CN109942404A - A kind of method that polyacid catalysis oxidation prepares phthalic acid - Google Patents
A kind of method that polyacid catalysis oxidation prepares phthalic acid Download PDFInfo
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- CN109942404A CN109942404A CN201910022013.1A CN201910022013A CN109942404A CN 109942404 A CN109942404 A CN 109942404A CN 201910022013 A CN201910022013 A CN 201910022013A CN 109942404 A CN109942404 A CN 109942404A
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Abstract
The present invention relates to a kind of methods that Anderson type polyacid catalysis oxidation prepares phthalic acid.Specific steps are as follows: ortho-xylene, Anderson type polyacid catalyst, additive, solvent are added in reactor；Magnetic agitation is reacted in oxygen atmosphere；100-220 DEG C of reaction temperature；12-24h is sufficiently stirred and obtains required product.The invention avoids highly corrosive is used in prior synthesizing method, high poison easily makes malicious reagent, the reaction condition of high temperature and pressure, and uses Anderson type polyacid for catalyst, has high reactivity, required reaction condition is mild, environmental-friendly；Single-minded selectivity is high, and recoverable is suitable for industrialized production.Hydrogen peroxide, air or oxygen reduce the generation of manufacturing cost and the three wastes, alleviate environmental protection pressure, but also have the characteristics that easily controllable and industrialized production as oxidant.
Description
Technical field
The invention belongs to the catalysis of technical field of catalytic chemistry, especially polyoxometallate, in particular to miscellaneous more
The method that acid catalyst is catalyzed ortho-xylene phthalic acid, belongs to filed of daily-use chemical industry.
Background technique
Ortho-xylene is colourless transparent liquid, there is a stink of similar toluene, and 144.4 DEG C of boiling point, 30 DEG C of flash-point, self-ignition point
463 DEG C, explosion limit 1%~7%, fusing point (DEG C): -25, boiling point (DEG C): 144.4, relative density (water=1): 0.88, relatively
Vapour density (air=1): 3.66, saturated vapour pressure (kPa): 1.33 (32 DEG C), the combustion heat (kJ/mol): -4845.3, face
Boundary's temperature (DEG C): 359, critical pressure (MPa): 3.7, Octanol/water Partition Coefficients: 3.12, flash-point (DEG C): 25 (CC), temperature of igniting
Spend (DEG C): 463, upper explosion limit (%): 7, lower explosion limit (%): 0.9, dissolubility: it is not soluble in water, be miscible in ethyl alcohol, ether,
The majority organic solvent such as chloroform.It is mainly used as industrial chemicals and solvent, can be used for producing phthalic anhydride, dyestuff, insecticide and drug, such as
Vitamin etc..Also it can be used as aviation gasoline additive.Other than it may be used as solvent, it is also used to manufacture phthalic anhydride, neighbour
The raw material of benzene dicarbonitrile, dimethlbenzene and dimethylaniline, aviation gasoline additive.It is mainly used as solvent and for synthetic oil
Paint, coating.
Phthalic acid, be colourless crystallization or crystalline powder, colourless monoclinic crystal, density (g/mL, 25/4 DEG C):
1.451, fusing point (DEG C): 227, crystal phase phase standard heat of combustion (enthalpy) (kJmol-1): -3223.6, crystal phase standard claims hot (enthalpy)
(kJ·mol-1): -782.0, crystal phase standard entropy (Jmol-1·K-1): 207.9, crystal phase standard free energy of formation (kJmol-1): -592.3, dissolubility: being dissolved in methanol and ethyl alcohol, is slightly soluble in water and ether, chloroform, benzene and petroleum ether are not dissolved in, index of refraction:
1.604, toxicity LD50 (mg/kg): rat oral 7900.Main application, preparing standard solution make alkalimetry standard.Calibrating cobalt,
Copper, germanium, mercury, nickel, potassium, strontium and zinc.Measure the organic syntheses such as cobalt, iodate and lead.Analytical reagent is also acted as, such as makees cooperation and covers
Agent is covered, buffer solution is prepared, makees chromatography standard substance.And can be used for manufacturing fuel, resin, drug and plasticizer etc..
The synthetic method of phthalic acid specifically includes that
(1) it is hydrolyzed by ditridecyl phthalate: Friel J M.Coating compositions containing
mono-or diester coalescing agents and a substrate coated therewith.:EP,
EP0026982 [P].1981.Ramia Z.Al Bakain,Samer R.Abulateefeh,Mutasem
O.Taha.Synthesis and characterization of chitosan-lactate–phthalate and
evaluation of the corresponding zinc-and aluminum-crosslinked beads as
potential controlled release matrices[J]. European Polymer Journal,2015,73
(6):402-412.
(2) by naphthalene and its naphthalene derivatives, catalysis oxidation is obtained under conditions of ruthenium salt is as catalyst: Patil R D,
Sasson Y.Naphthalenes Oxidation by Aqueous Sodium Hypochlorite Catalyzed by
Ruthenium Salts Under Phase-Transfer Catalytic Conditions[J].Catalysis
Letters, 2016,146(5):991-997.Patil R D,SassonY.Naphthalenes Oxidation by
Aqueous Sodium Hypochlorite Catalyzed by Ruthenium Salts Under Phase-Transfer
Catalytic Conditions[J].Catalysis Letters,2016,146(5):991-997.Patil R D,
Sasson Y. Naphthalenes Oxidation by Aqueous Sodium Hypochlorite Catalyzed by
Ruthenium Salts Under Phase-Transfer Catalytic Conditions[J].Catalysis
Letters,2016,146(5): 991-997.Patil R D,Sasson Y.Naphthalenes Oxidation by
Aqueous Sodium Hypochlorite Catalyzed by Ruthenium Salts Under Phase-Transfer
Catalytic Conditions[J].Catalysis Letters,2016,146(5):991-997.
The above synthetic method disadvantage is exactly reaction condition complexity, and using highly corrosive, high poison is easily made malicious reagent, and made
Use noble ruthenium as catalyst, to limit its application industrially.
It is the advantages of the method applied in the present invention, easy to operate using one kettle way, high income, mild condition, environment friend
It is good, it is easily recycled, high recycling rate, compared with organic metal, organic metal adds the reaction of ligand, matches after reaction
Body is easily separated with organic metal, so that residual is in the product, causes product impure.And this experiment uses polyoxometallate
As catalyst, it is not required to addition ligand, then avoids this disadvantage.Use base metal iron for hetero atom, economical and effective, more
With practicability.
Summary of the invention
The purpose of the present invention is to provide the method that one kind can prepare simultaneously high-quality phthalic acid, traditional adjacent benzene
Dioctyl phthalate production method is phthalic acid ester direct hydrolysis method production phthalic acid, but has prepared phthalic acid
Crude product complicated component, phthalic acid is of poor quality, directly affects the shortcomings that phthalic acid is applied in terms of pharmaceuticals industry.
And method provided by the invention has the life that environmentally protective, reaction condition is mild, at low cost, the three wastes are few, is easily industrialized
It produces, obtained product is widely used in the fields such as food, drug, daily use chemicals.It avoids in the oxidation reaction stage using initiator,
Especially halogen initiator uses hydrogen peroxide as oxidant, and product only has water, without other pollutants, using mild
Alkaline hydrolysis conditions the generation of manufacturing cost and the three wastes therefore is reduced using the circulation for realizing material from closed loop, mitigate
Environmental protection pressure, but also have the characteristics that easy, easily controllable and industrialized production.
Through research, the inventor has found that by the synthesis technology included the following steps, using ortho-xylene as raw material, in nothing
In the presence of halogen catalyst, by hydrogen peroxide oxidation, phthalic acid is generated, the phthalic acid of high-quality can be obtained,
Reactive chemistry formula are as follows:
Therefore, the method that heteropolyacid catalyst catalysis of the invention prepares phthalic acid, comprising the following steps:
Step 1) is added in reaction tube ortho-xylene, heteropolyacid catalyst, 30% hydrogen peroxide, additive and molten
Agent, reaction stop reaction after a certain period of time；
Step 2), after oxidation reaction, then Filtration of catalyst is added water and ethyl acetate, is repeatedly extracted
Obtain organic phase I and water phase I；If occurring emulsion in extraction process, suitable sodium chloride can be added and be demulsified, then shake again
It swings, liquid separation.
Anhydrous magnesium sulfate is added into organic phase I in step 3), hikes up until having shaked gently powder, then filters, by liquid
It is transferred in new eggplant-shape bottle, liquid is rotated, and decompression steams organic phase II to get phthalic acid is arrived；When revolving it is noted that
Temperature and the revolving time control.The revolving time is too short, and not exclusively, obtained target product is impure for product separation.
The following specifically describes the present invention.
In step 1 of the invention, first reaction tube is rinsed well with deionized water, is then baked to, then to clean
Reaction tube in be added ortho-xylene, heteropolyacid catalyst, carbonic acid sodium additives, 30% hydrogen peroxide and acetic acid solvent, instead
It should stop reacting after a certain period of time.
According to the present invention, solvent used in step 1 be organic carboxyl acid class, preferably acetic acid be oxidation reaction solvent.
The dosage of solvent for use acetic acid is 2~4ml, preferably 2ml.
Used catalyst is Fe-Anderson type heteropolyacid catalyst.
Additive therefor is sodium carbonate.
According to the present invention, catalyst of the transition metal salt as oxidation reaction is selected, it can be to avoid initiator be used, especially
Be without using halogen initiator so that do not contain micro initiator in final products phthalic acid, can satisfy completely food,
The safety requirements of medicine and other fields.
The mole dosage ratio of Fe-Anderson type heteropolyacid catalyst and ortho-xylene used be 1~50:1, preferably 1~
20:1.
The temperature of oxidation reaction is 80~150 DEG C, and preferable reaction temperature is 80~120 DEG C, more preferable 80~100 DEG C.
Oxidation pressure (gauge pressure) is 1~5.0MPa, preferably 1~4.0MPa, more preferable 1~2.0MPa, wherein work as table
Pressure carries out oxidation reaction when being 0 under normal pressure.
Oxidation time be 12~for 24 hours, preferably 1~20h, more preferable 5~12h.Reaction time is resolute, may cause anti-
Should not exclusively, the reaction time too long increase that may cause side reaction, to cause target product impure.
Step 1 through the invention uses cheap hydrogen peroxide as oxidant, ortho-xylene quilt in liquid phase
Catalysis oxidation uses hydrogen peroxide as oxidant, and product only has water, without other pollutants, mainly generates phthalic acid.
It in step 2 of the invention, after oxidation reaction, is filtered, removes Fe-Anderson type heteropoly acid catalysis
Agent, through washing, after ethyl acetate rinse, the recyclable recycling of Fe-Anderson type heteropolyacid catalyst.
After removing catalyst, needs that water and ethyl acetate is added, repeatedly extracted, obtain organic phase I and water phase I.If extraction
There is emulsion during taking, suitable sodium chloride can be added and be demulsified, then vibrate again, liquid separation.
Extraction times can be 1-5 times, and preferably washing times are 2-4 times, more preferable 3 times.Extraction times will cause very little
The waste of raw material.
The mole dosage ratio of extraction Shi Shuiyu ethyl acetate is 0.1~10:1, preferably 1~5:1, more preferable 1:1 every time.
In step 3 of the present invention, anhydrous magnesium sulfate is added into organic phase I, is hiked up until having shaked gently powder, then into
The liquid that row is obtained by filtration, liquid is transferred in a new clean eggplant-shape bottle, steams organic phase II through decompression to get arriving
Phthalic acid.
The additive is added in solid form, additive, ortho-xylene mole dosage ratio be 5~10:1, preferably
5~8:1, more preferable 5~6:1.
Decompression steams organic phase II, and the revolving time is 5~12min, preferably 7min, and the product that the time is so short that very much is impure.
Acid used is acetic acid.
In step 2 of the present invention, water phase I extraction and recovery water is not necessarily to any processing, can be directly used for recycling.
Alkali used in additive is crystals of sodium carbonate.
The purity of the additive is 99%.
The mole dosage of the additive and ortho-xylene ratio is 5~10:1, preferably 5~8:1, more preferable 5~6:1.
Reaction temperature is 80~120 DEG C, preferably 80~100 DEG C.
The beneficial effects are mainly reflected as follows the following aspects:
(1), the oxidation reaction stage selects Fe-Anderson type heteropolyacid catalyst, avoids the use of initiator, especially
Its use for being that of avoiding halogen initiator provides a kind of good method to produce the phthalic acid of high-quality simultaneously,
Obtained product can be used for the fields such as food, medicine, detergents and cosmetic.
(2), oxidation reaction uses hydrogen peroxide as oxidant, and product only has water, without other pollutants, has warp
The characteristics of Ji, environmental protection, green high-efficient.
(3), a kind of method for facilitating recycling catalyst is provided, and the catalyst recycled is applied repeatedly, does not find activity
Decaying.
(4), using self-closing circulation technology, the circulation of all materials is realized, manufacturing cost and the three wastes are greatly reduced
Generation, alleviate environmental protection pressure.
(5), the present invention also has the characteristics that easy, easily controllable and industrialized production.
Specific embodiment
The content of present invention is further explained and described above by specific embodiment, but case study on implementation is understood not to
Limiting the scope of the invention.
Case study on implementation 1
By the ortho-xylene of 1.0617g (0.01mol), 1% (0.0076g) Fe-Anderson type polyoxometallate,
The carbonic acid sodium additives of 1% (0.00106g) and the solvent acetic acid of 5equiv (0.3g) are put into dry reaction test tube, are risen
Reaction is placed in air and carries out to after 100 DEG C by temperature, in the case where pressure (gauge pressure) is 1.0MPa after insulation reaction 20h, stops anti-
It answers.Reaction system is extracted 3 times with ethyl acetate, solvent is removed under reduced pressure in obtained product, and column chromatography for separation obtains adjacent benzene two
Formic acid obtains product 0.8956g, yield 54%.
Case study on implementation 2
By the ortho-xylene of 1.0617g (0.01mol), 1% (0.076g) Fe-Anderson type polyoxometallate,
The carbonic acid sodium additives of 1% (0.00106g) and the solvent acetic acid of 5equiv (3g) put into the water of inner liner polytetrafluoroethylene
In thermal response kettle, it is noted that it first checks whether equipment has damage using preceding, solvent and raw material is added into hydrothermal reaction kettle container,
After stirring and dissolving, it is blown into nitrogen into container for a period of time, is in system in inert atmosphere, hydrothermal reaction kettle lid in use
It tightens and adds catalyst and place it in baking oven, after being warming up to 100 DEG C, connect oxygen tank, making pressure (gauge pressure) is 1.0MPa
Or so, after insulation reaction 12h, stop reaction.Kettle cover is opened to autoclave body cooled to room temperature, with ethyl acetate by reaction system
Extraction 3 times, solvent is removed under reduced pressure in obtained product, and column chromatography for separation obtains phthalic acid, obtains product 1.1113g, receives
Rate is 67%.
Case study on implementation 3
By the ortho-xylene of 1.0617g (0.01mol), the Fe-Anderson type polyoxometallate of 1% (0.0076g)
The carbonic acid sodium additives of catalyst, 1% (0.00106g), 30% hydrogen peroxide and 5equiv (0.3g) of 3equiv it is molten
Agent acetic acid is put into dry and clean pressure pipe, after being warming up to 100 DEG C, is kept the temperature in the case where pressure (gauge pressure) is 1.0MPa anti-
After answering 12h, stop reaction, extracted reaction system 3 times with ethyl acetate, solvent, column chromatography is removed under reduced pressure in obtained product
Isolated phthalic acid obtains product 1.2937g, yield 78%.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But without departing from the technical solutions of the present invention, according to the technical essence of the invention to above embodiments institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection scope of technical solution of the present invention, used herein is each
A bibliography, which is hereby incorporated by reference.
Detailed description of the invention:
(1) Fig. 1 is that Anderson type polyoxometallate is infrared (by taking iron is metal center as an example)
(2) Fig. 2 be Tris Derivatives Modified Anderson type polyacid it is infrared (be metal center with iron, Tris-NH2 modification
For polyacid)
(3) it (is metal center, Tris-NH2 modification with iron that Fig. 3, which is the Anderson type polyacid nuclear-magnetism of Tris Derivatives Modified,
For polyacid)
(4) Fig. 4 is the method that Anderson type polyacid catalysis oxidation prepares phthalic acid.
Claims (7)
1. by the preparation method of ortho-xylene to phthalic acid, which comprises the following steps:
Step 1), is added in reaction tube ortho-xylene, catalyst, 30% hydrogen peroxide, additive and solvent, and reaction is certain
Stop reaction after time.
The catalyst are as follows: polyacid parent: [NH4]3[M1Mo6O18(OH)6] or [NH4]4[M2Mo6O18(OH)6]
The parent of polyacid modification: [N (C4H9)4]3[M1Mo6O18(OH)3{(OCH2)3CR}]/[N(C4H9)4]4[M2Mo6O18(OH)3
{(OCH2)3CR }], wherein M1=manganese (Mn), iron (Fe), aluminium (Al), M2=copper (Cu), cobalt (Co), nickel (Ni) (select wherein it
One), the mole dosage of catalyst and toluene ratio: 0.1~1%:1；Oxidant used are as follows: air, oxygen, hydrogen peroxide；
The solvent is acetic acid, and the mole dosage ratio of acetic acid and ortho-xylene is 1~50:1,
Additive therefor are as follows: sodium acetate, sodium hydroxide, sodium carbonate.Mole of (selecting one of them), additive and ortho-xylene
Amount ratio: 1~10%:1；
Solvent for use are as follows: acetic acid, dimethyl succinate, diethyl succinate, diethyl malonate.(selecting one of them) is used
Amount: 2~10ml；
Step 2) after oxidation reaction, is filtered to remove heteropolyacid catalyst, adds ethyl acetate and water, repeatedly extract
To organic phase I and water phase I；
Step 3), is added anhydrous magnesium sulfate into organic phase I, and anhydrous magnesium sulfate is to shaking gently conical flask anhydrous slufuric acid magnesium dust
It can gently hike up, then filtering removal solid, obtained liquid, then be rotated, vacuum distillation obtains organic phase II, i.e., adjacent benzene two
Formic acid.
2. preparation method according to claim 1, which is characterized in that
In step 1, acetic acid dosage used is 2~4ml；The mole dosage ratio of heteropolyacid catalyst and ortho-xylene used is 0.1
~1%:1.
3. preparation method according to claim 1, which is characterized in that
In step 1, oxidizing reaction temperature is 80~120 DEG C；Oxidation reaction gauge pressure is 1~5.0MPa.
4. the preparation method described in one of according to claim 1, which is characterized in that
In step 2, molal weight ratio 1:1~2 of ethyl acetate and water are added.
5. the preparation method described in one of according to claim 1, which is characterized in that
In step 2, after ethyl acetate and water is added, the number of extraction is 2~4 times.If there is emulsion, suitable chlorine can be added
Change sodium to be demulsified, then vibrate again, liquid separation.
6. the preparation method described in one of according to claim 1, which is characterized in that
In step 3, the amount of anhydrous magnesium sulfate and the mole dosage ratio of ortho-xylene: 10~30:1 is added.
7. the preparation method described in one of according to claim 1, which is characterized in that
In step 3, the time of vacuum distillation is 5~15min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602393A (en) * | 2017-09-28 | 2018-01-19 | 安徽省庆云医药股份有限公司 | A kind of method that benzyl position C H keys are direct oxidation into ketone or acid |
| CN107698436A (en) * | 2016-08-09 | 2018-02-16 | 朱翠英 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
| CN108409552A (en) * | 2018-03-08 | 2018-08-17 | 上海应用技术大学 | A kind of method that the oxidation of Anderson heteropoly acid catalysis prepares terephthalic acid (TPA) |
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- 2019-01-10 CN CN201910022013.1A patent/CN109942404A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107698436A (en) * | 2016-08-09 | 2018-02-16 | 朱翠英 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
| CN107602393A (en) * | 2017-09-28 | 2018-01-19 | 安徽省庆云医药股份有限公司 | A kind of method that benzyl position C H keys are direct oxidation into ketone or acid |
| CN108409552A (en) * | 2018-03-08 | 2018-08-17 | 上海应用技术大学 | A kind of method that the oxidation of Anderson heteropoly acid catalysis prepares terephthalic acid (TPA) |
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Application publication date: 20190628 |