CN103012105B - 2-propyl heptanoic acid preparation method - Google Patents
2-propyl heptanoic acid preparation method Download PDFInfo
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- CN103012105B CN103012105B CN201110279165.3A CN201110279165A CN103012105B CN 103012105 B CN103012105 B CN 103012105B CN 201110279165 A CN201110279165 A CN 201110279165A CN 103012105 B CN103012105 B CN 103012105B
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Abstract
The present invention relates to a 2-propyl heptanoic acid preparation method, wherein 2-propyl heptanol is adopted as a raw material, a superior performance price ratio metal oxide is adopted as an oxidation catalyst, heating, pressure increase, and pressure holding are performed to complete an oxidation process, acidification, dehydration and rectification are performed to prepare the 2-propyl heptanoic acid, and a yield of the prepared finished product is high. According to the present invention, sodium sulfate discharged during a recovery dehydration process can be used for preparing a by-product mirabilite, such that three wastes are not discharged, and advantages of environmental protection and no pollution are provided; and the 2-propyl heptanoic acid prepared by the preparation method has characteristics of no toxicity and no harm, and can be made into a novel environment-friendly plastic plasticizer so as to replace phthalate plasticizers, and industrial scale production can be achieved.
Description
Technical field
The invention belongs to the preparation method of industrial chemicals, particularly relate to a kind of method that the 2-of employing propyl enanthol prepares 2-propylheptanoic acid, the method is suitable for industrial scale and produces.
Background technology
2-propylheptanoic acid, English name: 2-propylheptanoic acid, molecular formula:: C
10h
20o
2, structural formula:
for colourless transparent liquid.
At present, with the phthalate plastic plasticizer that dioctyl phthalate (DOP) (DOP), dimethyl phthalate (DMP) and dibutyl phthalate (DBP) etc. are representative, be recognized and had harm to environment, in the world by the endocrine disruption hormone of key monitoring, the arch-criminal causing man's reproductive problems, makeup containing it can increase the probability that women suffers from breast cancer, the reproductive system of the boy baby of harm female fertility, can cell mutation be caused when damaging serious, final to abnormal or carcinogenic.
The derivative of 2-propylheptanoic acid can be made into multiple excellent novel environmental friendly plastic plasticizer, can substitute poisonous and hazardous phthalate plastic plasticizer.But there is no the method preparing 2-propylheptanoic acid that can realize industrial scale and produce at present.
Summary of the invention
The object of this invention is to provide that a kind of yield is high, purity is high, environment friendly and pollution-free, the preparation method that can realize the 2-propylheptanoic acid that industrial scale is produced.
The present invention adopts following technical scheme, a kind of preparation method of 2-propylheptanoic acid, and the method adopts following steps:
(1) sheet alkali and 2-propyl enanthol are dropped in stills for air blowing, stir under catalyzer existent condition and be warming up to 265 ~ 295 DEG C, boost to 2.8 ~ 3.2Mpa, carry out oxidizing reaction, obtain solution A;
(2) by the water cooling of upper step solution A, dilution, by the 2-propylheptanoic acid sodium press-in acidifying still in solution A, under 60 ~ 90 DEG C of temperature condition, add sulphuric acid soln adjust ph to 3 ~ 4, carry out acidification reaction, isolate sodium sulfate mother liquor layer after completion of the reaction, remaining as solution B;
(3) upper step solution B is washed successively, decompression dehydration, obtain thick 2-propylheptanoic acid;
(4) rectification under vacuum is carried out to the thick 2-propylheptanoic acid of upper step gained, obtained finished product 2-propylheptanoic acid.
Catalyzer in described step (1) is one in zinc oxide, calcium oxide, silicon-dioxide, aluminum oxide or magnesium oxide or its mixture.
In described step (1), the mass ratio of catalyzer and 2-propyl enanthol is 1: 70 ~ 80.
Sheet alkali in described step (1) and the mol ratio of 2-propyl enanthol are 1: 1 ~ 1.5.
The quality added water in described step (2) accounts for 40% ~ 50% of added reaction mass quality in step (1).
In described step (3), dewatering pressure is-0.65 ~-0.9Mpa, and temperature is 85 ~ 95 DEG C.
In described step (4), rectifying pressure is-0.7 ~-0.9Mpa, and temperature is 210 ~ 220 DEG C.
In described step (2), (3), isolated sodium sulfate mother liquor layer obtains byproduct Sodium sulfate anhydrous.min(99) through precipitation, filtration, crystallization, separation, drying.
Positively effect of the present invention is as follows: the present invention adopts 2-propyl enanthol to be raw material, the superior metal oxide of cost performance is adopted to make oxide catalyst, oxidising process is completed through intensification, boosting, pressurize, 2-propylheptanoic acid is obtained again through acidifying, dehydration, rectifying, obtained product yield is high, and can reach more than 95%, finished product purity is high, can reach more than 99%, all technical all meets company standard Q/SZH21-2010.The inventive method reclaims the sodium sulfate discharged in dehydration procedure and can be used to make byproduct Sodium sulfate anhydrous.min(99), three-waste free discharge, environment friendly and pollution-free.The obtained 2-propylheptanoic acid of the inventive method is nontoxic, harmless, can be made into the plastic plasticizer of novel environmental friendly, is used for the plastic plasticizer of alternative phthalate, can realize industrial scale and produce.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
The inventive method chemical principle is as follows:
(1) oxidizing reaction:
(2) acidification reaction:
In the inventive method reaction process, the selection of each synthesis condition is determined:
1, the mol ratio (alkali alcohol mol ratio) of sheet alkali and 2-propyl enanthol
Under the mass ratio of oxidative pressure 3Mpa, oxidizing temperature 270 DEG C, catalyzer and 2-propyl enanthol is the condition of 1: 80, the relation of alkali alcohol mol ratio and each parameter of 2-propylheptanoic acid goods, in table 1:
Table 1 alkali alcohol mol ratio and 2-propylheptanoic acid product parameters relation table
2, catalyzer and 2-propyl enanthol mass ratio
In oxidative pressure 3Mpa, oxidizing temperature 270 DEG C, alkali alcohol mol ratio 1: 1.1, catalyzer is under the catalytic condition of Manganse Dioxide, the relation of catalyzer and 2-propyl enanthol mass ratio and each parameter of 2-propylheptanoic acid goods, in table 2:
Table 2 catalyzer and 2-propyl enanthol mass ratio and 2-propylheptanoic acid product parameter relation table
3, oxidizing reaction temperature
Under the catalytic condition of oxidative pressure 3Mpa, alkali alcohol mol ratio 1: 1.1, catalyst manganese dioxide, the relation of oxidizing reaction temperature and each parameter of 2-propylheptanoic acid goods, in table 3:
Table 3 oxidizing reaction temperature and 2-propylheptanoic acid product parameter relation table
4, oxidation pressure
Oxidizing temperature 270 DEG C, alkali alcohol mol ratio 1: 1.1, catalyzer is under the catalytic condition of Manganse Dioxide, the relation of oxidation pressure and each parameter of 2-propylheptanoic acid goods, in table 4:
Table 4 oxidation pressure and 2-propylheptanoic acid product parameter relation table
In sum, each condition of the inventive method is defined as: alkali alcohol mol ratio is 1: 1 ~ 1.5, and catalyzer and 2-propyl enanthol mass ratio are 1: 70 ~ 80, and oxidizing reaction temperature is 265 ~ 295 DEG C, and oxidation pressure is 2.8 ~ 3.2Mpa.
Below in conjunction with process flow sheet, the invention will be further described.
1, be oxidized
Quantitative sheet alkali and catalyzer are dropped in stills for air blowing, then adds quantitative 2-propyl enanthol, and stir, be warming up to 265 ~ 295 DEG C, boost to 2.8 ~ 3.2Mpa, pressurize 20 ~ 30min, then gets rid of hydrogen, pressure release is to 0Mpa, and oxidizing reaction completes, and obtains solution A.Whole oxidation time is 1.8h ~ 3h;
2, acidifying
Upwards walk the solution A interior injection water coolant obtained, the quality of added water coolant accounts for 40 ~ 50% of reaction mass quality added by oxidizing reaction, filtering solid catalyst and impurity, then 2-propylheptanoic acid sodium water solution is injected acidifying still, start stirring, adjust pH value to 3 ~ 4 by sparger instillation sulfuric acid, h 2 so 4 concentration used is 45 ~ 55%, control reacting liquid temperature 60 ~ 90 DEG C, carry out acidification reaction, acidificatoin time is 0.5h ~ 1h simultaneously.Add water stirring after completion of the reaction, and stratification isolates sodium sulfate mother liquor, remaining as solution B;
3, washing and dehydration
In the solution B that upper step obtains, add the water of 20 ~ 40 DEG C, washing twice, cross and filter residual sulphur acid sodium; Temperature 85 ~ 95 DEG C, under pressure-0.65 ~-0.9Mpa condition, add the dehydration of polyamide resin analog assistant, obtain thick 2-propylheptanoic acid;
4, rectifying
By the thick 2-propylheptanoic acid press-in rectifying tower after dehydration, temperature 210 ~ 220 DEG C, under pressure-0.7 ~-0.9Mpa condition, through condenser condenses, obtained finished product 2-propylheptanoic acid, its purity >=99%, acid number >=322.40mgKOH/g, moisture≤0.1%, colourity (platinum-cobalt colorimetric number)≤10.
5, byproduct Sodium sulfate anhydrous.min(99) is prepared
The sodium sulfate mother liquor of releasing in acidifying, washing and dehydration is introduced standing in storage tank storage and naturally cooling by 5.1.Temperature≤20 DEG C;
Metabisulfite solution in storage tanks is sucked precooling settling bath, temperature-5 DEG C by 5.2, precipitation;
Precooling mother liquor of precipitation of ammonium is filtered through film filter by 5.3, and filtering thing drops in crystallization kettle, and water-bearing mother liquor returns to storage tanks;
5.4 crystallisates are after filtering chilled to-5 DEG C ~-10 DEG C, crystallization in crystallization kettle;
Sodium sulfate crystal is separated by 5.5 in separating machine, and removing moisture, obtains saltcake sal glauberi (Na
2sO410H
2o), sal glauberi content>=99.0%, pH value is 5.0 ~ 8.0;
5.6 separated sodium sulfate crystals are put in drying machine, are heated to 110 ~ 120 DEG C, obtain byproduct Sodium sulfate anhydrous.min(99) and anhydrous sodium sulphate.
Below enumerate several specific embodiment:
Embodiment 1:
(1) first the sheet alkali (NaOH) of 1000Kg and 54.31Kg zinc oxide are dropped in stills for air blowing as catalyzer, cover tightly dog-house, 4345Kg2-propyl enanthol is dropped into again to stills for air blowing, open stirring, be warming up to 270 DEG C, boost to 3Mpa, pressurize 20min, get rid of hydrogen, pressure release, to 0Mpa, obtains solution A;
(2) in solution A, the water of 2160Kg is injected, water injection pressure 0.5Mpa.By in the 2-propylheptanoic acid sodium solution press-in acidifying still in stills for air blowing, drive to stir, keep the temperature 75 DEG C of reaction.Then at the uniform velocity instill sulfuric acid by sulfuric acid sparger to reaction solution, h 2 so 4 concentration used is 45%, regulates pH value to 3.After acidification reaction completes, add water and continue to stir 10min, the quality added water is 1.2 times that separate out sodium sulfate quality, after stratification, releases lower floor's sodium sulfate mother liquor in metabisulfite solution storage tank, remaining as solution B;
(3) in upper step, remaining solution B enters washing step, through adding water, stirs, stratification, discharge water, cross and filter residual sulphur acid sodium, so repeatedly once, after filter, add polyamide resin analog assistant, decompression-0.9Mpa, dewaters during temperature 90 DEG C, obtains thick 2-propylheptanoic acid;
(4) the thick 2-propylheptanoic acid after dehydration is depressed in rectifying tower, be warming up to 210 DEG C, rectifying under-0.8Mpa pressure, through condenser condenses, obtain goods 2-propylheptanoic acid 4513.37Kg, yield is 95.42%, is 99.07% by chromatographic instrument nominal purity, acid number 322.63mgKOH/g, platinum-cobalt colorimetric 5;
(5) byproduct Sodium sulfate anhydrous.min(99) is prepared
(5.1) the sodium sulfate mother liquor of releasing in acidifying, washing and dehydration is introduced standing in storage tank storage and naturally cooling.Temperature≤20 DEG C;
(5.2) metabisulfite solution in storage tanks is sucked precooling settling bath, temperature-5 DEG C, precipitation;
(5.3) precooling mother liquor of precipitation of ammonium filtered through film filter, filtering thing drops in crystallization kettle, and water-bearing mother liquor returns to storage tanks;
(5.4) crystallisate is after filtering chilled to-5 DEG C ~-10 DEG C, crystallization in crystallization kettle;
(5.5) be separated in separating machine by sodium sulfate crystal, removing moisture, obtains saltcake sal glauberi (Na
2sO410H
2o), sodium sulphate content>=99.0%, pH value is 5.0 ~ 8.0;
(5.6) separated sodium sulfate crystal is put in drying machine, is heated to 110 ~ 120 DEG C, obtains byproduct Sodium sulfate anhydrous.min(99) and anhydrous sodium sulphate.
Embodiment 2:
(1) first the sheet alkali (NaOH) of 1000Kg and 79Kg catalyzer are dropped in stills for air blowing, wherein catalyzer is the mixture of zinc oxide, calcium oxide, cover tightly dog-house, then drop into 5925Kg2-propyl enanthol to stills for air blowing, open stirring, be warming up to 295 DEG C, boost to 2.8Mpa, pressurize 25min, get rid of hydrogen, pressure release, to 0Mpa, obtains solution A;
(2) in solution A, the water of 3151.8Kg is injected, water injection pressure 0.7Mpa.By in the 2-propylheptanoic acid sodium solution press-in acidifying still in stills for air blowing, drive to stir, keep the temperature 60 C of reaction.Then at the uniform velocity instill sulfuric acid by sulfuric acid sparger to reaction solution, h 2 so 4 concentration used is 50%, regulates pH value to 4.After acidification reaction completes, add water and continue to stir 10min, the quality added water is 1.2 times that separate out sodium sulfate quality, after stratification, releases lower floor's sodium sulfate mother liquor in metabisulfite solution storage tank, remaining as solution B;
(3) in upper step, remaining solution B enters washing step, through adding water, stirs, stratification, discharge water, cross and filter residual sulphur acid sodium, so repeatedly once, after filter, add polyamide resin analog assistant, decompression-0.80Mpa, dewaters during temperature 95 DEG C, obtains thick 2-propylheptanoic acid;
(4) the thick 2-propylheptanoic acid after dehydration is depressed in rectifying tower, be warming up to 220 DEG C, rectifying under-0.9Mpa pressure, through condenser condenses, obtain goods 2-propylheptanoic acid 6172.65Kg, yield is 95.70%, is 99.20% by chromatographic instrument nominal purity, acid number 323.25mgKOH/g, platinum-cobalt colorimetric 4;
(5) step is identical with embodiment 1.
Embodiment 3:
(1) first the sheet alkali (NaOH) of 1000Kg and 56.43Kg catalyzer are dropped in stills for air blowing, wherein catalyzer is the mixture of zinc oxide, calcium oxide and silicon-dioxide, cover tightly dog-house, then drop into 3950Kg2-propyl enanthol to stills for air blowing, open stirring, be warming up to 265 DEG C, boost to 3.2Mpa, pressurize 30min, get rid of hydrogen, pressure release, to 0Mpa, obtains solution A;
(2) in solution A, the water of 2503.21Kg is injected, water injection pressure 0.6Mpa.By in the 2-propylheptanoic acid sodium solution press-in acidifying still in stills for air blowing, drive to stir, keep the temperature 90 DEG C of reaction.Then at the uniform velocity instill sulfuric acid by sulfuric acid sparger to reaction solution, h 2 so 4 concentration used is 50%, regulates pH value to 3.5.After acidification reaction completes, add water and continue to stir 10min, the quality added water is 1.2 times that separate out sodium sulfate quality, after stratification, releases lower floor's sodium sulfate mother liquor in metabisulfite solution storage tank, remaining as solution B;
(3) in upper step, remaining solution B enters washing step, through adding water, stirs, stratification, discharge water, cross and filter residual sulphur acid sodium, so repeatedly once, after filter, add polyamide resin analog assistant, decompression-0.65Mpa, dewaters during temperature 85 DEG C, obtains thick 2-propylheptanoic acid;
(4) the thick 2-propylheptanoic acid after dehydration is depressed in rectifying tower, be warming up to 215 DEG C, rectifying under-0.7Mpa pressure, through condenser condenses, obtain goods 2-propylheptanoic acid 4120.26Kg, yield is 95.82%, is 99.14% by chromatographic instrument nominal purity, acid number 324.12mgKOH/g, platinum-cobalt colorimetric 6;
(5) step is identical with embodiment 1.
The above; for better case study on implementation of the present invention; not invention is imposed any restrictions, every above embodiment is done according to the technology of the present invention essence any simple modification, change and equivalent structure change, all still belong in the protection domain of technical solution of the present invention.
Claims (6)
1. a preparation method for 2-propylheptanoic acid, is characterized in that, it adopts following steps:
(1) sheet alkali and 2-propyl enanthol are dropped in stills for air blowing, stir under catalyzer existent condition and be warming up to 265 ~ 295 DEG C, boost to 2.8 ~ 3.2MPa, carry out oxidizing reaction, obtain solution A, catalyzer is one or more in zinc oxide, calcium oxide, silicon-dioxide, and the mass ratio of catalyzer and 2-propyl enanthol is 1:70 ~ 80;
(2) by the water cooling of upper step solution A, dilution, by the 2-propylheptanoic acid sodium press-in acidifying still in solution A, under 60 ~ 90 DEG C of temperature condition, add sulphuric acid soln adjust ph to 3 ~ 4, carry out acidification reaction, isolate sodium sulfate mother liquor layer after completion of the reaction, remaining as solution B;
(3) upper step solution B is washed successively, decompression dehydration, obtain thick 2-propylheptanoic acid;
(4) rectification under vacuum is carried out to the thick 2-propylheptanoic acid of upper step gained, obtained finished product 2-propylheptanoic acid.
2. the preparation method of 2-propylheptanoic acid according to claim 1, is characterized in that, the sheet alkali in described step (1) and the mol ratio of 2-propyl enanthol are 1:1 ~ 1.5.
3. the preparation method of 2-propylheptanoic acid according to claim 1, is characterized in that, the quality added water in described step (2) accounts for 40% ~ 50% of added reaction mass quality in step (1).
4. the preparation method of 2-propylheptanoic acid according to claim 1, is characterized in that, in described step (3), dewatering pressure is-0.65 ~-0.9MPa, and temperature is 85 ~ 95 DEG C.
5. the preparation method of 2-propylheptanoic acid according to claim 1, is characterized in that, in described step (4), rectifying pressure is-0.7 ~-0.9MPa, and temperature is 210 ~ 220 DEG C.
6. the preparation method of 2-propylheptanoic acid according to claim 1, is characterized in that, in described step (2), (3), isolated sodium sulfate mother liquor layer obtains byproduct Sodium sulfate anhydrous.min(99) through precipitation, filtration, crystallization, separation, drying.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87104094A (en) * | 1986-06-12 | 1988-02-10 | 施托福化学公司 | The synthetic method of fatty acid |
| JPH06122649A (en) * | 1992-10-12 | 1994-05-06 | Daisan Kasei Kk | Production of higher alpha-branched fatty acid |
| US5654453A (en) * | 1993-01-29 | 1997-08-05 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of α-branched aliphatic monocarboxylic acids |
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2011
- 2011-09-20 CN CN201110279165.3A patent/CN103012105B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87104094A (en) * | 1986-06-12 | 1988-02-10 | 施托福化学公司 | The synthetic method of fatty acid |
| JPH06122649A (en) * | 1992-10-12 | 1994-05-06 | Daisan Kasei Kk | Production of higher alpha-branched fatty acid |
| US5654453A (en) * | 1993-01-29 | 1997-08-05 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of α-branched aliphatic monocarboxylic acids |
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