Mother Solution "; The condensed mother liquor water obtained, can as the reaction solvent of Mono Chloro Acetic Acid and sodium carbonate and the recycling of preparation sodium hydroxide solution in this circulation; Condensed mother liquor is recycle in this step also.Namely sodiumphenoxyacetate washing, except in phenol step, uses solvent wash sodiumphenoxyacetate in cycle 2, reclaims the phenol carried secretly, is " washings circulation "; This part phenol conversion is, after sodium phenylate, turn back in circulation 1 by recycling sodium hydroxide solution, participates in generating sodium phenylate, phenol is fully used and makes washing mother liquor obtain regeneration to make its recycle in this step.Generate in phenoxy acetic acid step in circulation 3 i.e. sodiumphenoxyacetate acidifying, sodiumphenoxyacetate generates phenoxy acetic acid by four phase reactions, decrease temperature crystalline, realizes " salification cycles "; The acidified mother liquor of this step and water can recycles in this step.
2, the present invention feeds intake and adopts the excessive reactive mode of phenol, and phenol excessive in initial action is dissolved in condensed mother liquor, makes phenol and chloroacetic ratio in follow-up three circulating reaction processes remain at 1.2:(1 ~ 1.05); Adopt the mode containing phenol solution circulation, greatly reduce chloroacetic percent hydrolysis, the reactive mode that Mono Chloro Acetic Acid is excessive than ever reduces the raw material consumption being no less than 15%.
3, the present invention is in sodiumphenoxyacetate and sodium chloroacetate condensation reaction, have employed new catalyzer---and iron protochloride-EDTA-sodium iodide, this reaction is reacted in solvent-water two-phase, and the reaction times is short, productive rate is high, improves the efficiency of condensation reaction.The principle of three components catalyzer is: react and carry out in aqueous phase; it is a typical SN2 type reaction; the existence of sodium iodide can activate the carbon chlorine key in sodium chloroacetate thus improve speed of response; and the existence of ferrous ion; the activity of phenol can be improved on the one hand thus the selectivity of raising phenoxy acetic acid; on the other hand; due to the complexing action of EDTA; the not oxidized effect of protection phenol can be played making ferrous ion, can also ensure can not precipitate to catalyst component when weakly acidic pH at adjust pH.
4, utilize the solubleness of sodium chloroacetate, sodium carbonate, sodium hydroxide and other matter under certain condition all higher than the character of sodium-chlor, adopt the mode of condensed mother liquor water cycle, effectively make use of condensed mother liquor water, eliminate the waste water produced in reaction process.
5, adopt the mode of washing sodium salt, reclaim in sodium salt the phenol carried secretly, further increase the utilization ratio of phenol on the one hand, improve the Recycling ability of acidified mother liquor by purifying sodium salt on the other hand.
6, adopt four phase processing modes of organic phase-water-solids-gases in acidification step, effectively accomplished being separated of side product chlorinated sodium and product phenoxy acetic acid, and do not have unnecessary waste water to produce.
7, the productive rate of present method, reaches 98% in phenol, more significantly improves, and also reaches 94 ~ 95% in the productive rate of Mono Chloro Acetic Acid; The product purity that present method obtains is high, reaches more than 98%.
8, whole technological process does not produce waste water, operation be all feed intake, heat, cool, crystallization, filtration, the routine operation such as making beating, be easy to industrialization.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
The chemical adopted in the embodiment of the present invention is all industrial goods.
Embodiment 1
In 250mL single port flask, add 38.4mL water and 29.76g Mono Chloro Acetic Acid stirring and dissolving, then add 16.7g sodium carbonate solid to the inside, make pH value of solution=6, obtain sodium chloroacetate solution;
In 500mL there-necked flask, drop into 150mL chlorobenzene, drop into 33.84g phenol, dripping 36g mass concentration is while stirring the sodium hydroxide solution of 40%, makes pH value of solution=12, obtains sodium phenylate solution;
This there-necked flask of reflux, keep solution temperature 91 ± 1 DEG C, add catalyzer (iron protochloride-EDTA-sodium iodide) 0.1g, again the above-mentioned sodium chloroacetate solution be obtained by reacting is added drop-wise in this flask, about dropping 30 minutes, dropwise rear backflow 1 hour, and remain system pH=11.5 ~ 12; After reaction terminates, this flask is cooled to 40 DEG C, dripping 5mL mass concentration is the concentrated hydrochloric acid of 30%, makes system pH=7; Suction filtration, obtain phenoxy acetic acid sodium salt and sodium chloride mixture, mother liquor is divided into two-layer, and organic phase is condensed mother liquor, and aqueous phase is condensed mother liquor water, for subsequent use;
Get 150mL chlorobenzene as washing mother liquor, by the phenoxy acetic acid sodium salt of above-mentioned acquisition and sodium chloride mixture making beating, the phenol in purging compound, at room temperature stirs after 30 minutes and filters, and obtains phenoxy acetic acid sodium salt and sodium chloride mixture and contains phenol washing mother liquor; The sodium hydroxide solution extraction being 32% containing phenol washing mother liquor 45g mass concentration removes phenol, and washing mother liquor is regenerated, in this washing except phenol step cycle uses; Containing the sodium hydroxide solution of phenol for carrying phenol liquid caustic soda, give over to next recycled;
Washed sodiumphenoxyacetate and sodium chloride mixture proceed in 500mL reaction flask and carry out acidification reaction, add 150mL chlorobenzene and 30mL water, are heated to 50 DEG C, pass into hydrogen chloride gas to pH value of solution=1, filtered while hot, obtain sodium-chlor and mother liquor, mother liquor layering, aqueous phase is that acidified water is continued to employ, and organic layer adds thermal distillation and carries out solvent azeotropic dehydration, after fluid dewatering to be distillated, be cooled to 15 DEG C, crystallization, suction filtration, filtrate is acidified mother liquor; Filtration cakes torrefaction, weigh, obtaining phenoxy acetic acid is white solid, 37.8g, purity 98% (HPLC).
Embodiment 2
In 250mL single port flask, add in 51.2g embodiment 1 the condensed mother liquor water and 29.76g Mono Chloro Acetic Acid that are separated and obtain, stirring and dissolving, adds 16.7g sodium carbonate solid, makes pH value of solution=6, obtain sodium chloroacetate solution to the inside;
Get the condensed mother liquor water being separated in remaining 28.8g embodiment 1 and obtaining, add 14.4g solid sodium hydroxide, obtain sodium hydroxide solution, for next cyclic regeneration washing mother liquor;
In 500mL there-necked flask, drop into embodiment 1 be separated the condensed mother liquor obtained, drop into 28.2g phenol, stir, then add and carry phenol liquid caustic soda in embodiment 1, make pH=12 in system, obtain sodium phenylate solution;
Add catalyst component iron protochloride 0.014g, be added in there-necked flask, finish disposable for sodium chloroacetate solution obtained above, heating keeps solution temperature 91 ± 1 DEG C, refluxes 1.5 hours, and remains system pH=11.5 ~ 12; Cool to 40 DEG C after reaction terminates, dripping mass concentration is the concentrated hydrochloric acid of 30%, and to system pH=6, suction filtration obtains phenoxy acetic acid sodium salt (sodium chloride-containing);
Washing mother liquor in Example 1, pulls an oar the sodium salt of above-mentioned acquisition, the phenol in washing sodium salt, at room temperature stirs filtration after 30 minutes and obtains sodium salt and contain phenol washing mother liquor; Containing phenol washing mother liquor with the extraction of the sodium hydroxide solution of above-mentioned preparation except phenol, washing mother liquor is regenerated, containing the liquid caustic soda of phenol for carrying phenol liquid caustic soda, as next recycled;
Washed sodiumphenoxyacetate proceeds in 500mL reaction flask and carries out acidification reaction, adds the acidified mother liquor in embodiment 1 and acidified water, is heated to 50 DEG C, passes into hydrogen chloride gas to pH=1, filtered while hot, obtains sodium-chlor and mother liquor, and mother liquor is cooled to 15 DEG C, crystallization, suction filtration, filtrate is acidified mother liquor; Filtration cakes torrefaction, weigh, obtaining phenoxy acetic acid is white solid, 44.7g, productive rate 98.0%.
Following table lists the operation according to embodiment 2, applies mechanically the result of 10 times:
Embodiment 3
In 250mL single port flask, add 59.5mL water and 29.77g Mono Chloro Acetic Acid stirring and dissolving, then add 16.70g sodium carbonate solid to the inside, make pH value of solution=6, obtain sodium chloroacetate solution;
In 500mL there-necked flask, drop into 200mL toluene, drop into 35.25g phenol, dripping 46.88g mass concentration is while stirring the sodium hydroxide solution of 32%, makes pH value of solution=12, obtains sodium phenylate solution;
This there-necked flask of reflux, keep solution temperature 94 ± 1 DEG C, add catalyzer (iron protochloride-EDTA-sodium iodide) 0.1g, the above-mentioned sodium chloroacetate solution be obtained by reacting is added drop-wise in this flask, about dropping 40 minutes, dropwise rear backflow 2 hours, and remain system pH=11 ~ 11.5; After reaction terminates, this flask is cooled to 30 DEG C, dripping 6mL mass concentration is the concentrated hydrochloric acid of 36%, makes system pH=5; Suction filtration, obtain phenoxy acetic acid sodium salt and sodium chloride mixture, mother liquor is divided into two-layer, and organic phase is condensed mother liquor, and aqueous phase is condensed mother liquor water, for subsequent use;
Get 100mL toluene as washing mother liquor, by the phenoxy acetic acid sodium salt of above-mentioned acquisition and sodium chloride mixture making beating, the phenol in purging compound, at room temperature stirs after 15 minutes and filters, and obtains phenoxy acetic acid sodium salt and sodium chloride mixture and contains phenol washing mother liquor; The sodium hydroxide solution extraction being 50% containing phenol washing mother liquor 27.2g mass concentration removes phenol, and washing mother liquor is regenerated, in this washing except phenol step cycle uses; Containing the sodium hydroxide solution of phenol for carrying phenol liquid caustic soda, give over to next recycled;
Washed sodiumphenoxyacetate and sodium chloride mixture proceed in 500mL reaction flask and carry out acidification reaction, add 180mL toluene and 30mL water, are heated to 70 DEG C, pass into hydrogen chloride gas to pH value of solution=2, filtered while hot, obtains sodium-chlor and mother liquor, mother liquor layering, water layer is acidified water, continue to employ, organic layer is cooled to 20 DEG C, crystallization, suction filtration, filtrate is acidified mother liquor; Filtration cakes torrefaction, weigh, obtaining phenoxy acetic acid is white solid, 36.5g, purity 98% (HPLC).
Embodiment 4
In 250mL single port flask, add in 67g embodiment 3 the condensed mother liquor water and 28.35g Mono Chloro Acetic Acid that are separated and obtain, stirring and dissolving, adds 15.9g sodium carbonate solid, makes pH value of solution=6, obtain sodium chloroacetate solution to the inside;
Get the condensed mother liquor water being separated in remaining 28g embodiment 3 and obtaining, add 13.8g solid sodium hydroxide, obtain liquid caustic soda, for next cyclic regeneration washing mother liquor;
In 500mL there-necked flask, drop into embodiment 3 be separated the condensed mother liquor obtained, drop into 28.2g phenol, stir, then add and carry phenol liquid caustic soda in embodiment 3, make pH=12 in system, obtain sodium phenylate solution;
Add catalyst component 0.009g, be all added in there-necked flask by sodium chloroacetate solution obtained above, finish, heating keeps solution temperature 93 ± 1 DEG C, refluxes 1.5 hours, and remains system pH=11 ~ 11.5; Cool to 30 DEG C after reaction terminates, dripping mass concentration is the concentrated hydrochloric acid of 33%, and to system pH=5, suction filtration obtains phenoxy acetic acid sodium salt (sodium chloride-containing);
Washing mother liquor in Example 3, pulls an oar the sodium salt of above-mentioned acquisition, the phenol in washing sodium salt, at room temperature stirs filtration after 15 minutes and obtains sodium salt and contain phenol washing mother liquor; Containing phenol washing mother liquor with the extraction of the liquid caustic soda of above-mentioned preparation except phenol, washing mother liquor is regenerated, containing the liquid caustic soda of phenol for carrying phenol liquid caustic soda, as next recycled;
Washed sodiumphenoxyacetate proceeds in 500mL reaction flask and carries out acidification reaction, adds the acidified mother liquor in embodiment 3 and acidified water, is heated to 70 DEG C, passes into hydrogen chloride gas to pH=2, filtered while hot, obtains sodium-chlor and mother liquor, and mother liquor is cooled to 20 DEG C, crystallization, suction filtration, filtrate is acidified mother liquor; Filtration cakes torrefaction, weigh, obtaining phenoxy acetic acid is white solid, 43.3g, productive rate 95%.
Embodiment 5
In 250mL single port flask, add 48.7mL water and 28.35g Mono Chloro Acetic Acid stirring and dissolving, then add 15.9g sodium carbonate solid to the inside, make pH value of solution=6, obtain sodium chloroacetate solution;
In 500mL there-necked flask, drop into 180mL zellon, drop into 32.43g phenol, dripping 27.6g mass concentration is while stirring the sodium hydroxide solution of 50%, makes pH value of solution=12, obtains sodium phenylate solution;
This there-necked flask of reflux, keep solution temperature 93 ± 1 DEG C, add catalyzer (iron protochloride-EDTA-sodium iodide) 0.09g, the above-mentioned sodium chloroacetate solution be obtained by reacting is added drop-wise in this flask, about dropping 30 minutes, dropwise rear backflow 2 hours, and remain system pH=11.5 ~ 12; After reaction terminates, this flask is cooled to 20 DEG C, pass into HCl gas 24mL, make system pH=6; Suction filtration, obtain phenoxy acetic acid sodium salt and sodium chloride mixture, mother liquor is divided into two-layer, and organic phase is condensed mother liquor, and aqueous phase is condensed mother liquor water, for subsequent use;
Get 130mL zellon as washing mother liquor, by the phenoxy acetic acid sodium salt of above-mentioned acquisition and sodium chloride mixture making beating, phenol in purging compound, at room temperature stirs after 20 minutes and filters, and obtains phenoxy acetic acid sodium salt and sodium chloride mixture and washs mother liquor containing phenol; The sodium hydroxide solution extraction being 50% containing phenol washing mother liquor 30g mass concentration removes phenol, and washing mother liquor is regenerated, in this washing except phenol step cycle uses; Containing the sodium hydroxide solution of phenol for carrying phenol liquid caustic soda, give over to next recycled;
Washed sodiumphenoxyacetate and sodium chloride mixture proceed in 500mL reaction flask and carry out acidification reaction, add 160mL zellon and 40mL water, are heated to 60 DEG C, pass into hydrogen chloride gas to pH value of solution=2, filtered while hot, obtain sodium-chlor and mother liquor, mother liquor layering, water layer is acidified water, continues to employ, organic layer adds thermal distillation and carries out solvent azeotropic dehydration, after fluid dewatering to be distillated, be cooled to 10 DEG C, crystallization, suction filtration, filtrate is acidified mother liquor; Filtration cakes torrefaction, weigh, obtaining phenoxy acetic acid is white solid, 35.7g, purity 98% (HPLC).
Embodiment 6
In 250mL single port flask, add in 60g embodiment 5 the condensed mother liquor water and 29.77g Mono Chloro Acetic Acid that are separated and obtain, stirring and dissolving, adds 16.7g sodium carbonate solid, makes pH value of solution=6, obtain sodium chloroacetate solution to the inside;
Get the condensed mother liquor water being separated in remaining 30g embodiment 5 and obtaining, add 15g solid sodium hydroxide, obtain sodium hydroxide solution, for next cyclic regeneration washing mother liquor;
In 500mL there-necked flask, drop into embodiment 5 be separated the condensed mother liquor obtained, drop into 28.2g phenol, stir, then add and carry phenol liquid caustic soda in embodiment 5, make pH=12 in system, obtain sodium phenylate solution;
Add catalyst component 0.017g, be all added in there-necked flask by sodium chloroacetate solution obtained above, finish, heating keeps solution temperature 93 ± 1 DEG C, refluxes 2 hours, and remains system pH=11 ~ 11.5; Cool to 30 DEG C after reaction terminates, dripping 4.5mL mass concentration is the HCl of 35%, and to system pH=7, suction filtration obtains phenoxy acetic acid sodium salt (sodium chloride-containing);
Washing mother liquor in Example 5, pulls an oar the sodium salt of above-mentioned acquisition, the phenol in washing sodium salt, at room temperature stirs filtration after 25 minutes and obtains sodium salt and contain phenol washing mother liquor; Containing phenol washing mother liquor with the extraction of the liquid caustic soda of above-mentioned preparation except phenol, washing mother liquor is regenerated, containing the liquid caustic soda of phenol for carrying phenol liquid caustic soda, as next recycled;
Washed sodiumphenoxyacetate proceeds in 500mL reaction flask and carries out acidification reaction, adds the acidified mother liquor in embodiment 5, is heated to 65 DEG C, passes into hydrogen chloride gas to pH=2, filtered while hot, obtains sodium-chlor and mother liquor, and mother liquor is cooled to 20 DEG C, crystallization, suction filtration, filtrate is acidified mother liquor; Filtration cakes torrefaction, weigh, obtaining phenoxy acetic acid is white solid, 44.2g, productive rate 97%.
Embodiment 7
Step is with embodiment 1, and the organic solvent of employing is dimethylbenzene.
Finally obtaining phenoxy acetic acid is white solid, 37.4g, purity 98% (HPLC).
Embodiment 8
Step is with embodiment 1, and the organic solvent of employing is dichlorobenzene.
Finally obtaining phenoxy acetic acid is white solid, 37.5g, purity 98% (HPLC).
Embodiment 9
Step is with embodiment 1, and the organic solvent of employing is ethylene dichloride.
Finally obtaining phenoxy acetic acid is white solid, 36.7g, purity 98% (HPLC).
Claims (9)
1. " three circulations " formula prepares a method for phenoxy acetic acid without waste water, it is characterized in that, comprises the steps:
(1) sodium phenylate and sodium chloroacetate condensation generate sodiumphenoxyacetate
Get Mono Chloro Acetic Acid and sodium carbonate reacts in water, pH value of solution is adjusted to 6, generate the sodium chloroacetate aqueous solution;
In condensed mother liquor, add phenol and aqueous sodium hydroxide solution reacts, pH value of solution is adjusted to 12, generate sodium phenylate solution;
By above-mentioned sodium phenylate solution and sodium chloroacetate aqueous solution, add catalyzer and react, reaction terminates, then solution ph is adjusted to 5 ~ 7;
Wherein, described catalyzer is iron protochloride-EDTA-sodium iodide; In described catalyzer, the mol ratio of iron protochloride, EDTA, sodium iodide is 1:1:1;
By reacting liquid filtering, obtain solid and mother liquor, mother liquor be divided into organic phase and aqueous phase two-layer; Wherein, solid is sodiumphenoxyacetate and sodium chloride mixture; Organic phase is condensed mother liquor, recycles in this step; Aqueous phase reuse, prepares the reaction solvent of sodium chloroacetate as Mono Chloro Acetic Acid and sodium carbonate, and preparation sodium hydroxide solution;
(2) sodiumphenoxyacetate washing is except phenol
The sodiumphenoxyacetate obtain step (1) and sodium chloride mixture, with washing mother liquor making beating process; After filtration, solid phase is sodiumphenoxyacetate and sodium chloride mixture, and liquid phase is washings; By liquid phase sodium hydroxide solution extraction recovery phenol wherein, obtain washing mother liquor after separation respectively and contain phenol sodium hydroxide solution;
Described washing mother liquor recycles in this step, returns step (1) for preparing sodium phenylate with phenol reactant containing phenol sodium hydroxide solution;
(3) sodiumphenoxyacetate acidifying generates phenoxy acetic acid
Solid phase dispersed with stirring in acidified mother liquor and water mixed liquid that step (2) is obtained, then pass into hydrogen chloride gas, reach 1 ~ 2 to acidified mother liquor pH value; After filtration from sodium chloride, solution is lowered the temperature, crystallization, and after filtration, drying obtains phenoxy acetic acid solid; Liquid phase is acidified mother liquor and water, recycles in this step.
2. one according to claim 1 " three circulations " formula prepares the method for phenoxy acetic acid without waste water, it is characterized in that, initial feed ratio ratio, phenol: Mono Chloro Acetic Acid: sodium carbonate: sodium hydroxide: hydrogen chloride gas=(1.15 ~ 1.25): (1 ~ 1.05): (0.5 ~ 0.525): (1.15 ~ 1.25): (1.15 ~ 1.25); Whole process feed ratio is calculated in molar ratio as, phenol: Mono Chloro Acetic Acid: sodium carbonate: sodium hydroxide: hydrogen chloride gas=1:(1 ~ 1.05): (0.5 ~ 0.525): (1.15 ~ 1.25): (1.15 ~ 1.25).
3. one according to claim 1 " three circulations " formula prepares the method for phenoxy acetic acid without waste water, and it is characterized in that, described in step (1), catalyst charge is, catalyzer: sodium chloroacetate is 1g:(3 ~ 3.3) mol.
4. one according to claim 1 " three circulations " formula prepares the method for phenoxy acetic acid without waste water, it is characterized in that, in described step (1), the reaction conditions of sodium phenylate solution and the sodium chloroacetate aqueous solution is: keep temperature of reaction 90 ~ 95 DEG C, reaction soln pH=11.0 ~ 12, back flow reaction 1 ~ 2 hour.
5. one according to claim 1 " three circulations " formula prepares the method for phenoxy acetic acid without waste water, it is characterized in that, in described step (1), after sodium phenylate solution and sodium chloroacetate reactant aqueous solution terminate, reaction solution is cooled to after below 40 DEG C, by hydrochloric acid or the HCl gas regulation solution ph of mass concentration >=30%.
6. one according to claim 1 " three circulations " formula prepares the method for phenoxy acetic acid without waste water, and it is characterized in that, in described step (2), the making beating treatment time is 15 ~ 30 minutes.
7. one according to claim 1 " three circulations " formula prepares the method for phenoxy acetic acid without waste water, it is characterized in that, in described step (3), the cumulative volume of acidified mother liquor and water is 3 ~ 4 times of solid volume, and the volume ratio of acidified mother liquor and water is 4 ~ 6:1; And the mixed solution of acidified mother liquor and water is heated to 50 ~ 70 DEG C.
8. one according to claim 1 " three circulations " formula prepares the method for phenoxy acetic acid without waste water, and it is characterized in that, in described step (3), solution is cooled to less than 20 DEG C.
9. one according to claim 1 " three circulations " formula prepares the method for phenoxy acetic acid without waste water, it is characterized in that, the solvent in described condensed mother liquor, washing mother liquor and acidified mother liquor is chlorine benzene,toluene,xylene, dichlorobenzene, ethylene dichloride or zellon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410337292.8A CN104151152B (en) | 2014-07-16 | 2014-07-16 | A kind of three circulating methods preparing phenoxy acetic acid without waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410337292.8A CN104151152B (en) | 2014-07-16 | 2014-07-16 | A kind of three circulating methods preparing phenoxy acetic acid without waste water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104151152A CN104151152A (en) | 2014-11-19 |
| CN104151152B true CN104151152B (en) | 2015-11-04 |
Family
ID=51876817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410337292.8A Expired - Fee Related CN104151152B (en) | 2014-07-16 | 2014-07-16 | A kind of three circulating methods preparing phenoxy acetic acid without waste water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104151152B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829447B (en) * | 2015-05-11 | 2017-04-26 | 浙江工业大学 | Continuous synthetic method of phenoxy acetic acid |
| CN106397176A (en) * | 2016-08-30 | 2017-02-15 | 枣阳市福星化工有限公司 | Production method of sodium phenoxyacetate |
| CN106397177A (en) * | 2016-08-31 | 2017-02-15 | 枣阳市福星化工有限公司 | Full circle sodium phenoxyacetate preparation method |
| CN107473953A (en) * | 2017-08-21 | 2017-12-15 | 湖北沙隆达股份有限公司 | A kind of method for melting the D of separating-purifying 2,4 acid |
| CN108467343A (en) * | 2018-04-03 | 2018-08-31 | 湘潭大学 | The preparation method of 2,4- dichlorphenoxyacetic acids |
| CN111440061A (en) * | 2019-01-16 | 2020-07-24 | 姜林 | Preparation method of phenoxyacetic acid |
| CN113788750B (en) * | 2021-10-27 | 2024-04-16 | 安庆朗坤药业有限公司 | Preparation method of sodium phenoxyacetate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO112278B1 (en) * | 1996-03-05 | 1997-07-30 | Sc Oltchim Sa | 2,4-dichlorinephenoyacetic acid preparation process |
| CN103058855A (en) * | 2011-10-20 | 2013-04-24 | 上海泰禾化工有限公司 | Method for synthesizing phenoxyacetic acid derivative |
-
2014
- 2014-07-16 CN CN201410337292.8A patent/CN104151152B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO112278B1 (en) * | 1996-03-05 | 1997-07-30 | Sc Oltchim Sa | 2,4-dichlorinephenoyacetic acid preparation process |
| CN103058855A (en) * | 2011-10-20 | 2013-04-24 | 上海泰禾化工有限公司 | Method for synthesizing phenoxyacetic acid derivative |
Non-Patent Citations (1)
| Title |
|---|
| "邻甲苯氧乙酸生产中脱酚废水的回用";李俊杰等;《化学世界》;20001231(第S1期);51，19 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104151152A (en) | 2014-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104151152B (en) | A kind of three circulating methods preparing phenoxy acetic acid without waste water | |
| CN106336388B (en) | The synthetic method of benzofuran -2- (3H) -one | |
| CN104649300B (en) | The method of recovery and refining sodium bromide from dipropyl cyanoacetate mixture | |
| CN104628513A (en) | Method for resource utilization of fluoroform | |
| CN103570568A (en) | Clean production process of glycine in coproduction with ammonium chloride | |
| CN105254575B (en) | A kind of synthetic method of sulphadiazine | |
| CN115722255A (en) | Supported catalyst for producing 1,2, 3-pentachloropropane and preparation method and application thereof | |
| CN105503513B (en) | The method of silicon dioxide carried catalysis of phosphotungstic acid synthesis 4,4 '-dichloromethyl biphenyl | |
| CN103420842B (en) | Preparation method for 2,3,4-trifluoronitrobenzene | |
| CN104628679B (en) | Bitopertin synthetic method and its intermediate | |
| CN102381947B (en) | Synthesis method of chiral 2,2 '- di-alkoxy-1, 1'-binaphthyl | |
| CN101792387B (en) | Preparation method of 2,3,4-trimethoxybenzoic acid | |
| CN107445180A (en) | A kind of handling process of amine salt waste water | |
| CN105536873B (en) | A kind of composite catalyst and its application | |
| CN106810546A (en) | A kind of umeclidinium compound | |
| CN103950893B (en) | A kind of method that reclaims purification iodine | |
| CN105480948A (en) | Method and system for recycling by-product hydrogen chloride in fatty acid or fatty acyl chloride chlorination production process | |
| CN102206134A (en) | Preparation method of 2-bromine-3,3,3-trifluoropropene | |
| CN105016963A (en) | Synthetic method of 2-bromo-5-iodotoluene | |
| CN104310504B (en) | The treatment process of organic pollutant in a kind of dyeing waste water | |
| JP5790533B2 (en) | Method for purifying phenylhydrazine-β-carboxylate compounds | |
| CN108203390A (en) | A kind of method using organic solvent production glycine | |
| CN104356003B (en) | The synthetic method of aromatic series fluoro-containing intermediate m-fluoroaniline | |
| CN110950416B (en) | Method for treating mother liquor containing 4-pyridylpyridine chloride hydrochloride | |
| CN105669539B (en) | A kind of preparation process of 2- amino -3- fluorine pyridines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151104 Termination date: 20160716 |