CN107963964A - The preparation method of M-phthalic acid - Google Patents

The preparation method of M-phthalic acid Download PDF

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Publication number
CN107963964A
CN107963964A CN201711066085.3A CN201711066085A CN107963964A CN 107963964 A CN107963964 A CN 107963964A CN 201711066085 A CN201711066085 A CN 201711066085A CN 107963964 A CN107963964 A CN 107963964A
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reaction
meta
preparation
xylene
oxidation
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孙伟振
赵玲
吕全明
董健
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East China University of Science and Technology
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East China University of Science and Technology
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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
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • 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
    • C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of preparation method of M-phthalic acid, the preparation method includes the following steps：In meta-xylene oxidation system, meta-xylene reacts to obtain M-phthalic acid through once oxidation；The meta-xylene oxidation system includes catalyst, oxidant and solvent, and the catalyst is Co Mn Br catalyst, and the oxidant contains 5~21% O2, 0.04%~79% CO2, and N2, the percentage is percent by volume；At the end of the once oxidation, oxygen partial pressure is 1.21%~6% in tail gas.The preparation method of the present invention contributes to the formation of active peroxy carbonates, can effectively accelerate reaction speed, weakens burning reaction, and by O in tail gas2Content is controlled in safe range, adds the processing safety of reaction.

Description

The preparation method of M-phthalic acid
Technical field
The present invention relates to a kind of preparation method of M-phthalic acid.
Background technology
A series of commercialized oxidized compounds are typically to be spread out using air or oxygen direct oxidation oil or natural gas Biology, such as preparing benzaldehyde by oxidizing toluene and benzoic acid, p xylene oxidation prepare terephthalic acid (TPA) and phenol isopropylbenzene, Dimethylbenzene (MX) oxidation prepares M-phthalic acid (IPA) etc..This kinds of oxidation reaction typically occurs in that there are air or oxygen Under the conditions of, form peroxide and hydrogenation oxide.Also, as automatic oxidation reaction, even if under cryogenic, oxidation reaction Also can occur.
In general, MX oxidations have direct relation with oxygen content in liquid phase, and within certain limits, partial pressure of oxygen is bigger, meaning Under certain air mass flow, more bubbles are enclosed in below liquid level, are conducive to the raising of reaction rate.But in hyperoxia qi leel Pressure, combustion reaction also aggravates, therefore suitable partial pressure of oxygen is very important.In the industrial production, air intake is root Judge according to oxygen content in reaction end gas.Anoxia phenomenon can occur when oxygen content is low in tail gas in reactor, cause product matter Measure poor, intermediate product increases, and product is very big to the flow effect of subsequent material in light yellow.If oxygen content mistake in tail gas Height, can not only aggravate combustion reaction and there are certain security threat.Therefore, in actual production operation, to prevent reaction to lack Oxygen is suitably superfluous by oxygen content in tail gas, and still, tail too high oxygen level has explosion danger, therefore Amoco oxidation technologies are advised safely It is fixed：Tail oxygen content sends alarm when reaching 6%, and blowing air is automatically stopped when reaching 8%.
The content of the invention
The technical problems to be solved by the invention are to overcome oxygen partial pressure and air intake existing in the prior art It is unmanageable, and oxygen content is either excessive there are security risk or too small burning reaction is serious asks in the tail gas triggered Topic, and provide a kind of preparation method of M-phthalic acid.The preparation method of the present invention contributes to the shape of active peroxy carbonates Into, it can effectively accelerate reaction speed, weaken burning reaction, and by O in tail gas2Content is controlled in safe range, is increased The processing safety of reaction is added.
The present invention provides a kind of preparation method of M-phthalic acid, the preparation method includes the following steps：Two In toluene oxidation system, meta-xylene reacts to obtain M-phthalic acid through once oxidation；The meta-xylene oxidation system includes urging Agent, oxidant and solvent, the catalyst are Co-Mn-Br catalyst, and the oxidant contains 5~21% O2, 0.04% ~79% CO2, and N2, the percentage is percent by volume；At the end of the once oxidation, oxygen partial pressure is in tail gas 1.21%~6%.
It is preferred that the M-phthalic acid prepared by above-mentioned preparation method is also after secondary oxidation and hydrofinishing, then pass through The M-phthalic acid filter, wash, being dried to obtain after refining.Wherein, it is preferred that the oxidation system of the secondary oxidation, technique The oxidation system of condition and the once oxidation, process conditions are identical.For simplicity being all referred to as in description afterwards anti- Should.
Wherein, the hydrofinishing is this area conventional steps.The condition of the hydrofinishing is preferably：Turning basket formula Reaction kettle carries out, and catalyst is platinum carbon catalyst, and the rotating speed of agitating paddle is 500~1000ppm, and temperature is 180-270 DEG C, reaction Pressure is 0.8-3.0MPa, and the reaction time is counted as 30~90min using the mean residence time of solvent.
In the present invention, it is preferred that the oxidant is air and CO2Mixture, generally by gas mixer into Row mixing, by varying the flow of two strands of gas, to control O in inlet gas2、CO2, CO concentration and proportioning.Air and CO2 Volume ratio be preferably 0.1~9, be more preferably 0.1~2.Wherein, the air has this area conventional sense, wherein having Body component includes：The volume fraction of nitrogen is about 78%, and the volume fraction of oxygen is about 21%, rare gas (helium, neon, argon, Krypton, xenon, radon) volume fraction be about 0.934%, the volume fraction of carbon dioxide is about 0.04%, and (such as water steams for other materials Gas, impurity etc.) volume fraction be about 0.002%.
In the present invention, N in the oxidant2Content be preferably 0.78%~78%.
In the present invention, generally also contain micro CO, such as 0.0002%~0.002% in the oxidant.Due to This content is too low, and analytical instrument is difficult to detect, and can only substantially be calculated by mixed proportion.
In the present invention, it is preferred that also containing catalytic additive in the meta-xylene oxidation system.
Wherein, the catalytic additive is preferably comprised rare earth metal acetate, alkali metal acetate and transition metal vinegar One or more in hydrochlorate, addition of the catalytic additive in meta-xylene oxidation system are 50~1500ppm.
Wherein, the rare earth metal acetate is preferably by the one or more in Ce, Nd, Pr, Gd, Dy, Sm and La The acetate composition of rare earth metal, more preferably, the rare earth metal acetate is molten by rare-earth oxide or rare earth metal salt It is prepared in acetic acid.The alkali metal acetate is preferably by the vinegar of one or more alkali metal in KAc, KOH and NaOH Hydrochlorate forms, and is more preferably prepared for alkali metal is dissolved in acetic acid, or alkali is prepared as acetate, wherein the alkali gold Category includes lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs) and francium (Fr) this 6 kinds of elements.The transition metal acetate compared with It is made of goodly the one or more in the acetate of Hf, Zr, Fe and the acetate of organic-molybdenum.The transition metal acetate In, the acetate of Hf is more preferable than the effect of Zr.
In the present invention, addition of the catalytic additive in meta-xylene oxidation system be preferably 100~ 300ppm.In the present invention, the meta-xylene oxidation system has this area conventional sense, includes the collection of all reaction raw materials Close.
In the present invention, the preferred scope of addition of the rare earth metal acetate in meta-xylene oxidation system is 50ppm~500ppm.
In the present invention, the preferred scope of addition of the alkali metal acetate in meta-xylene oxidation system is 50ppm~500ppm.
In the present invention, the preferred scope of addition of the transition metal acetate in meta-xylene oxidation system is 50ppm~500ppm.In the present invention, if with the addition gauge of transition metal ions, its content preferably 20~350ppm.
In the present invention, the catalyst is preferably the mixture of cobalt acetate, manganese acetate and sodium bromide or hydrobromic acid, its In, cobalt acetate, manganese acetate, the Co ion concentrations of sodium bromide or hydrobromic acid, Mn ion concentrations, Br ion concentration ranges are this area Normal ranges, respectively preferably 200~1000ppm, 200~1000ppm, 200~1600ppm.
In the present invention, it is preferred that the catalyst and catalytic additive are first uniformly mixed before reactions.
In the reaction system of the present invention, the solvent is this area Conventional solvents, preferably the liquid of water and acetic acid composition Body.Wherein, the content of water in the reaction system is preferably 3%~12%.
In the reaction system of the present invention, solvent ratio ((HAc+H2O)/MX) 1~20 is preferably, it is more preferably 3~20.
In the present invention, the rotating speed of the reaction is conventional for this area, preferably 500~1000rpm, is more preferably 400 ~800ppm；The temperature of the reaction is conventional for this area, and preferably 150~240 DEG C, be more preferably 150-190 DEG C；It is described The pressure of reaction is conventional for this area, preferably 0.45~2.5MPa, is more preferably 0.45-2.0MPa.The reaction when Between be this area normal condition, in terms of the mean residence time of solvent, the time of the reaction is preferably 30~120min, More preferably it is 30~60min.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can be combined, each preferably real up to the present invention Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is：1. the preparation method of M-phthalic acid provided by the invention contributes to activity The formation of peroxy carbonates, enhances catalytic activity and selectivity to aromatic carboxylic acid, 2. effectively accelerates reaction speed, 3. weakens Burning reaction, and 4. by O in tail gas2Content is controlled in safe range, adds the processing safety of reaction.
Brief description of the drawings
Fig. 1 is the process flow diagram that Action In The Liquid Phase Oxidation of Xylene produces M-phthalic acid among the embodiment of the present invention.
Fig. 2 is the liquid chromatogram that the embodiment of the present application measures.
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality Apply among a scope.The experimental method of actual conditions is not specified in the following example, according to conventional methods and conditions, or according to business Product specification selects.
In following embodiments, the process flow diagram of meta-xylene oxidation production M-phthalic acid is as shown in Figure 1.
In following embodiments, IPA yields are tested using high-efficient liquid phase chromatogram technique analysis, and specific instrument and test condition are such as Under：
HPLC detection methods use 1120 high performance liquid chromatographs of U.S. Agilent, autosampler, Agilent 1120 type UV/Vis detectors, 2 data handling systems of Empower.
Chromatographic condition：
Chromatographic column：Agilent TC-C18 chromatographic columns (4.6 × 250mm, 5 μm)；Mobile phase A is 100% acetonitrile, mobile phase B is+83% water of 17% methanol；Condition of gradient elution：A is from 30% to 100% during 0~20min, and B is from 100% during 20~25min To 30%, B is from 70% to 0% during 0~20min, and B is from 0% to 70% during 20~25min；Flow velocity：1ml·min-1；Column temperature：30 ℃；Detection wavelength：260nm；Sample size：20μL.Retention time of M-phthalic acid main peak is 5.3min or so under the conditions of this, The retention time of carboxyl benzaldehyde main peak is 6.5min or so, and the retention time of m-methyl benzoic acid main peak is 9.5min or so, Between tolyl aldehyde main peak retention time for 11.4min or so, the retention time of meta-xylene main peak is 16.8min or so, Specifically see Fig. 2.Wherein, peak 1- M-phthalic acids, carboxyl benzaldehyde between peak 2-, peak 3- benzoic acid, peak 4- m-methyl benzoic acids, Tolyl aldehyde between peak 5-, peak 6- meta-xylenes.
For Fig. 2, it is necessary to illustrate at following 2 points：
First, by making the standard curve of different material, the absorption peak area of different material in product is measured in experiment, it is right It should can calculate the concentration of different material.Since the absorption intensity of every kind of material is different, corresponding absorption peak area is also just different. Therefore, the peak area size of different material can not directly judge how much is content.
In addition, in embodiment, the yield of IPA is carried out according to calculation commonly used in the art, is specially：Yield= MX concentration in concentration/raw material of IPA in product.It should be noted that the concentration of IPA refers in liquid-phase chromatographic analysis in product In, it is configured to the concentration after sample needed for liquid phase detection.
The detection device and test condition of infrared gas analyser are as follows：
CO2Concentration analysis with CO is using the GXH-510 infrared ray gas analyzers of Thebe instrument production, the analyzer Belong to not beam splitting type infrared analyzer, its optical system is by light source, gas chamber and detector three parts composition.Before electric system has Put amplifier and temperature control and power supply three parts composition.Its operation principle is the selective absorbing to infrared ray according to specific gas Feature, obtains by certain function association conversion.Instrument employs advanced single light source, and single tube is every half gas chamber and high stable Property, the new pyroelectric detector of high reliability.Continuous infra-red radiation is modulated into 6.25Hz by light source part to be continued to radiate and hands over Alternately by the analysis of gas chamber while and during reference, finally absorbed by detector.
Oxygen analysis (calculates CO2, CO generating rates formula in need the concentration of oxygen, therefore oxygen analysis instrument is For measuring O in tail gas2Concentration) using EN-560 types magnetic oxygen analyser (Shanghai English contain instrument preferential company), EN- 560 type magnetic oxygen analyser being integrated fixed installation formula online analytical instruments.The operation principle of instrument is the paramagnetic based on oxygen Characteristic, has high magnetic susceptibility, under non-uniform magnetic-field effect, is formed " magnetic wind ", thermomagnetic convection is produced in sensing element, So as to produce " cooling " effect to sensing element, its resistance value is set to change and work.
Embodiment 1A
Meta-xylene, acetic acid, water, cobalt acetate, manganese acetate, hydrobromic acid are uniformly mixed according to a certain percentage, then pumped Enter in oxidizing reactor.The temperature of rotating speed of agitator and heating jacket is set when experiment starts, at the same time, by O2、CO2、N2Press Admixture of gas, which is made into, according to certain proportion is introduced into initiated oxidation reaction in reactor.Oxidation reaction condition is that rotating speed of agitator is 800ppm, temperature are 180 DEG C, reaction pressure 2.0MPa, and the reaction time is counted as 90min using the mean residence time of solvent, into The mass ratio for expecting solvent and meta-xylene is 10:1, H2O/HAc=5%, using ionometer catalyst concn Co as 800ppm, Mn is 400ppm, Br 1200ppm, O in admixture of gas2Content is 17.9%, N2Content is 67.4%, CO2Content is 14.7%.Product after once oxidation is pumped into secondary oxidation reactor, adjusts the temperature, pressure and gas stream of reaction Amount.Secondary oxidation reaction condition is that rotating speed of agitator is 300ppm, and temperature is 170 DEG C, reaction pressure 1.5MPa, with solvent The mean residence time meter reaction time is 45min.The material of secondary oxidation is washed, is dissolved with water.Using turning basket Formula reaction kettle, catalyst are platinum carbon catalyst, and rotating speed of agitator 500ppm, temperature is 230 DEG C, reaction pressure 2.1MPa, Reaction time is counted as 30min using the mean residence time of solvent.
Embodiment 2A
Meta-xylene, acetic acid, water, cobalt acetate, manganese acetate, hydrobromic acid are uniformly mixed according to a certain percentage, then pumped Enter in oxidizing reactor.The temperature of rotating speed of agitator and heating jacket is set when experiment starts, at the same time, by O2、CO2、N2Press Admixture of gas, which is made into, according to certain proportion is introduced into initiated oxidation reaction in reactor.Oxidation reaction condition is that rotating speed of agitator is 800ppm, temperature are 180 DEG C, reaction pressure 2.0MPa, and the reaction time is counted as 90min using the mean residence time of solvent, into The mass ratio for expecting solvent and meta-xylene is 10:1, H2O/HAc=5%, using ionometer catalyst concn Co as 800ppm, Mn is 400ppm, Br 1200ppm, O in admixture of gas2Content is 12.6%, N2Content is 47.4%, CO2Content is 40.0%.Product after once oxidation is pumped into secondary oxidation reactor, adjusts the temperature, pressure and gas stream of reaction Amount.Secondary oxidation reaction condition is that rotating speed of agitator is 300ppm, and temperature is 170 DEG C, reaction pressure 1.5MPa, with solvent The mean residence time meter reaction time is 45min.The material of secondary oxidation is washed, is dissolved with water.Using turning basket Formula reaction kettle, catalyst are platinum carbon catalyst, and rotating speed of agitator 500ppm, temperature is 230 DEG C, reaction pressure 2.1MPa, Reaction time is counted as 30min using the mean residence time of solvent.
Embodiment 3A
Meta-xylene, acetic acid, water, cobalt acetate, manganese acetate, hydrobromic acid are uniformly mixed according to a certain percentage, then pumped Enter in oxidizing reactor.The temperature of rotating speed of agitator and heating jacket is set when experiment starts, at the same time, by O2、CO2、N2Press Admixture of gas, which is made into, according to certain proportion is introduced into initiated oxidation reaction in reactor.Oxidation reaction condition is that rotating speed of agitator is 800ppm, temperature are 180 DEG C, reaction pressure 2.0MPa, and the reaction time is counted as 90min using the mean residence time of solvent, into The mass ratio for expecting solvent and meta-xylene is 10:1, H2O/HAc=5%, using ionometer catalyst concn Co as 800ppm, Mn is 400ppm, Br 1200ppm, O in admixture of gas2Content is 8.4%, N2Content is 31.6%, CO2Content is 60.0%.Product after once oxidation is pumped into secondary oxidation reactor, adjusts the temperature, pressure and gas stream of reaction Amount.Secondary oxidation reaction condition is that rotating speed of agitator is 300ppm, and temperature is 170 DEG C, reaction pressure 1.5MPa, with solvent The mean residence time meter reaction time is 45min.The material of secondary oxidation is washed, is dissolved with water.Using turning basket Formula reaction kettle, catalyst are platinum carbon catalyst, and rotating speed of agitator 500ppm, temperature is 230 DEG C, reaction pressure 2.1MPa, Reaction time is counted as 30min using the mean residence time of solvent.
Embodiment 4A
Meta-xylene, acetic acid, water, cobalt acetate, manganese acetate, hydrobromic acid are uniformly mixed according to a certain percentage, then pumped Enter in oxidizing reactor.The temperature of rotating speed of agitator and heating jacket is set when experiment starts, at the same time, by O2、CO2、N2Press Admixture of gas, which is made into, according to certain proportion is introduced into initiated oxidation reaction in reactor.Oxidation reaction condition is that rotating speed of agitator is 800ppm, temperature are 180 DEG C, reaction pressure 2.0MPa, and the reaction time is counted as 90min using the mean residence time of solvent, into The mass ratio for expecting solvent and meta-xylene is 10:1, H2O/HAc=5%, using ionometer catalyst concn Co as 800ppm, Mn is 400ppm, Br 1200ppm, O in admixture of gas2Content is 4.41%, N2Content is 16.59%, CO2Content is 79.0%.Product after once oxidation is pumped into secondary oxidation reactor, adjusts the temperature, pressure and gas stream of reaction Amount.Secondary oxidation reaction condition is that rotating speed of agitator is 300ppm, and temperature is 170 DEG C, reaction pressure 1.5MPa, with solvent The mean residence time meter reaction time is 45min.The material of secondary oxidation is washed, is dissolved with water.Using turning basket Formula reaction kettle, catalyst are platinum carbon catalyst, and rotating speed of agitator 500ppm, temperature is 230 DEG C, reaction pressure 2.1MPa, Reaction time is counted as 30min using the mean residence time of solvent.
Embodiment 5A
Meta-xylene, acetic acid, water, cobalt acetate, manganese acetate, hydrobromic acid are uniformly mixed according to a certain percentage, then pumped Enter in oxidizing reactor.The temperature of rotating speed of agitator and heating jacket is set when experiment starts, at the same time, by O2、CO2、N2Press Admixture of gas, which is made into, according to certain proportion is introduced into initiated oxidation reaction in reactor.Oxidation reaction condition is that rotating speed of agitator is 800ppm, temperature are 190 DEG C, reaction pressure 2.2MPa, and the reaction time is counted as 90min using the mean residence time of solvent, into The mass ratio for expecting solvent and meta-xylene is 10:1, H2O/HAc=5%, using ionometer catalyst concn Co as 800ppm, Mn is 400ppm, Br 1200ppm, O in admixture of gas2Content is 12.6%, N2Content is 47.4%, CO2Content is 40.0%.Product after once oxidation is pumped into secondary oxidation reactor, adjusts the temperature, pressure and gas stream of reaction Amount.Secondary oxidation reaction condition is that rotating speed of agitator is 300ppm, and temperature is 170 DEG C, reaction pressure 1.5MPa, with solvent The mean residence time meter reaction time is 45min.The material of secondary oxidation is washed, is dissolved with water.Using turning basket Formula reaction kettle, catalyst are platinum carbon catalyst, and rotating speed of agitator 500ppm, temperature is 230 DEG C, reaction pressure 2.1MPa, Reaction time is counted as 30min using the mean residence time of solvent.
Embodiment 6A
Meta-xylene, acetic acid, water, cobalt acetate, manganese acetate, hydrobromic acid are uniformly mixed according to a certain percentage, then pumped Enter in oxidizing reactor.The temperature of rotating speed of agitator and heating jacket is set when experiment starts, at the same time, by O2、CO2、N2Press Admixture of gas, which is made into, according to certain proportion is introduced into initiated oxidation reaction in reactor.Oxidation reaction condition is that rotating speed of agitator is 800ppm, temperature are 200 DEG C, reaction pressure 2.1MPa, and the reaction time is counted as 90min using the mean residence time of solvent, into The mass ratio for expecting solvent and meta-xylene is 10:1, H2O/HAc=5%, using ionometer catalyst concn Co as 800ppm, Mn is 400ppm, Br 1200ppm, O in admixture of gas2Content is 12.6%, N2Content is 47.4%, CO2Content is 40.0%.Product after once oxidation is pumped into secondary oxidation reactor, adjusts the temperature, pressure and gas stream of reaction Amount.Secondary oxidation reaction condition is that rotating speed of agitator is 300ppm, and temperature is 180 DEG C, reaction pressure 1.5MPa, with solvent The mean residence time meter reaction time is 45min.The material of secondary oxidation is washed, is dissolved with water.Using turning basket Formula reaction kettle, catalyst are platinum carbon catalyst, and rotating speed of agitator 500ppm, temperature is 220 DEG C, reaction pressure 2.3MPa, Reaction time is counted as 45min using the mean residence time of solvent.
Embodiment 1B~embodiment 6B
Embodiment 1B is to add catalytic additive on the basis of embodiment 1A, its species is Ce (Ac)3, content is 300ppm, remaining raw material and preparation process condition are the same as embodiment 1A in meta-xylene oxidation system.
Embodiment 2B is to add catalytic additive on the basis of embodiment 2A, its species is La (Ac)3, content is 200ppm, remaining raw material and preparation process condition are the same as embodiment 2A in meta-xylene oxidation system.
Embodiment 3B is to add catalytic additive on the basis of embodiment 3A, its species is Dy (Ac)6, content is 200ppm, remaining raw material and preparation process condition are the same as embodiment 3A in meta-xylene oxidation system.
Embodiment 4B is to add catalytic additive on the basis of embodiment 4A, its species is Hf (Ac)4, content is 200ppm, remaining raw material and preparation process condition are the same as embodiment 4A in meta-xylene oxidation system.
Embodiment 5B is to add catalytic additive on the basis of embodiment 5A, its species is NaAc, and content is 250ppm, remaining raw material and preparation process condition are the same as embodiment 5A in meta-xylene oxidation system.
Embodiment 6B is to add catalytic additive on the basis of embodiment 6A, its species is KAc, and content is 250ppm, remaining raw material and preparation process condition are the same as embodiment 6A in meta-xylene oxidation system.
The once oxidation reaction effect contrast of embodiment 1~6 is as shown in table 1：
The experimental data of 1 embodiment 1~6 of table
Remarks：3-CBA, yield, CO in table 12、CO、O2It is the result measured for oxidation end for the first time.
Can be seen that the application according to 1 result of table and can control 3-CBA (ppm) content is 500-3000ppm, and IPA is received At least more than 95%, CO tail gas point rate can be controlled 0.4%~10% rate.
Further, since CO in tail gas2Divide CO in rate and oxidant with CO2There is the relation of interwoveness with the content of CO, because This, the application uses O in tail gas2Point rate evaluate the quality of the inhibition of burning reaction, safe range (6% with Under) in, O2Divide rate higher, illustrate burning reaction produce CO2It is lower with CO contents, the suppression effect for burning reaction Fruit is better.

Claims (10)

1. a kind of preparation method of M-phthalic acid, it is characterised in that the preparation method includes the following steps：In meta-xylene In oxidation system, meta-xylene reacts to obtain M-phthalic acid through once oxidation；The meta-xylene oxidation system includes catalysis Agent, oxidant and solvent, the catalyst are Co-Mn-Br catalyst, and the oxidant contains 5~21% O2, 0.04%~ 79% CO2, and N2, the percentage is percent by volume；At the end of the once oxidation, oxygen partial pressure is in tail gas 1.21%~6%.
2. preparation method as claimed in claim 1, it is characterised in that the M-phthalic acid prepared by above-mentioned preparation method also passes through After crossing secondary oxidation and hydrofinishing, then M-phthalic acid that is filtered, washing, be dried to obtain after refining；Wherein it is preferred that institute It is identical to state the oxidation system of secondary oxidation, the oxidation system of process conditions and the once oxidation, process conditions；The hydrogenation essence The condition of system is preferably：Being carried out turning basket formula reaction kettle, catalyst be platinum carbon catalyst, the rotating speed of agitating paddle is 500~ 1000ppm, temperature be 180-270 DEG C, reaction pressure 0.8-3.0MPa, in terms of the mean residence time of solvent the reaction time be 30~90min.
3. preparation method as claimed in claim 1, it is characterised in that the oxidant is air and CO2Mixture；Air And CO2Volume ratio be preferably 0.1~9, be more preferably 0.1~2.
4. preparation method as claimed in claim 3, it is characterised in that N in the oxidant2Content be 0.78%~78%； Also contain CO in the oxidant, the content of CO is preferably 0.0002%~0.002%.
5. preparation method as claimed in claim 1, it is characterised in that also add in the meta-xylene oxidation system containing catalysis Add agent；
Wherein, the catalytic additive is preferably comprised rare earth metal acetate, alkali metal acetate and transition metal acetate In one or more, addition of the catalytic additive in meta-xylene oxidation system is 50~1500ppm.
6. preparation method as claimed in claim 5, it is characterised in that the rare earth metal acetate include Ce, Nd, Pr, The acetate of one or more rare earth metals in Gd, Dy, Sm and La；
And/or the alkali metal acetate includes the acetate of one or more alkali metal in Li, Na, K, Rb, Cs and Fr；
And/or the transition metal acetate includes the acetate of one or more transition metal in Hf, Zr, Fe and Mo.
7. preparation method as claimed in claim 5, it is characterised in that the catalytic additive is in meta-xylene oxidation system Addition be 100~300ppm.
8. preparation method as claimed in claim 5, it is characterised in that the rare earth metal acetate is in meta-xylene oxysome Addition in system is 50ppm~500ppm；
And/or addition of the alkali metal acetate in meta-xylene oxidation system is 50ppm~500ppm；
And/or addition of the transition metal acetate in meta-xylene oxidation system is 50ppm~500ppm；With mistake Cross the addition gauge of metal ion, its content preferably 20~350ppm.
9. preparation method as claimed in claim 1, it is characterised in that the catalyst is cobalt acetate, manganese acetate and bromination The mixture of sodium or hydrobromic acid, wherein, cobalt acetate, manganese acetate, the Co ion concentrations of sodium bromide or hydrobromic acid, Mn ion concentrations, Br ion concentration ranges are preferably 200~1000ppm, 200~1000ppm, 200~1600ppm；
And/or the catalyst and catalytic additive are first uniformly mixed before reactions.
10. preparation method as claimed in claim 1, it is characterised in that in meta-xylene oxidation system, the solvent for water with The liquid of acetic acid composition；Wherein, the content of water in the reaction system is preferably 3%~12%；Solvent ratio ((HAc+H2O)/ MX 1~20) is preferably, is more preferably 3~20；
The rotating speed of the reaction is 500~1000rpm, preferably 400~800ppm；The temperature of the reaction is 150~240 DEG C, preferably 150-190 DEG C；The pressure of the reaction is 0.45~2.5MPa, preferably 0.45-2.0MPa；It is described anti- The time answered is 30~120min, preferably 30~60min.
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US5132450A (en) * 1990-06-25 1992-07-21 Mitsubishi Gas Chemical Company, Inc. Process for producing high purity isophthalic acid
US5359133A (en) * 1993-09-28 1994-10-25 Joint-Stock Company Of Research And Design Institute Of Monomers (Ao Nipim) Process for producing highly purified benzenedicarboxylic acid isomers
CN1333743A (en) * 1998-12-22 2002-01-30 三星综合化学株式会社 Production method of aromatic carboxylic acids
CN1512976A (en) * 2001-06-04 2004-07-14 �Ϻ���ͨ��ѧ Two stage oxidation process for production of aromatic dicarboxylic acids
CN1958552A (en) * 2006-08-18 2007-05-09 中国石油化工股份有限公司 Method for producing aromatic carboxylic acid
CN101161625A (en) * 2006-10-12 2008-04-16 高化环保技术有限公司 Process for the reduction of sulfur, nitrogen and the production of useful oxygenates from hydrocarbon materials via one-pot selective oxidation
CN101279904A (en) * 2007-04-03 2008-10-08 波克股份有限公司 Improved method for preparing aromatic carboxyl acid
CN102584572A (en) * 2012-01-18 2012-07-18 逸盛大化石化有限公司 Production method of mixed fragrant dioctyl phthalate

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5132450A (en) * 1990-06-25 1992-07-21 Mitsubishi Gas Chemical Company, Inc. Process for producing high purity isophthalic acid
US5359133A (en) * 1993-09-28 1994-10-25 Joint-Stock Company Of Research And Design Institute Of Monomers (Ao Nipim) Process for producing highly purified benzenedicarboxylic acid isomers
CN1333743A (en) * 1998-12-22 2002-01-30 三星综合化学株式会社 Production method of aromatic carboxylic acids
CN1512976A (en) * 2001-06-04 2004-07-14 �Ϻ���ͨ��ѧ Two stage oxidation process for production of aromatic dicarboxylic acids
CN1958552A (en) * 2006-08-18 2007-05-09 中国石油化工股份有限公司 Method for producing aromatic carboxylic acid
CN101161625A (en) * 2006-10-12 2008-04-16 高化环保技术有限公司 Process for the reduction of sulfur, nitrogen and the production of useful oxygenates from hydrocarbon materials via one-pot selective oxidation
CN101279904A (en) * 2007-04-03 2008-10-08 波克股份有限公司 Improved method for preparing aromatic carboxyl acid
CN102584572A (en) * 2012-01-18 2012-07-18 逸盛大化石化有限公司 Production method of mixed fragrant dioctyl phthalate

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