CN107954850A - The preparation method of M-phthalic acid - Google Patents
The preparation method of M-phthalic acid Download PDFInfo
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- CN107954850A CN107954850A CN201711066086.8A CN201711066086A CN107954850A CN 107954850 A CN107954850 A CN 107954850A CN 201711066086 A CN201711066086 A CN 201711066086A CN 107954850 A CN107954850 A CN 107954850A
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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
Abstract
The invention discloses a kind of preparation method of M-phthalic acid, the preparation method includes the following steps：Under catalyst and catalytic additive effect, meta-xylene is aoxidized in a solvent, reacts to obtain M-phthalic acid；The catalyst is Co Mn Br catalyst, and the catalytic additive includes the one or more in rare earth metal acetate, alkali metal acetate and transition metal acetate, and addition of the catalytic additive in meta-xylene oxidation system is 50~1500ppm.Carboxyl benzaldehyde content is low between the preparation method of the present invention has, the effect that manganese precipitation, bromine oxidation, equipment corrosion phenomenon weaken.
Description
Technical field
The present invention relates to a kind of preparation method of M-phthalic acid.
Background technology
M-phthalic acid (Iso-phthalic Acid, IPA) is a kind of faster organic chemical industry's intermediate feed of development,
The modified monomer of PET resin is mainly used as, to improve the processing of PET resin and product properties；It is high-strength for replacing phthalic anhydride to produce
Spend unsaturated-resin resistant to chemical etching；Instead of the alkyd resin of phthalic anhydride production high-performance high solids content.IPA has been obtained abroad
It is widely applied, development prospect is had an optimistic view of, and many major companies are prepared for expanding production capacity and create IPA devices.With device
The continuous expansion of scale, its cost will be reduced constantly, and application field and the market share will constantly expand.The application of China IPA is
There is certain basis, at present in bottle grade PET resin and the high-grade painting of polyester cation-dyeable fiber, unsaturated-resin, alkyd resin
Material field has all been applied, but its source is mainly solved by import.As external many major company's sophistications expand life
Production capacity power and newly-built IPA devices, the competitiveness of these devices there will be it is larger the problem of.
MX high-temperature S removal processes use Co-Mn-Br three-component compound systems as catalyst, its catalytic mechanism pertinent literature
There is detailed description.Co is the major catalyst in MX oxidizing process, and in all transition metal, Co is to MX air oxidation processes
Catalytic activity it is maximum；Mn is co-catalyst, and oxidations of the Mn as Co to MX has catalytic action, the catalysis that Mn is used alone
Effect is far away from Co, but Mn can produce synergistic effect with Co, and the catalytic activity after both combine is much larger than simple Co or Mn
Catalysis；Bromine is good radical reaction accelerating agent, and quickly electricity can occur between Co (III), the Mn (III) of high-valence state
Son transfer generation bromine free radical, so as to accelerate to react.
It is anti-with the generation of catalyst Mn deposited phenomenons, this precipitation during MX high-temperature S removals prepare IPA
The content of not only spent catalyst Mn is answered, reduces reaction rate, and influence the color and luster of product.In the aerobic environment of high temperature,
With the generation of catalyst Br oxidative phenomenas, the content of this oxidation reaction spent catalyst Br, reduces oxidizing reaction rate.Cause
This, adds the 4th kind of metal or nonmetallic compound as catalytic additive to improve in original Co-Mn-Br catalyst system and catalyzings
The catalytic performance of system, technological transformation and expanding production for IPA devices seem particularly significant.
Above-mentioned the 4th kind of metal or the nonmetallic compound of being added in original Co-Mn-Br catalyst system and catalyzings is added as catalysis
The method of agent, or reaction can be accelerated and reduce side reaction, but carboxyl between cannot being all effectively reduced in coarse isophthalic acid
The content of benzaldehyde (3-CBA).Usually, the too high levels of 3-CBA will cause product color poor in coarse isophthalic acid,
Need further hydrofinishing.Therefore, to the optimization of the catalyst of MX oxidation reaction systems, catalytic additive, acetic acid, water content
Adjusting is very important.
The content of the invention
The technical problems to be solved by the invention are to overcome the thick of meta-xylene oxidation production existing in the prior art
The problems such as carboxyl benzaldehyde too high levels, burning reaction are serious among M-phthalic acid, manganese precipitates, bromine aoxidizes, equipment corrosion,
And provide a kind of preparation method of M-phthalic acid.The preparation method of the present invention has the thick isophthalic of meta-xylene oxidation production
The characteristics of carboxyl benzaldehyde content is low among dioctyl phthalate, and manganese precipitation, bromine oxidation, equipment corrosion phenomenon weaken.
The present invention provides a kind of preparation method of M-phthalic acid, the preparation method includes the following steps：It is being catalyzed
Under agent and catalytic additive effect, meta-xylene is aoxidized in a solvent, reacts to obtain M-phthalic acid；The catalyst is Co-Mn-
Br catalyst, the catalytic additive include one in rare earth metal acetate, alkali metal acetate and transition metal acetate
Kind is a variety of, and addition of the catalytic additive in meta-xylene oxidation system is 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.
Inventor is shown experimentally that：Zr, Hf, K, Na, Ce etc. are respectively provided with acceleration to oxidation, but Zr easily sinks
Form sediment, remaining Zr can make the catalyst poisoning that follow-up hydrogenation refines in thick IPA.And Ce etc. has the function that to prevent that manganese from precipitating, from
Commercial viability considers that Zr is unsuitable for large-scale industrial application.Therefore, rare earth metal acetate, alkali metal acetate should
Pay the utmost attention to, transition metal acetate can only aid in using, using rare earth metal acetate, alkali metal acetate etc., or with mistake
Cross metal acetate salt to be applied in combination, reduce deposited phenomenon, and can accelerated oxidation reaction.
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, considered with effect data global index, the catalytic additive is preferably rare earth metal acetic acid
Salt and/or alkali metal acetate, are more preferably La (Ac)3, NaAc and Dy (Ac)6With mass ratio 2:1:1 mixture formed.It is single
From the inhibition for burning reaction, there are following preference relation：Dy(Ac)6＞ La (Ac)3＞ Ce (Ac)3；Hf
(Ac)4＞ Ce (Ac)3；NaAc ＞ Ce (Ac)3。
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, in the catalyst, cobalt acetate, manganese acetate, the Co ions of sodium bromide, Mn ions, Br ions are dense
Degree scope is this area normal ranges, respectively preferably 100~2000ppm, 100~2000ppm, 100~2000ppm.
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, oxidant is generally air, and the solvent is this area Conventional solvents, preferably
The liquid of water and acetic acid composition.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) it is preferably 3~20.
In the present invention, the temperature of the reaction is conventional for this area, preferably 150~250 DEG C；The pressure of the reaction
It is conventional for this area, preferably 0.5~2.5MPa.The time of the reaction is conventional for this area, preferably 20~
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：The catalytic additive that the present invention especially selects effectively improves meta-xylene
The reaction effect of the M-phthalic acid of production is aoxidized, can be applied in the industrial production of M-phthalic acid.And the system of the present invention
Preparation Method has carboxyl benzaldehyde content among the coarse isophthalic acid of meta-xylene oxidation production low, and manganese precipitation, bromine oxidation, set
The characteristics of standby corrosion phenomenon weakens.
Brief description of the drawings
Fig. 1 is the liquid chromatogram that the embodiment of the present application measures.
Fig. 2 is CO in embodiment 12, CO generating rates fitting schematic diagram.
Fig. 3 is CO in embodiment 22, CO generating rates fitting schematic diagram.
Fig. 4 is CO in embodiment 32, CO generating rates fitting schematic diagram.
Fig. 5 is CO in embodiment 42, CO generating rates fitting schematic diagram.
Fig. 6 is CO in embodiment 52, CO generating rates fitting schematic diagram.
Fig. 7 is CO in embodiment 62, CO generating rates fitting schematic diagram.
Fig. 8 is CO in embodiment 72, CO generating rates fitting schematic diagram.
Fig. 9 is CO in embodiment 82, CO generating rates fitting schematic diagram.
Figure 10 is CO in embodiment 92, CO generating rates fitting schematic diagram.
Figure 11 is that CO generating rates are fitted contrast schematic diagram in embodiment 10.
Figure 12 is CO in embodiment 102Generating rate is fitted contrast schematic diagram.
Figure 13 is the reaction process schematic diagram of embodiment 6.
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 instrument and test condition of efficient liquid phase chromatographic analysis：
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, flowing
Phase B is+83% water of 17% methanol；Condition of gradient elution：A is from 30% to 100% during 0~20min, during 20~25min B from
B is from 70% to 0% when 100% to 30%, 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 left for 5.3min under the conditions of this
The right side, the retention time of a carboxyl benzaldehyde main peak is 6.5min or so, and the retention time of m-methyl benzoic acid main peak is 9.5min
Left and right, the retention time of a tolyl aldehyde main peak is 11.4min or so, and the retention time of meta-xylene main peak is 16.8min
Left and right, specifically see Fig. 1.Wherein, peak 1- M-phthalic acids, carboxyl benzaldehyde between peak 2-, peak 3- benzoic acid, methyl between peak 4-
Benzoic acid, tolyl aldehyde between peak 5-, peak 6- meta-xylenes.
For Fig. 1, 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.
In following embodiments, suitable experiment condition is chosen as base condition, rare earth metal is added under base condition
Class, alkali metal class, transition metal-type catalytic additive, obtained CO2With the CO under CO formation curves and base condition2It is bent with CO
Line compares, and judges influence of the catalytic additive to combustion reaction by reacting the end time, passes through 3-CBA in reaction product
Content judges influence of the catalytic additive to main reaction, thereby confirms that the effect of catalytic additive.
The material condition used in following embodiments is all MX:HAc=1:3, H2O/HAc=5%, convert to obtain solvent ratio
((HAc+H2O)/MX) it is 3.15, in addition, the content of water in the reaction system is specially 3.61%, the percentage is quality
Percentage.
From mechanism, burning reaction is that MX and acetic acid generate CO by oxidation2With the process of CO, in experiment mainly with
Reaction time, (in 15min) was to CO2Generating rate is quadratured, and obtaining acetic acid combustion equivalent, (approximation is made of the area below curve
Compare), inhibition is evaluated with this.If combustion equivalent is approximate, evaluation criterion is used as using the generating rate at the end of reaction.
In the application, due to the addition of the species of each catalytic additive so that oxidation rate speed is different, causes at the end,
Different catalyst system and catalyzing degree of oxidation is different.Therefore, some is also in rising trend in 15min, and some then tends towards stability.
Embodiment 1
Weigh 1.5g Ce2O3, first it is allowed to be completely dissolved with a small amount of acetic acid, then all move into 250ml volumetric flasks, at 20 DEG C
It is lower to be settled to graduation mark with acetic acid, the corresponding Acetate Solution of the oxide can be obtained.According to following catalyst, reactant,
Solvent burden ratio prepares MX oxidation systems：Catalytic additive Ce (Ac)3For 300ppm, MX:HAc=1:3, Co additive amounts are
350ppm, Co:Mn:Br=1:1:1, H2O/HAc=5%, air inflow 10L/min.It it is 191 DEG C in temperature, pressure is
Under the conditions of 1.3MPa, MX oxidations 20min obtains thick IPA.Even if the reaction time reaches 60 minutes, still so that IPA product colours
White is remained, and working as in system does not have Ce3+In the presence of, even if there are micro Br in system-, black is still presented in product.It is real
Verify that the bright Ce that added in Co-Mn-Br catalyst system and catalyzings can play suppression MnO really2The effect of precipitation.By high-efficient liquid phase color
Spectrum analysis product understands that the yield of IPA reaches 96.5%, and 3-CBA contents are 491ppm in thick IPA.Pass through infrared gas analysis
CO in instrument analysis tail gas2(specific as shown in Figure 2), the repressed situation of burning reaction are can be seen that with CO change curves.
Embodiment 2
Weigh 1.0g La2O3, first it is allowed to be completely dissolved with a small amount of acetic acid, then all move into 250ml volumetric flasks, at 20 DEG C
It is lower to be settled to graduation mark with acetic acid, the corresponding Acetate Solution of the oxide can be obtained.According to following catalyst, reactant,
Solvent burden ratio prepares MX oxidation systems：Catalytic additive La (Ac)3For 200ppm, MX:HAc=1:3, Co additive amounts are
350ppm, Co:Mn:Br=1:1:1, H2O/HAc=5%, air inflow 10L/min.It it is 191 DEG C in temperature, pressure is
Under the conditions of 1.3MPa, MX oxidations 20min obtains thick IPA.Understand that the yield of IPA reaches by efficient liquid phase chromatographic analysis product
3-CBA contents are 500ppm in 97%, thick IPA.CO in tail gas is analyzed by infrared gas analyser2Can with CO change curves
Know, compared with Fig. 2 that embodiment 1 obtains, the burning reaction of the present embodiment is inhibited by a certain extent, specifically such as Fig. 3 institutes
Show.
Embodiment 3
Catalytic additive La (Ac) is prepared according to above-described embodiment 13, it is uniformly mixed with Co-Mn-Br catalyst, is added
Enter MX oxidation systems.MX oxidation systems are prepared according to following catalyst, reactant, solvent burden ratio：Catalytic additive La (Ac)3
For 200ppm, MX:HAc=1:3, Co additive amounts are 350 ppm, Co:Mn:Br=1:1:1, H2O/HAc=5%, air inflow are
10L/min.It it is 210 DEG C in temperature, under the conditions of pressure is 1.3MPa, MX oxidations 25min obtains thick IPA.By high-efficient liquid phase color
Spectrum analysis product understands that the yield of IPA reaches 98.1%, and 3-CBA contents are 300ppm in thick IPA.Pass through infrared gas analysis
CO in instrument analysis tail gas2Understood with CO change curves, it is specific as shown in Figure 4.Combustion equivalent is significantly lower than Fig. 2 in Fig. 4, i.e., originally
The burning reaction of embodiment is more preferable than 1 inhibition of embodiment.
Embodiment 4
The DyO of precise 1.0g3, 10ml distilled water is added, the carbonic acid of 1M is added dropwise while stirring on magnetic stirring apparatus
Amine aqueous solution, to make rare earth metal be completely reformed into carbonate deposition, amine carbonate is slightly excessive (with solution PH>Subject to 10), then
Filtration washing precipitates 3~5 times, is precipitated to obtain rare earth acetate solutions with acetate dissolution after precipitation drying, solution is crystallized,
It just can obtain lanthanon acetate.MX oxidation systems are prepared according to following catalyst, reactant, solvent burden ratio：Catalytic additive Dy
(Ac)6200 ppm, MX:HAc=1:3, Co additive amounts are 350ppm, Co:Mn:Br=1:1:1, H2O/HAc=5%, air inflow
For 10L/min.It it is 191 DEG C in temperature, under the conditions of pressure is 1.3MPa, MX oxidations 42min obtains thick IPA.By efficient liquid phase
Chromatography product understands that the yield of IPA reaches 97.1%, and 3-CBA contents are 450ppm in thick IPA.Pass through infrared-gas point
CO in analyzer analysis tail gas2Understood with CO change curves, compared with Fig. 2 that embodiment 1 obtains, the burning pair of the present embodiment
Reaction is inhibited by a certain extent, specific as shown in Figure 5.
Embodiment 5
Catalytic additive Dy (Ac) is prepared according to above-described embodiment 46, it is uniformly mixed with Co-Mn-Br catalyst, is added
Enter MX oxidation systems.MX oxidation systems are prepared according to following catalyst, reactant, solvent burden ratio：Catalytic additive Dy (Ac)6
For 200ppm, MX:HAc=1:3, Co additive amounts are 350ppm, Co:Mn:Br=1:1:1, H2O/HAc=5%, air inflow are
10L/min.It it is 200 DEG C in temperature, under the conditions of pressure is 1.3MPa, MX oxidations 25min obtains thick IPA.By high-efficient liquid phase color
Spectrum analysis product understands that the yield of IPA reaches 97.6%, and 3-CBA contents are 365 ppm in thick IPA.Pass through infrared gas analysis
CO in instrument analysis tail gas2Understood with CO change curves, specifically as shown in fig. 6, the combustion equivalent of Fig. 6 is significantly lower than Fig. 4, reaction
At the end of generating rate be also significantly lower than Fig. 4.Illustrate that burning reaction is more preferable than 3 inhibition of embodiment in the present embodiment.
Embodiment 6
With HfOCl2For raw material, Hf (Ac) is prepared using the precipitation method4, idiographic flow is as shown in figure 13.
MX oxidation systems are prepared according to following catalyst, reactant, solvent burden ratio：Catalytic additive is Hf (Ac)4
200ppm, MX:HAc=1:3, Co additive amounts are 350ppm, Co:Mn:Br=1:1:1, H2O/HAc=5%, air inflow are
10L/min.It it is 191 DEG C in temperature, under the conditions of pressure is 1.3MPa, MX oxidations 42min obtains thick IPA.By high-efficient liquid phase color
Spectrum analysis product understands that the yield of IPA reaches 96.5%, and 3-CBA contents are 600ppm in thick IPA.Pass through infrared gas analysis
CO in instrument analysis tail gas2Understood with CO change curves, compared with Fig. 2 that embodiment 1 obtains, the burning reaction of the present embodiment
It is inhibited by a certain extent, it is specific as shown in Figure 7.
Embodiment 7
Catalytic additive NaAc is prepared according to above-described embodiment 1, it is uniformly mixed with Co-Mn-Br catalyst, adds MX
Oxidation system.MX oxidation systems are prepared according to following catalyst, reactant, solvent burden ratio：Catalytic additive NaAc is
250ppm, MX:HAc=1:3, Co additive amounts are 350ppm, Co:Mn:Br=1:1:1, H2O/HAc=5%, air inflow are
10L/min.It it is 200 DEG C in temperature, under the conditions of pressure is 1.3MPa, MX oxidations 25min obtains thick IPA.By high-efficient liquid phase color
Spectrum analysis product understands that the yield of IPA reaches 98.1%, and 3-CBA contents are 343ppm in thick IPA.Pass through infrared gas analysis
CO in instrument analysis tail gas2Understood with CO change curves, specifically as shown in figure 8, the combustion equivalent of Fig. 8 is significantly lower than Fig. 2, explanation
Burning reaction is more preferable than 1 inhibition of embodiment.
Embodiment 8
Catalytic additive NaAc is prepared according to above-described embodiment 1, it is uniformly mixed with Co-Mn-Br catalyst, adds MX
Oxidation system.MX oxidation systems are prepared according to following catalyst, reactant, solvent burden ratio：Catalytic additive NaAc is
250ppm, MX:HAc=1:3, Co additive amounts are 350ppm, Co:Mn:Br=1:1:1, H2O/HAc=5%, air inflow are
10L/min.It it is 220 DEG C in temperature, under the conditions of pressure is 1.3MPa, MX oxidations 25min obtains thick IPA.By high-efficient liquid phase color
Spectrum analysis product understands that the yield of IPA reaches 98.5%, and 3-CBA contents are 303ppm in thick IPA.Pass through infrared gas analysis
CO in instrument analysis tail gas2Understood with CO change curves, specifically as shown in figure 9, combustion equivalent is significantly lower than Fig. 2, Fig. 9 in Fig. 9
Generating rate at the end of reaction is also significantly lower than Fig. 2.Illustrate the burning reaction of the present embodiment than 1 inhibition of embodiment more
It is good.
Embodiment 9
Catalytic additive La (Ac) is prepared according to above-described embodiment 13、NaAc、Dy(Ac)6, itself and Co-Mn-Br are catalyzed
Agent is uniformly mixed, and adds MX oxidation systems.MX oxidation systems are prepared according to following catalyst, reactant, solvent burden ratio：Catalysis adds
Add agent La (Ac)3、NaAc、Dy(Ac)6Respectively 100ppm, 50ppm, 50ppm, MX:HAc=1:3, Co additive amounts are
350ppm, Co:Mn:Br=1:1:1, H2O/HAc=5%, air inflow 10L/min.It it is 220 DEG C in temperature, pressure is
Under the conditions of 1.3MPa, MX oxidations 25min obtains thick IPA.Understand that the yield of IPA reaches by efficient liquid phase chromatographic analysis product
3-CBA contents are 251ppm in 99.1%, thick IPA.CO in tail gas is analyzed by infrared gas analyser2With CO change curves
Understand, burning reaction is more preferable than 1 inhibition of embodiment, specific as shown in Figure 10, reaches optimum reaction condition.Pass through contrast
It was found that on this condition, combustion equivalent is not high, but product yield has reached highest.Therefore, it is relatively low in combustible loss
In the case of, it ensure that very high yield and purity, therefore can consider that condition at this time is optimum reaction condition.
Embodiment 10
The acetate of Zr, Na, Hf, Dy is prepared respectively as catalytic additive according to above-described embodiment 1, by itself and Co-Mn-
Br catalyst is uniformly mixed, and adds MX oxidation systems.MX oxidation systems are prepared according to following catalyst, reactant, solvent burden ratio：
The acetate of catalytic additive Zr, Na, Hf, Dy all add 100ppm, MX:HAc=1:3, Co additive amounts are 350ppm, Co:Mn:
Br=1:1:1, H2O/HAc=5%, air inflow 10L/min.It is 220 DEG C in temperature, under the conditions of pressure is 1.3MPa, MX oxygen
Change 25min and obtain thick IPA.Understood by efficient liquid phase chromatographic analysis product, under conditions of above-mentioned four kinds of catalytic additives,
The yield of IPA has respectively reached 97.8%, 98.1%, 97.9%, 98.3%, in thick IPA 3-CBA contents be respectively 381ppm,
365ppm、375ppm、355ppm.CO in tail gas is analyzed by infrared gas analyser2Understood with CO change curves, the vinegar of Zr
When hydrochlorate is as catalytic additive, burning reaction is the most serious, specifically as shown in Figure 11,12.From Figure 11,12, by Zr
Acetate as catalytic additive when, the generating rate at the end of the combustion equivalent of acetic acid and reaction is the largest, and is fired at this time
It is the most serious to burn side reaction.That is, it is single from the inhibition for burning reaction, the acetate of several elements
Preference relation is as follows：Dy ＞ Hf ＞ Na ＞ Zr.
Embodiment 11
In the present embodiment, the catalytic additive species added is LiAc, its content, remaining raw material type, content and
Process conditions are the same as embodiment 7.The embodiment can realize that 3-CBA contains in the IPA yield values suitable with embodiment 7 and thick IPA
Value, and the effect of suitable suppression burning reaction.
Embodiment 12
In the present embodiment, the catalytic additive species added is KAc, its content, remaining raw material type, content and work
Skill condition is the same as embodiment 7.The embodiment can realize 3-CBA contents in the IPA yield values suitable with embodiment 7 and thick IPA
Value, and the effect of suitable suppression burning reaction.
Embodiment 13
In the present embodiment, the catalytic additive species added is RbAc, its content, remaining raw material type, content and
Process conditions are the same as embodiment 7.The embodiment can realize that 3-CBA contains in the IPA yield values suitable with embodiment 7 and thick IPA
Value, and the effect of suitable suppression burning reaction.
Embodiment 14
In the present embodiment, the catalytic additive species added is CsAc, its content, remaining raw material type, content and
Process conditions are the same as embodiment 7.The embodiment can realize that 3-CBA contains in the IPA yield values suitable with embodiment 7 and thick IPA
Value, and the effect of suitable suppression burning reaction.
Embodiment 15
In the present embodiment, the catalytic additive species added is FrAc, its content, remaining raw material type, content and
Process conditions are the same as embodiment 7.The embodiment can realize that 3-CBA contains in the IPA yield values suitable with embodiment 7 and thick IPA
Value, and the effect of suitable suppression burning reaction.
Embodiment 16
In the present embodiment, the catalytic additive species added is Nd (Ac)3, its content, remaining raw material type, content with
And process conditions are the same as embodiment 1.The embodiment can realize 3-CBA in the IPA yield values suitable with embodiment 1 and thick IPA
Content value, and the effect of suitable suppression burning reaction.
Embodiment 17
In the present embodiment, the catalytic additive species added is Pr (C2H3O2)3·4H2O, its content, remaining raw material kind
Class, content and process conditions are the same as embodiment 1.The embodiment can realize the IPA yield value suitable with embodiment 1 and thick
3-CBA content values in IPA, and the effect of suitable suppression burning reaction.
Embodiment 18
In the present embodiment, the catalytic additive species added is Gd (C2H3O2)3·4H2O, its content, remaining raw material kind
Class, content and process conditions are the same as embodiment 1.The embodiment can realize the IPA yield value suitable with embodiment 1 and thick
3-CBA content values in IPA, and the effect of suitable suppression burning reaction.
Embodiment 19
In the present embodiment, the catalytic additive species added is Sm (C2H3O2)3·4H2O, its content, remaining raw material kind
Class, content and process conditions are the same as embodiment 1.The embodiment can realize the IPA yield value suitable with embodiment 1 and thick
3-CBA content values in IPA, and the effect of suitable suppression burning reaction.
Embodiment 20
In the present embodiment, the catalytic additive species added is Fe (Ac)3, its content, remaining raw material type, content with
And process conditions are the same as embodiment 6.The embodiment can realize 3-CBA in the IPA yield values suitable with embodiment 6 and thick IPA
Content value, and the effect of suitable suppression burning reaction.
Embodiment 21
In the present embodiment, the catalytic additive species added is Mo2(Ac)4, its content, remaining raw material type, content with
And process conditions are the same as embodiment 6.The embodiment can realize 3-CBA in the IPA yield values suitable with embodiment 6 and thick IPA
Content value, and the effect of suitable suppression burning reaction.
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 catalyst and
Under catalytic additive effect, meta-xylene is aoxidized in a solvent, reacts to obtain M-phthalic acid；The catalyst is urged for Co-Mn-Br
Agent, the catalytic additive include rare earth metal acetate, alkali metal acetate and one kind in transition metal acetate or
A variety of, addition of the catalytic additive in meta-xylene oxidation system is 50~1500ppm.
2. preparation method as claimed in claim 1, 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.
3. preparation method as claimed in claim 1, it is characterised in that the catalytic additive is in meta-xylene oxidation system
Addition be 100~300ppm.
4. preparation method as claimed in claim 1, it is characterised in that the catalytic additive for rare earth metal acetate and/
Or alkali metal acetate.
5. preparation method as claimed in claim 4, it is characterised in that the catalytic additive is La (Ac)3, NaAc and Dy
(Ac)6With mass ratio 2:1:1 mixture formed.
6. preparation method as claimed in claim 1, 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.
7. preparation method as claimed in claim 6, it is characterised in that the rare earth metal acetate is in meta-xylene oxysome
Addition in system is 200~300ppm；
And/or addition of the alkali metal acetate in meta-xylene oxidation system is 200~300ppm；
And/or addition of the transition metal acetate in meta-xylene oxidation system is 200~300ppm.
8. preparation method as claimed in claim 1, it is characterised in that the addition of the transition metal acetate is with transition gold
Belong to the addition gauge of ion, be 20~350ppm.
9. preparation method as claimed in claim 1, it is characterised in that in the catalyst, cobalt acetate, manganese acetate, bromination
Co ions, Mn ions, the Br ion concentration ranges of sodium are respectively 100~2000ppm, 100~2000ppm, 100~2000ppm；
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, oxidant is air,
The liquid that the solvent forms for water with acetic acid；Wherein, the content of water in the reaction system is 3%~12%；Solvent ratio (HAc+
H2O)/MX is 3~20；
And/or the temperature of the reaction is 150~250 DEG C；The pressure of the reaction is 0.5~2.5MPa；The reaction when
Between be 20~60min.
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Citations (6)
| 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 |
| CN1334792A (en) * | 1999-04-28 | 2002-02-06 | 三星综合化学株式会社 | Method for production of aromatic carboxylic 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 |
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2017
- 2017-11-02 CN CN201711066086.8A patent/CN107954850A/en active Pending
Patent Citations (6)
| 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 |
| CN1334792A (en) * | 1999-04-28 | 2002-02-06 | 三星综合化学株式会社 | Method for production of aromatic carboxylic 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 |
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