CN107935843A - A kind of method that 4 Hydroxy M Phthalic Acids are extracted in the salicylic waste residue from production - Google Patents
A kind of method that 4 Hydroxy M Phthalic Acids are extracted in the salicylic waste residue from production Download PDFInfo
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- CN107935843A CN107935843A CN201711269286.3A CN201711269286A CN107935843A CN 107935843 A CN107935843 A CN 107935843A CN 201711269286 A CN201711269286 A CN 201711269286A CN 107935843 A CN107935843 A CN 107935843A
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- hydroxyisophthalic
- salicylic
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- 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
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method that 4 Hydroxy M Phthalic Acids are extracted in salicylic waste residue from production, belong to chemical field.The present invention be to produce salicylic waste residue as raw material, by alkali soluble, decoloration, acid out and etc. obtained 4 Hydroxy M Phthalic Acid sterlings.Operating process step is simple, avoids using complicated production equipment and technique.By these steps, the recycling that production salicylic acid process produces waste residue is realized.
Description
Technical field
The invention belongs to chemical field, and in particular to put forward disubstituted-4-hydroxy isophthalic in a kind of salicylic waste residue from production
The method of dioctyl phthalate
Background technology
4 hydroxyisophthalic acid and its derivative are a kind of important organic intermediate compounds, in biology, medicine, are changed
The fields such as work have a wide range of applications.Such as platelet aggregation inhibitor pyrrole is prepared as raw material using 4 hydroxyisophthalic acid and examines him
Amine and its analogue (Nature, 1955,175:206；Cardiovasc Drug Rev,1995,13:353；US
4698354,US6525078)。
The method for the synthesis 4 hydroxyisophthalic acid reported at present mainly has：Using salicylic acid or P-hydroxybenzoic acid as original
Material, through potassium carbonate into after salt, under the conditions of 250 DEG C, 14MPa, is made (US3089905) with carbon dioxide carboxylation.This method needs
High-temperature and high-pressure conditions are wanted, therefore there are the problem of process safety and equipment applicability.Rahim M A etc. carry out the above method
Improve, using methanol as reaction medium, (pH 3-4) detailed examination under 200 DEG C or so, 5MPa pressure conditions under acid condition
Phenol, salicylic acid, P-hydroxybenzoic acid selective carbon dioxide pressurization carboxylation method (Bull Chem Soc Jpn, 2003,
76(11):2191).Although reducing reaction temperature and pressure by process modification, this method there is also byproduct of reaction it is more,
The shortcomings that product yield low (23%).Patent US7335791 is reported using 4- bromines M-phthalic acid as raw material, in mantoquita and ligand
The technique that the lower hydrolysis of effect prepares 4 hydroxyisophthalic acid.The technique causes process costs liter using expensive amine ligand
Height, and raw material 4- bromines M-phthalic acid is mainly made by the selective bromination of dimethylbenzene, methyl oxidation process.Meta-xylene
Bromo-reaction poor selectivity, result in 4- bromines M-phthalic acid manufacture cost it is higher, production and supply are restricted.Zhu Hui etc. is reported
Using 4- methoxy benzoic acids or 4-methoxybenzaldehyde as raw material, through Blanc chloromethylations, oxidation, de- methylether protecting groups etc.
Step synthesizes method (Chinese Journal of Pharmaceuticals, 2011,42 (5) of 4 hydroxyisophthalic acid：328；CN104370735A).
This method equally exists the problem of cost of material is excessive, reaction scheme is long, process side reaction is more, product purification difficult.Therefore,
4 hydroxyisophthalic acid synthesis technique through report can not large-scale industrial production, cause 4 hydroxyisophthalic acid height
High price, limits 4 hydroxyisophthalic acid large-scale application.
Salicylic acid and its derivative have a wide range of applications in the field such as biology, medicine, chemical industry, material.Salicylic life
Production has one-hundred-year history, and industrial production salicylic acid utilizes Kolbe-Schmitt reaction industries mainly using phenol as raw material at present
Prepare (CN101613270A, US3342857A, SU184748A, DE1198375A etc.), wherein 4 hydroxyisophthalic acid is anti-
Answer process Main By product (Report of Chemistry Research Board, 1952:66).Industrial bigcatkin willow
Acid crude contains substantial amounts of 4- hydroxyls after sublimation of salicylic Acid mainly by sublimed method purifying high-purity salicylic acid in remaining residue
M-phthalic acid (4 hydroxyisophthalic acid (82%), salicylic acid (10%), 2- Hydroxy M Phthalic Acids (2%), inorganic salts
(6%), Report of Chemistry Research Board, 1952:66).Hunt etc. reports solvent method and vapor
The way of distillation extracted after SUBLIMATE SALICYLIC ACID in residue 4 hydroxyisophthalic acid method (J Chem Soc, 1956:3099).Though
Right two methods can obtain 4 hydroxyisophthalic acid, but solvent method need to consume substantial amounts of carbon tetrachloride, chloroform etc. it is poisonous
Solvent, solubility of the product 4 hydroxyisophthalic acid in carbon tetrachloride, chloroform is extremely low, and extraction time is longer, and actual behaviour
It is relatively low that product purity is obtained in work.Steam distillation also needs the longer reaction time, and process energy consumption is higher, practical operation
Middle product purity is low.
China produces the largely residue containing 4 hydroxyisophthalic acid per annual meeting as salicylic big country is produced,
These residues industrially fall as Solid state fermentation.Recycling extraction 4 hydroxyisophthalic acid, provides improving from these waste residues
Source utilization rate, reduces environmental pollution.Therefore, in order to improve resource utilization, improve and extract 4- hydroxyls from production salicylic acid waste residue
The yield and purity of base M-phthalic acid, inventor devise in a kind of salicylic waste residue from production and put forward disubstituted-4-hydroxy isophthalic two
The technique of formic acid, greatly realizes the recycling of resource, reduces the cost of production 4 hydroxyisophthalic acid.
The content of the invention
Lack the present invention overcomes technology path in existing 4 hydroxyisophthalic acid preparation process is long, product yield is low
A kind of point, it is proposed that technique that 4 hydroxyisophthalic acid is extracted from the new salicylic waste residue of production.
Comprise the following steps from the technique for producing extraction 4 hydroxyisophthalic acid in salicylic waste residue：
The first step：Salicylic waste residue will be produced to be dissolved in aqueous slkali
Using water as reaction dissolvent, produce salicylic waste residue and reacted with alkaloids, filter out insoluble matter after reaction, obtain
Solution containing 4 hydroxyisophthalic acid salt；
Second step：Solution decoloration containing 4 hydroxyisophthalic acid salt：
Decolorising agent is added in the solution containing 4 hydroxyisophthalic acid salt, is decolourized to solution；
3rd step：The precipitation of 4 hydroxyisophthalic acid solid：
After solution decoloration containing 4 hydroxyisophthalic acid salt, adjusting solution acid-basicity to pH≤4, in acid condition
Solid is separated out, collects filter cake, vacuum drying.
The present invention using produce salicylic acid process generation waste residue as raw material, by alkali soluble, decoloration, acid out and etc. isolate
4 hydroxyisophthalic acid sterling, reaction process are easy to operate.Alkali, decolorising agent, the acid etc. of process consumption are cheap, react
Journey can carry out in general reactor, it is not necessary to complicated production equipment.Above step is with industrial production salicylic acid mistake
The waste residue that journey produces extracts 4 hydroxyisophthalic acid for raw material, avoids needed for existing 4 hydroxyisophthalic acid synthetic technology
High-temperature and high-pressure conditions, to production equipment require it is low, reduce production 4 hydroxyisophthalic acid energy consumption.Reported from life
4 hydroxyisophthalic acid extracting method needs to consume substantial amounts of toxic solvent in the waste residue that production salicylic acid process produces, it is also necessary to
Continuous extraction and steam distillation device.Compared with existing extracting method, this method extraction step avoids poisonous organic molten
The use of agent, the chemical reagent of process consumption is cheap, and the device and reaction process that step need not be complicated.
Wherein, the above-mentioned first step produces salicylic waste residue and is dissolved in aqueous slkali, and reaction dissolvent is water, and the alkali used is carbon
Sour hydrogen sodium, saleratus, calcium bicarbonate or ammonium hydrogen carbonate, 4 hydroxyisophthalic acid：The molar ratio of alkali is 1:1-10, reaction temperature
Spend for 20-100 DEG C.Preferably, the alkali used is sodium acid carbonate, 4 hydroxyisophthalic acid：The molar ratio of alkali is 1:1-4, instead
Answer 50-90 DEG C of temperature.
Wherein, above-mentioned second step contains in the solution decoloration of 4 hydroxyisophthalic acid salt, and the decolorising agent used is activity
Charcoal, diatomite, carclazyte, sodium hydrosulfite, bleaching powder, aluminium oxide, kaolin etc., the amount of required decolorising agent is decolorising agent：Solid gives up
Slag mass ratio is 1:1-150.Preferably, decolorising agent for activated carbon, aluminium oxide, diatomite, decolorising agent：Solid slag mass ratio 1:
10-20。
Wherein, in the precipitation of above-mentioned 3rd step 4 hydroxyisophthalic acid solid, acid used is hydrochloric acid, sulfuric acid, nitric acid
Or perchloric acid, the acid-base property scope that solution separates out 4 hydroxyisophthalic acid is pH≤4.Preferably, acid used is hydrochloric acid, pH
=1-2.
Beneficial effect：
The present invention be to produce salicylic waste residue as raw material, by alkali soluble, decoloration, acid out and etc. obtained 4- hydroxyls
M-phthalic acid sterling.Operating process step is simple, avoids using complicated production equipment and technique.It is real by these steps
The recycling that production salicylic acid process produces waste residue is showed.
Embodiment
The waste residue that the production salicylic acid process used of the present invention produces is provided by Jiangsu Pu Yuan Chemical Co., Ltd.s, waste residue
Middle 4 hydroxyisophthalic acid (4 hydroxyisophthalic acid (82-85%), salicylic acid (8-10%), 2- Hydroxy M Phthalic Acids
(1-2%), inorganic salts (1-6%)
Embodiment 1
Under room temperature, stirring condition, 100.00g waste residues are poured into 2000mL sodium bicarbonate solutions and (contain sodium acid carbonate
95.46g), finish, solution is in dark brown starchiness.Under stirring, the temperature of heated solution is to 80 DEG C.With stirring into
OK, fraction solids are dissolved in solution, there is gas releasing in solution.Stop heating, cooling solution to room after when heating stirring 1 is small
Temperature.Filtering, collects filtrate, obtains deep brown solution.It is stirred at room temperature under state, adds 5g activated carbons, heated solution in the solution
To 90 DEG C or so, when decoloring reaction 1 is small.It is cooled to room temperature after reaction, crosses and filter out activated carbon.Solution after decoloration adds salt
Acid for adjusting pH separates out white solid to 1-2.Filtering, filter cake are dried in vacuo after being washed with water, and obtain 60.57g 4- hydroxyl isophthalic
Dioctyl phthalate solid.
Embodiment 2
Under room temperature, stirring condition, 100.00g waste residues are poured into 1000mL sodium bicarbonate solutions and (contain sodium acid carbonate
75.64g), finish, solution is in dark brown starchiness.Under stirring, the temperature of heated solution is to 90 DEG C.With stirring into
OK, fraction solids are dissolved in solution, there is gas releasing in solution.Stop heating, cooling solution to room after when heating stirring 2 is small
Temperature.Filtering, collects filtrate, obtains deep brown solution.It is stirred at room temperature under state, adds 5g activated carbons in the solution.After heat it is molten
Liquid temperature degree to 90 DEG C reflux decoloration 1 it is small when.After decoloration, cooling solution to room temperature, crosses and filters out activated carbon.Salt is added in filtrate
Acid-conditioning solution pH to 1-2, separates out white solid.Filtering, is dried in vacuo after filter cake washing, obtains 48.73g 4- hydroxyl isophthalic
Dioctyl phthalate solid.
Embodiment 3
Under room temperature, stirring condition, 100.00g waste residues are poured into 500mL potassium bicarbonate solutions and (contain saleratus
112.13g), finish, solution is in dark brown starchiness.Under stirring, the temperature of heated solution is to 70 DEG C.With stirring into
OK, fraction solids are dissolved in solution, there is gas releasing in solution.Stop heating after when heating stirring 1.5 is small, cooling solution is extremely
Room temperature.Filtering, collects filtrate, obtains deep brown solution.It is stirred at room temperature under state, adds 5g activated carbons in the solution, heating is molten
Liquid is to 90 DEG C or so, when decoloring reaction 1 is small.It is cooled to room temperature after reaction, crosses and filter out activated carbon.Solution after decoloration adds
Salt acid for adjusting pH separates out white solid to 1-2.Filtering, filter cake are dried in vacuo after being washed with water, and obtain 58.29g4- hydroxyl isophthalic
Dioctyl phthalate solid.
Embodiment 4
Under room temperature, stirring condition, 100.00g waste residues are poured into 2000mL sodium bicarbonate solutions and (contain sodium acid carbonate
95.46g), finish, solution is in dark brown starchiness.Under stirring, the temperature of heated solution is to 80 DEG C.With stirring into
OK, fraction solids are dissolved in solution, there is gas releasing in solution.Stop heating, cooling solution to room after when heating stirring 1 is small
Temperature.Filtering, collects filtrate, obtains deep brown solution.It is stirred at room temperature under state, adds dilute hydrochloric acid in the solution, adjusts pH value of solution
To 6-7,6.5g activated aluminas are added.Afterwards heated solution temperature to 100 DEG C reflux decoloration 2 it is small when.After decoloration, cooling is molten
Liquid filters alumina to room temperature.Hydrochloric acid conditioning solution pH to 1-2 is added in filtrate, separates out white solid.Filtering, filter cake water
It is dried in vacuo after washing, obtains 55.39g 4 hydroxyisophthalic acid solids.
Embodiment 5
Under room temperature, stirring condition, 100.00g waste residues are poured into 2000mL sodium bicarbonate solutions and (contain sodium acid carbonate 95g),
Finish, solution is in dark brown starchiness.Under stirring, the temperature of heated solution is to 80 DEG C.As the progress of stirring, part are solid
Body is dissolved in solution, there is gas releasing in solution.Stop heating, cooling solution to room temperature after when heating stirring 1 is small.Filtering,
Filtrate is collected, obtains deep brown solution.It is stirred at room temperature under state, adds dilute hydrochloric acid in the solution, adjusts pH value of solution to 6-7, add
Enter 7g diatomite.Afterwards heated solution temperature to 100 DEG C reflux decoloration 3 it is small when.After decoloration, cooling solution to room temperature, filtering
Except diatomite.Hydrochloric acid conditioning solution pH to 1-2 is added in filtrate, separates out white solid.Filtering, is dried in vacuo after filter cake washing,
Obtain 56.41g 4 hydroxyisophthalic acid solids.
Embodiment of above is only the preferred embodiment of the present invention, it is impossible to the scope of protection of the invention is limited with this,
The change of any unsubstantiality and substitute the protection for belonging to the present invention that those skilled in the art is done on the basis of the present invention
Scope.
Claims (7)
- It is 1. a kind of from the method for producing extraction 4 hydroxyisophthalic acid in salicylic waste residue, it is characterised in that：Including following Step：The first step：Salicylic waste residue will be produced to be dissolved in aqueous slkali, using water as reaction dissolvent, produce salicylic waste residue Reacted with alkaloids, obtain the solution containing 4 hydroxyisophthalic acid salt；Second step：Solution decoloration containing 4 hydroxyisophthalic acid salt：Decolorising agent is added in the solution containing 4 hydroxyisophthalic acid salt, is decolourized to solution；3rd step：The precipitation of 4 hydroxyisophthalic acid solid：After solution decoloration containing 4 hydroxyisophthalic acid salt, it is 0-4 to adjust solution acid-basicity to pH value, in acid condition Solid is separated out, collects filter cake, vacuum drying.
- 2. according to the method described in claim 1, it is characterized in that：The first step reaction dissolvent is water, the alkali used for The molar ratio of sodium acid carbonate, saleratus, calcium bicarbonate or ammonium hydrogen carbonate, 4 hydroxyisophthalic acid and alkali is 1:1-10, instead It is 20-100 DEG C to answer temperature.
- 3. according to the method described in claim 2, it is characterized in that：The alkali is sodium acid carbonate, 4 hydroxyisophthalic acid Molar ratio with alkali is 1:1-4,50-90 DEG C of reaction temperature.
- 4. according to the method described in claim 1, it is characterized in that：The decolorising agent that the second step uses is activated carbon, silicon Diatomaceous earth, carclazyte, sodium hydrosulfite, bleaching powder, aluminium oxide, kaolin, the amount of the decolorising agent is decolorising agent and solid slag quality Than for 1:1-150.
- 5. according to the method described in claim 4, it is characterized in that：The decolorising agent is activated carbon, aluminium oxide, diatomite, Decolorising agent and solid slag mass ratio 1:10-20.
- 6. according to the method described in claim 1, it is characterized in that：The acid that 3rd step uses is hydrochloric acid, sulfuric acid, nitric acid Or perchloric acid, the acid-base property scope that solution separates out 4 hydroxyisophthalic acid is that pH value is 0-4.
- 7. according to the method described in claim 6, it is characterized in that：The acid is hydrochloric acid, pH value 1-2.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159347A (en) * | 2020-10-27 | 2021-01-01 | 常州工程职业技术学院 | Preparation method of picolitamide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105949047A (en) * | 2016-06-21 | 2016-09-21 | 东南大学 | Method for extracting 4-hydroxy-m-phthalic acid from wintergreen oil production waste slag |
-
2017
- 2017-12-05 CN CN201711269286.3A patent/CN107935843A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105949047A (en) * | 2016-06-21 | 2016-09-21 | 东南大学 | Method for extracting 4-hydroxy-m-phthalic acid from wintergreen oil production waste slag |
Non-Patent Citations (2)
| Title |
|---|
| S. E. HUNT ET AL: "4-Hydroxyisophthalic acid", 《J CHEM SOC》 * |
| 刘仕艳: "水杨酸工业生产副产物的开发与利用研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159347A (en) * | 2020-10-27 | 2021-01-01 | 常州工程职业技术学院 | Preparation method of picolitamide |
| CN112159347B (en) * | 2020-10-27 | 2022-06-07 | 常州工程职业技术学院 | Preparation method of picolitamide |
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