CN1865214A - Method for producing aromatic carboxylic acid using nitrogen oxide as catalytic additive - Google Patents
Method for producing aromatic carboxylic acid using nitrogen oxide as catalytic additive Download PDFInfo
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Abstract
This invention provides a method for producing aromatic carboxylic acids with oxynitrides as catalytic additive, which is realized by adding a small amount of oxynitrides with specific structures to the current MC-type liquid catalytic system. Compared to the conventional MC type catalytic oxidation process, the adding of oxynitrides with specific structures significantly accelerates the oxidation reaction of the methyl aromatic hydrocarbons, stimulating the process of transforming methyl aromatic hydrocarbons to aromatic carboxylic acids. The adding of oxynitrides with specific structures can also improve the selectivity of the reaction process, and decrease combustion side reaction. Besides, it can moderately decrease the bromine concentration in the system, thus decrease the etching of the reaction system to the apparatus and the bromine-containing toxic gas discharging.
Description
Technical field
The invention discloses a kind of methylarenes liquid phase catalytic oxidation that is used for and produce improving one's methods of aromatic carboxylic acid.
Background technology
Since the methylarenes liquid phase catalytic oxidation was produced MC method (US2245528) appearance of aromatic carboxylic acid, this method was extensive use of industrial.The catalyzer that this method adopts is cobalt-manganese-bromine three-component compound system, and the solvent of employing is the aliphatic carboxylic acid (adopting acetic acid usually) of C1～C6, and temperature of reaction is 100～320 ℃, keeps reaction pressure to make the aliphatic carboxylic acid kind solvent be in liquid state.Using the product that this method commercially produces has a lot, as terephthalic acid, m-phthalic acid, phthalic acid, naphthalic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic anhydride, 1,3,5-benzenetricarboxylic acid, pyromellitic dianhydride, benzene pentacarbonic acid, benzene hexacarboxylic acid, 4,4 '-biphenyl carboxylic acids two and phenylformic acid, wherein the industrial scale maximum is terephthalic acid.Aromatic carboxylic acid is the important source material of producing trevira and resin, and the aromatic carboxylic acid of producing with the MC method accounts for more than 80% of all aromatic carboxylic acid ultimate productions.
In the production process of aromatic carboxylic acid, it is very important improving reaction efficiency, by accelerated reaction is reduced in the reaction times, can boost productivity, and reduces cost; The selectivity of improving catalytic process also is to improve the important directions of product competitiveness, and the selectivity that improves catalyst system can reduce the burning consumption of methylarenes and solvent, thereby reduces cost, improves the quality of products.
In methylarenes liquid phase catalytic oxidation process, add the 4th kind of metal catalyst to reach the existing many cases of the purpose of strengthening reaction to cobalt-manganese-bromine three-way catalyst system, the metal component of interpolation mainly is the related salts of transition metal, rare earth metal and alkaline-earth metal.
US47867530, US4992580, US5110984 and US6153790 disclose the method for the soluble salts compound that adds nickel (Ni), molybdenum (Mo), chromium (Cr), tungsten (W), zirconium (Zr), hafnium transition metal such as (Hf) in former catalyst system, the main reaction activity all there is in various degree raising, makes reaction process obtain quickening.Although above-mentioned metallic additions can improve the synergistic effect of catalyst system as the 4th catalysis catalyst component, improve oxidizing reaction rate, improve quality product.But on using, also there are some problems, as obvious not enough to the acceleration effect of reaction, the burning reaction that also makes that has increases, and what have costs an arm and a leg, what have has the follow-up refining step of certain residual influence etc. at solid phase prod, has therefore influenced the practicality of above-mentioned technology.
Patent US5453538 has announced the method for adding the lanthanide rare metal ion to the MC catalyst system, add a certain amount of lanthanide metal ion and can reduce the usage quantity of bromine, thereby reduce discharge of harmful gases and reduce the corrodibility of system, but also the colourity of having improved product has improved the quality of product.In all lanthanide metal ions that added with cerium the best.
Patent US6194607 and CN1333743A propose to add the method for alkalimetal ion and alkaline-earth metal ions in the MC catalyst system, this method also can improve TA yield and quality product significantly.In the alkaline-earth metal ions that is added with potassium ion the best.
In addition, stable organic compound also can be used as effective the 4th activator of MC catalyst system.The organic compound component of adding mainly is the nitrogenous class organic bases with rock steady structure, as polyamino compound, guanidine compound, the interpolation of these compounds can increase cobalt-manganese-bromine system catalytic activity, improve the selectivity of reaction and the corrodibility of reduction system.
CN200310106324.5, CN200310106325.X disclose the method for adding diamino compounds and guanidine compound in former catalyst system, the main reaction activity all there is in various degree raising, make reaction process obtain quickening, the introducing of polyamino and guanidine compound can also improve the selectivity of reaction process, reduces burning reaction.Similarly, the catalytic additive of the present invention's employing also is constitutionally stable organic compound.Be different from disclosed polyamino and guanidine compound, the oxynitride with ad hoc structure that the present invention adopts is as catalytic additive, to improve the performance of existing MC catalyzer.The feature of these ad hoc structures comprises groups such as N=O base, N-hydroxyl, N-acyloxy, interpolation with oxynitride of this constitutional features can make the methylarenes oxidizing reaction obtain quickening more significantly, also reduce side reaction simultaneously, improved the selectivity of reaction process.On the other hand, have the oxynitride of this kind structure, itself have the catalysis similar, can partly or entirely substitute the bromine component, thereby the bromine component is to the corrosive nature of equipment and the discharging of brominated toxic gas in the reduction MC catalyst system with bromine.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of purpose of strengthening reaction that not only can reach, and can also increase the selectivity of reaction, reduces side reaction, weakens the novel method of corrosive liquid phase catalytic oxidation production aromatic carboxylic acid of reaction system.
The present invention carries out improvedly on existing liquid phase catalytic oxidation production aromatic carboxylic acid's method basis, it is characterized in that:
A, be solvent, adopt gas cyaniding methyl aromatic hydrocarbon or its partial oxidation intermediary product of oxygen-containing molecules directly to obtain the aromatic carboxylic acid product with the aliphatic carboxylic acid;
B, employing catalyst system are cobalt-manganese-bromo-oxynitride quaternary compound system, promptly add oxynitride as catalyst activator in existing cobalt-manganese-bromine MC catalyst system;
Above-mentioned catalyst system can also add an amount of other rare earth metals, transition metal, basic metal and alkaline-earth metal ions except that cobalt and manganese.
The oxynitride class catalyst activator that uses among the present invention can be one or more any oxynitride that contains N=O base, N-hydroxyl, N-acyloxy special groups feature.
The oxynitride catalyst activator that the present invention uses comprises the compound of N=O base with rock steady structure, N-hydroxyl, N-acyloxy.
This oxynitride class catalyst activator must be the compound that this process adopts solubility in the solvent system, uses with the form that is dissolved in the solvent.The oxynitride class catalyst activator that adds and the mol ratio of Co-Mn metal total ion concentration approximately are 0.05～20, or preferred 1～5.
The N=O base class catalyst activator that the present invention uses is selected from N-oxidation triazine, N-oxidation pyrimidine, N-oxidation pyrazine, N-pyridine oxide, N-oxidation quinoline, N-oxidation acridine, N, N '-titanium dioxide pyrimidine, N, N '-titanium dioxide pyrazine, N, N '-titanium dioxide triazine, N, N '; N " the N=O radical derivative of-three oxidation triazines and other nitrogen heterocyclic, preferred single N=O based compound, most preferably N-pyridine oxide.
The N-hydroxy kind catalyst activator that the present invention uses is selected from N-hydroxyphthalimide (NHPI), N-hydroxyl maleimide (NHAI), N-hydroxyl urazole, N-hydroxyl isocyanuric acid, N, N '-dihydroxyl isocyanuric acid, N, N ', N "-other derivatives of trihydroxy-isocyanuric acid and N-hydroxyl dicarboximide.Preferred N-hydroxyphthalimide, N-hydroxyl maleimide, N, N ', N "-trihydroxy-isocyanuric acid, most preferably N-hydroxyphthalimide.
The N-acyl-oxygen base class catalyst activator that the present invention uses is selected from N-acetoxyl group phthalic imidine (NAPI), N-acetoxyl group maleimide, N-acetoxyl group urazole etc.Preferred N-acetoxyl group compound, most preferably N-hydroxyphthalimide.
Aforementioned acyloxy is selected from the fat acyloxy of 2～6 carbon atoms, comprises acetoxyl group, propionyloxy, butyryl acyloxy, penta acyloxy, hexylyloxy.
The solvent that the present invention uses can adopt C
1～C
6Aliphatic carboxylic acid, as formic acid, acetic acid, propionic acid, butanic acid, valeric acid, caproic acid, trimethylacetic acid etc., the mixture of preferred acetic acid or acetic acid and water is generally the vinegar stock that contains 2～25% quality water.Solvent ratio (mass ratio of aromatic hydrocarbons reactant and solvent) is generally 1～10.
The gas of oxygen-containing molecules of the present invention comprises the gaseous mixture and the pure oxygen of air, oxygen-rich air, oxygen and rare gas element such as nitrogen, is preferably air.
Oxidation initiator methylarenes of the present invention is meant and has one or more substituent methyls the compound of benzene, naphthalene or the class quasi-aromatic compound of the functional group of oxidation methyl (or have), comprise p-Xylol, m-xylene, o-Xylol, pseudocumol (1,2, the 4-Three methyl Benzene), sym-trimethylbenzene (1,3, the 5-trimethylbenzene), durene (1,2,4,5-tetramethyl-benzene), pentamethylbenzene, hexamethyl-benzene, dimethylnaphthalene, 4,4 '-dimethyl diphenyl and toluene.
The methyl aromatic hydrocarbon intermediate oxidation product of partial oxidation of the present invention is selected from p-methylbenzoic acid, m-methyl benzoic acid, o-toluic acid, p-tolyl aldehyde, a tolyl aldehyde, o-methyl-benzene formaldehyde, 4-carboxyl benzaldehyde, 3-carboxyl benzaldehyde and 2-carboxyl benzaldehyde.
The oxidation target product that the present invention relates to is an aromatic carboxylic acid, selected is to have the compound that one or more replace benzene, naphthalene or the class quasi-aromatic compound of carboxyl, terephthalic acid, m-phthalic acid, phthalic acid, Tetra hydro Phthalic anhydride, naphthalic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic anhydride, 1,3,5-benzenetricarboxylic acid, pyromellitic dianhydride, benzene pentacarbonic acid, benzene hexacarboxylic acid, 4,4 '-biphenyl carboxylic acids two and phenylformic acid.
Described rare earth metal, transition metal, basic metal and alkaline-earth metal ions are selected from cerium, samarium, zirconium, hafnium, molybdenum, chromium, nickel, tungsten, potassium, sodium and calcium.
Basic catalyst system among the present invention is a Co-Mn-Br ternary MC catalyst system, also can add other transition metal or rare earth metal component.In basic catalyst system, the mol ratio of Co/Mn is 0.1～100, preferred 0.2～20.The mol ratio of Br/ (Co+Mn) is 0.1～10, preferred 0.5～2.The concentration of cobalt is 50～10 of weight of solvent, and 000ppm is preferred 100～2,000ppm.The bromine source can be taken from bromine-containing compound, as hydrogen bromide, Potassium Bromide, tetrabromoethane etc.; As for manganese and cobalt source, can be dissolved in solvent contain manganese and cobalt compound all can, as acetate, carbonate, acetate tetrahydrate, bromide etc.Preferred cobalt, manganese, bromine source are respectively Co (OAc)
24H
2O, Mn (OAc)
24H
2O and hydrogen bromide.
The temperature of reaction that the present invention is suitable for is 100～255 ℃, and preferred 155～205 ℃, reaction pressure is determined that by temperature of reaction reaction pressure is about 0.5～1.5MPa usually, or selects 1.0～1.4MPa.
The present invention is a solvent with aliphatic carboxylic acid (as acetic acid), find and use the oxynitride compounds first as methylarenes liquid-phase oxidation catalyst activator, adopt cobalt-manganese-bromo-oxynitride quaternary composite catalyst system, aroamtic hydrocarbon raw material is carried out liquid phase oxidation reaction with the gas that contains oxygen molecule.Compare with existing MC method for oxidation, the interpolation of oxynitride is quickened the arene oxidizing reaction significantly, under the identical reaction times, for given transformation efficiency, the reaction conditions that the present invention needs is gentle (lower catalyst concn or lower temperature of reaction), simultaneously can significantly reduce side reaction, improve the selectivity of reaction process, so the present invention not only can improve the productivity of aromatic carboxylic acid, can also reduce material consumption, improve the quality of products, reduce production costs.And because cobalt-manganese-bromo-oxynitride quaternary composite catalyst system is a kind of eco-friendly catalyzer, so the present invention can reduce the consumption of bromine component, the discharging of minimizing poisonous fume, the corrosion of reduction equipment significantly.
Embodiment
Below will set forth the present invention in more detail by embodiment.
Embodiment 1～5: by embodiment 1-5 the catalytic activity of the different N=O base heterocyclic compound of different concns as catalyst activator is described, to select suitable N=O base heterocyclic additive, the results are shown in table 1.
Embodiment 1
To volume is that 500 milliliters of titanium material autoclaves add 300 milliliters of reaction solutions, feeds nitrogen as protection gas, and with reaction solution heat temperature raising to 195 ℃, pressure rises to 1.7MPa when stirring.Reaction solution (being reaction mixture) consist of 9% (28.05g, 264.5mmol) the acetic acid of p-Xylol and 91% (280.5g), wherein catalyst concn be the bromine of manganese, 400ppm of cobalt, the 350ppm of 200ppm and the N-pyridine oxide of 107ppm (ppm all be with acetic acid benchmark wherein the mol ratio of cobalt, manganese, bromine and N-pyridine oxide be 3: 5.63: 4.42: 1).Use Cobalt diacetate tetrahydrate, four water acetic acid manganese, hydrogen bromide and N-pyridine oxide as catalyzer.Be reflected under 195 ℃ of pressure 1.7MPa of temperature condition and carry out, feed high-pressure air in the reaction process continuously, the constant air flow is 12L/min, and the tail gas oxygen concn adopts magnetic oxygen analyser on-line analysis, CO and CO
2Concentration detects with infrared on line analyzer, and the tail gas concentration data carries out data acquisition-and-recording by computer, can calculate the oxygen consumption rate and different total oxygen-consumption constantly of reaction process by tail gas oxygen concn data, by tail gas CO and CO
2Concentration data can calculate reaction process CO and CO respectively
2Generating rate and total growing amount.Time of 95% of generally getting oxygen-consumption and be theoretical oxygen-consumption (793.5mmol) (because reaction process does not have oxygen consumption, illustrate that reaction finishes) and finishes to react as the response feature time when the reaction end gas oxygen concn reaches 21%.Experiment condition, reaction concluding time and CO
XGrowing amount is shown in Table 1.
Embodiment 2
The mode identical with embodiment 1 carried out the oxidizing reaction of p-Xylol, just the N-pyridine oxide that is added in this enforcement changes to N-oxidation pyrimidine, the catalyzer of its interpolation consist of the bromine of manganese, 400ppm of the cobalt of 200ppm, 350ppm and the N-oxidation pyrimidine of 108ppm (ppm all be with acetic acid benchmark wherein the mol ratio of cobalt, manganese, bromine and N-oxidation pyrimidine be 3: 5.63: 4.42: 1).It needs 17.13 minutes during to oxygen-consumption to theoretical total oxygen-consumption 95%, and the COX growing amount is 166.6mmol, the results are shown in table 1.
Embodiment 3
The mode identical with embodiment 2 carried out the oxidizing reaction of p-Xylol, N-oxidation pyrimidine change N-oxidation pyrazine that just in this embodiment will be original, and the concentration of cobalt, manganese, bromine and N-oxide compound is constant in the maintenance catalyst system, the results are shown in table 1.
Embodiment 4
The mode identical with embodiment 1 carried out the oxidizing reaction of p-Xylol, just the N-pyridine oxide that is added in this enforcement changes to N, N '-titanium dioxide pyrimidine, the catalyzer of its interpolation consists of the cobalt of 200ppm, the manganese of 350ppm, the bromine of 400ppm and the N of 127ppm, (ppm all is benchmark wherein cobalt, manganese, bromine and N with acetic acid to N '-titanium dioxide pyrimidine, the mol ratio of N '-titanium dioxide pyrimidine is 3: 5.63: 4.42: 1), the results are shown in table 1.
Embodiment 5
The mode identical with embodiment 4 carried out the oxidizing reaction of p-Xylol, just in this embodiment with original N, and N '-titanium dioxide pyrimidine change N, N '-titanium dioxide pyrazine, the concentration of cobalt, manganese, bromine and N-oxide compound is constant in the maintenance catalyst system.It needs 18.40 minutes during to oxygen-consumption to theoretical total oxygen-consumption 95%, and the COX growing amount is 169.8mmol.
Embodiment 6
The mode identical with embodiment 1 carried out the oxidizing reaction of p-Xylol, just the N-pyridine oxide that is added in this enforcement changes to N-oxidation quinoline, the catalyzer of its interpolation consist of the bromine of manganese, 400ppm of the cobalt of 200ppm, 350ppm and the N-oxidation quinoline of 146ppm (ppm all be with acetic acid benchmark wherein the mol ratio of cobalt, manganese, bromine and N-oxidation quinoline be 3: 5.63: 4.42: 1).It needs 17.33 minutes during to oxygen-consumption to theoretical total oxygen-consumption 95%, and the COX growing amount is 167.7mmol.
The comparative example 1
Carry out the oxidizing reaction of p-Xylol with the mode identical, just in catalyst system, do not introduce the acetic acid N-pyridine oxide with embodiment 1.It needs 19.93 minutes during to oxygen-consumption to theoretical total oxygen-consumption 95%, and the COX growing amount is 175.2mmol, and the result compares in table 1.
PX oxidation results under table 1 different N=O base heterocyclic compound activator condition
| Embodiment | Catalyst component concentration (ppm) | Reaction times (minute) * | COX growing amount (mmol) ** | ||||
| Co | Mn | Br | N=O base heterogeneous ring compound | Concentration (ppm) | |||
| 1 | 200 | 350 | 400 | N-pyridine oxide | 107 | 16.92 | 160.3 |
| 2 | 200 | 350 | 400 | N-oxidation pyrimidine | 108 | 17.13 | 166.6 |
| 3 | 200 | 350 | 400 | N-oxidation pyrazine | 108 | 17.57 | 168.2 |
| 4 | 200 | 350 | 400 | N, N '-titanium dioxide pyrimidine | 127 | 17.75 | 170.1 |
| 5 | 200 | 350 | 400 | N, N '-titanium dioxide pyrazine | 127 | 18.40 | 169.8 |
| 6 | 200 | 350 | 400 | N-oxidation quinoline | 146 | 17.33 | 167.7 |
| The comparative example 1 | 200 | 350 | 400 | Do not have | Do not have | 19.93 | 175.2 |
* reaction times, get oxygen-consumption to time of theoretical total oxygen-consumption 95% as response feature time (theoretical total oxygen-consumption is 793.5mmol, and its 95% amount is 754.0mmol).
* COX growing amount is got oxygen-consumption to interior CO of the time of theoretical total oxygen-consumption 95%
2Generate total amount with CO.
Table 1 is the result show, along with the interpolation of certain N=O base heterocyclic compound, the reaction times shortens significantly, and the COX growing amount obviously reduces.This explanation, N=O base heterocyclic compound can quicken the PX oxidation reaction process effectively, can also suppress the burning reaction of solvent and reactant simultaneously.Relatively can get with embodiment 1, the N-pyridine oxide that adds 107ppm can make about 18% (the reducing to 17 fens by about 20 minutes) of reaction rate accelerates, and burning reaction reduces about 10% (the COX growing amount drops to 160.3mmol by 175.2mmol).The catalytic activity that table 1 result also shows N=O base heterocyclic compound is difference to some extent.Though the N=O that embodiment 1,2,3,4,5 and 6 is added base heterocyclic compound molar weight equates, and they are to the booster action of main reaction and bigger to the restraining effect effect difference of burning reaction.Comparative example 2 and embodiment 4, embodiment 3 and embodiment 5 as can be seen, many N=O base heterocyclic compounds are active lower than single N=O base heterocyclic compound.Therefore in N=O base heterocyclic compound, single N=O base heterocyclic compound is preferred.
Comparative example 1, embodiment 2, embodiment 3 and embodiment 6 as can be seen, in the single N=O base heterocyclic compound, the PX oxidising process reactive behavior of adding N-pyridine oxide is the highest, selectivity is best.In the N=O of above-mentioned investigation base heterocyclic compound, the molecular weight of N-pyridine oxide is minimum, and molecular structure also is the most stable.And for other N=O base heterocyclic compound, the easier acquisition of N-pyridine oxide has lower cost, thus in single N=O base heterocyclic compound more preferably N-pyridine oxide as catalytic additive.
Embodiment 7-11: by embodiment 7-11 the catalytic activity of the N-pyridine oxide of different concns as catalyst activator is described,, the results are shown in table 2 to select the interpolation concentration of suitable N-pyridine oxide industrial application.
The mode identical with embodiment 1 carried out the oxidizing reaction of p-Xylol, and just the concentration of the N-pyridine oxide that is added in embodiment 7,8,9,10 and 11 is changed into 50ppm respectively, 100ppm, 200ppm, 500ppm and 1000ppm.Always the time of oxygen-consumption 95% was respectively 18.11 minutes, 16.92 minutes, 15.75 minutes, 14.17 minutes, 13.00 minutes oxygen-consumption to theory; The COX growing amount is respectively 167.7mmol, 159.5mmol, 150.3mmol, 138.6mmol, 129.7mmol.All experimental results are summarized in table 2.
PX oxidation results under table 2 different N-pyridine oxide activator addition condition
| Embodiment | Catalyst component concentration (ppm) | Reaction times (minute) * | COX growing amount (mmol) * | |||
| Co | Mn | Br | N-pyridine oxide | |||
| 7 | 200 | 350 | 400 | 50 | 18.11 | 167.7 |
| 8 | 200 | 350 | 400 | 100 | 16.92 | 159.5 |
| 9 | 200 | 350 | 400 | 200 | 15.75 | 150.3 |
| 10 | 200 | 350 | 400 | 500 | 14.17 | 138.6 |
| 11 | 200 | 350 | 400 | 1000 | 13.00 | 129.7 |
| The comparative example 1 | 200 | 350 | 400 | Do not have | 19.93 | 176.2 |
* in the reaction times, the meaning of COX growing amount is with table 1.
Table 2 is the result show, along with the increase of the addition of N-pyridine oxide, the reaction times shortens significantly, and the COX growing amount obviously reduces.This explanation, the amount that N-pyridine oxide adds is many more, and the PX oxidizing reaction rate is fast more, and burning reaction is few more.But, when the N-pyridine oxide addition surpasses when a certain amount of, impact effect to reaction system can become more and more not obvious, as when N-pyridine oxide concentration when 500ppm is increased to 1000ppm, reaction times just shortens 1.2 minutes (being reduced to 13.00 minutes by 14.17 minutes), the COX growing amount reduced by 9 the milli rub (by 138.6 the milli rub be reduced to 129.7 the milli rub); And the N-pyridine oxide addition is from 0) when being increased to 200ppm, the reaction times has shortened 4.2 minutes more than (being reduced to 15.75 minutes by 19.93 minutes) unexpectedly, and the COX growing amount reduces and to reach 26 millis rub (rubbed by 176.2 millis and be reduced to 150.3 millis and rub).Therefore can determine that under the reaction conditions of being investigated, the N-pyridine oxide suitable addition is in 50～200ppm scope.
Embodiment 12-18: the catalytic activity by embodiment 12-18 illustrates N-hydroxyl and N-acyloxylation compound the results are shown in table 3.
Embodiment 12
The mode identical with embodiment 1 carried out the oxidizing reaction of p-Xylol, just the N-pyridine oxide that is added in this enforcement changes to N-hydroxyphthalimide (NHPI), the catalyzer of its interpolation consists of the cobalt of 200ppm, the manganese of 350ppm, the bromine of 400ppm and the NHPI of 553ppm, and (ppm all is benchmark with acetic acid, and wherein the mol ratio of cobalt, manganese, bromine and NHPI is 3: 5.63: 4.42: 3).The results are shown in table 3.
Embodiment 13
The mode identical with embodiment 12 carried out the oxidizing reaction of p-Xylol, just in this embodiment original NHPI is changed to N-hydroxyl maleimide (NHAI), the catalyzer of its interpolation consists of the cobalt of 200ppm, the manganese of 350ppm, the bromine of 400ppm and the NHAI of 376ppm, and (ppm all is benchmark with acetic acid, and wherein the mol ratio of cobalt, manganese, bromine and NHPI is 3: 5.63: 4.42: 3).The results are shown in table 3.
Embodiment 14
The mode identical with embodiment 12 carried out the oxidizing reaction of p-Xylol, just adjusted the catalyzer composition in this embodiment, keeps cobalt in the catalyst system, manganese, bromine concentration constant, and the concentration with NHPI is increased to 1% by 553ppm simultaneously.The results are shown in table 3.
Embodiment 15
The mode identical with embodiment 13 carried out the oxidizing reaction of p-Xylol, just adjusted the catalyzer composition in this embodiment, keeps cobalt in the catalyst system, manganese, bromine concentration constant, and the concentration with NHAI is increased to 1% by 376ppm simultaneously.The results are shown in table 3.
Embodiment 16
The mode identical with embodiment 14 carried out the oxidizing reaction of p-Xylol, just adjusted the catalyzer composition in this embodiment, cobalt manganese concentration is constant in the maintenance catalyst system, bromine concentration is reduced by 50%, promptly drop to 200ppm by 400ppm, the concentration with the N-hydroxyphthalimide is increased to 2% by 1% simultaneously.The results are shown in table 3.
Embodiment 17
The mode identical with embodiment 1 carried out the oxidizing reaction of p-Xylol, just the N-pyridine oxide that is added in this enforcement changes to N-acetyl oxygen phthalic imidine (NAPI), and the catalyzer of its interpolation consists of the manganese of the cobalt of 200ppm, 350ppm, the bromine of 400ppm and 1% NAPI.The results are shown in table 3.
Embodiment 18
The mode identical with embodiment 15 carried out the oxidizing reaction of p-Xylol, just adjusted the catalyzer composition in this embodiment, cobalt manganese concentration is constant in the maintenance catalyst system, bromine concentration is reduced by 50%, promptly drop to 200ppm by 400ppm, the concentration with N-acetyl oxygen phthalic imidine is increased to 2% by 1% simultaneously.The results are shown in table 3.
The comparative example 2
Carry out the oxidizing reaction of p-Xylol with the mode identical with comparative example 1, just adjusted the catalyzer composition in this embodiment, cobalt manganese concentration is constant in the maintenance catalyst system, and bromine concentration is reduced by 50%, promptly drop to 200ppm by 400ppm, the result compares in table 3.
PX oxidation results under table 3 different N-hydroxyl and the N-acyloxylation compound adding conditional
| Embodiment | Catalyst component concentration (ppm) | Reaction times (minute) * | COX growing amount (mmol) * | ||||
| Co | Mn | Br | Additive | Concentration | |||
| 12 | 200 | 350 | 400 | NHPI | 553 | 18.17 | 181.9 |
| 13 | 200 | 350 | 400 | NHAI | 376 | 19.25 | 197.5 |
| 14 | 200 | 350 | 400 | NHPI | 10000 | 16.47 | 189.7 |
| 15 | 200 | 350 | 400 | NHAI | 10000 | 17.33 | 206.6 |
| 16 | 200 | 350 | 200 | NHPI | 20000 | 23.75 | 212.1 |
| 17 | 200 | 350 | 400 | NAPI | 10000 | 14.37 | 179.3 |
| 18 | 200 | 350 | 200 | NAPI | 20000 | 22.83 | 207.3 |
| The comparative example 2 | 200 | 350 | 200 | Do not have | Do not have | 33.53 | 237.8 |
* in the reaction times, the meaning of-COX growing amount is with table 1.
Compare with comparative example 1, embodiment 12,13,14,15 and 17 result show that along with the interpolation of N-hydroxyl and N-acyl-oxygen compounds, the reaction times shortens, but the COX growing amount increases.This explanation, N-hydroxyl and N-acyl-oxygen compounds can quicken the PX oxidation reaction process effectively, and burning reaction is also had to a certain degree acceleration.Wherein better with main reaction and the side reaction index of NHPI and HAPI, so preferred NHPI and HAPI.
Compare with comparative example 1, comparative example 2, embodiment 16 and 18 result show, can reach the purpose that reduces Br component (reducing by 50%) significantly by the N-acetyl oxygen phthalic imidine (NAPI) or the N-hydroxyphthalimide (NHPI) of interpolation 2%, and every index of main reaction and side reaction can reach level preferably.Wherein with the HAPI best results, so HAPI most preferably.
In a word, the present invention discloses improving one's methods of a kind of aromatics family's carboxylic acid production, with the aliphatic carboxylic acid that contains 1-6 carbon atom is solvent, methylarenes adopts the gas that contains oxygen molecule to carry out oxidizing reaction in bromo-manganese-bromine catalyst system, and the oxynitride component that simultaneously one or more is had ad hoc structure is added in this catalyst system to optimize oxidising process.This method can be used in oxidation or the purifying methyl aromatic hydrocarbon comes in the various industrial application processes of production aromatic acid product, and carries out condition optimizing at different reaction process.
The present invention has found first and discloses to use and contained the catalyst activator of the oxynitride of N=O base, N-hydroxyl, N-acyloxy special groups as methylarenes liquid-phase oxidation MC type catalyst system.The particularly important is, compare with common MC type liquid-phase oxidation technology, the present invention has more characteristics: (a) can strengthen the reactive behavior of catalyst system, thereby the promote the oxidation process reaches the purpose of strengthening reaction; (b) can reduce the burning reaction of reaction system, thereby the selectivity that increases oxidising process reaches the purpose that reduces material consumption; (c) under identical temperature of reaction and pressure condition, add minor N-pyridine oxide, HAPI etc., can adopt lower bromine concentration just to obtain and the general identical reaction throughput of MC method, thereby reduce the corrodibility of brominated toxic gas discharging and reactive system; Or under identical temperature of reaction and pressure condition, add minor N-pyridine oxide, HAPI etc., can adopt lower total catalyst concentration just to obtain and the general identical reaction throughput of MC method, thereby reduce the waste of catalyzer; (d) under identical cobalt manganese bromine concentration condition, add minor N-pyridine oxide, HAPI etc., can adopt the reaction conditions (as lower temperature of reaction and pressure) of milder just obtain with the identical reaction throughput of MC method, thereby reduced the energy consumption and the material consumption of reaction process.
The invention is not restricted to these disclosed embodiments, the present invention will cover the scope described in the patent claims, and the various modification of claim scope and equivalence variation.
Claims (13)
1, a kind of method of producing aromatic carboxylic acid with nitrogen oxide as catalytic additive is characterized in that:
A, be solvent, adopt gas cyaniding methyl aromatic hydrocarbon or its partial oxidation intermediary product of oxygen-containing molecules directly to obtain the aromatic carboxylic acid product with the aliphatic carboxylic acid;
B, employing catalyst system are cobalt-manganese-bromo-oxynitride quaternary compound system, promptly add oxynitride as catalyst activator in existing cobalt-manganese-bromine MC catalyst system;
2, according to the described method of producing aromatic carboxylic acid of claim 1, it is characterized in that with nitrogen oxide as catalytic additive:
Catalyst system can also add one or more other rare earth metals, transition metal, basic metal and alkaline-earth metal ions except that cobalt and manganese.
3, according to claim 1 or 2 described methods of producing aromatic carboxylic acid with nitrogen oxide as catalytic additive, it is characterized in that: described oxynitride catalyst activator comprises the compound of N=O base with rock steady structure, N-hydroxyl, N-acyloxy.
4, according to the described method of producing aromatic carboxylic acid with nitrogen oxide as catalytic additive of claim 3, it is characterized in that: described N=O base class catalyst activator is selected from N-oxidation triazine, N-oxidation pyrimidine, N-oxidation pyrazine, N-pyridine oxide, N-oxidation quinoline, N-oxidation acridine, N, N '-titanium dioxide pyrimidine, N, N '-titanium dioxide pyrazine, N, N '-titanium dioxide triazine, N, N ', N " the N=O radical derivative of-three oxidation triazines and other nitrogen heterocyclic.
5, want 3 described methods of producing aromatic carboxylic acid with nitrogen oxide as catalytic additive according to right, it is characterized in that: described N-hydroxy kind catalyst activator is selected from N-hydroxyphthalimide (NHPI), N-hydroxyl maleimide (NHAI), N-hydroxyl urazole, N-hydroxyl isocyanuric acid, N, N '-dihydroxyl isocyanuric acid, N, N ', N "-other derivatives of trihydroxy-isocyanuric acid and N-hydroxyl dicarboximide.
6, according to the described method of producing aromatic carboxylic acid with nitrogen oxide as catalytic additive of claim 3, it is characterized in that: wherein N-acyl-oxygen base class catalyst activator is selected from the acyl derivative of N-hydroxy kind compound in the claim 5.
7, according to the described method of producing aromatic carboxylic acid with nitrogen oxide as catalytic additive of claim 6, wherein acyloxy is selected from the fat acyloxy of 2～6 carbon atoms, comprises acetoxyl group, propionyloxy, butyryl acyloxy, penta acyloxy, hexylyloxy.
8, according to claim 1 or 2 described methods of producing aromatic carboxylic acid with nitrogen oxide as catalytic additive, it is characterized in that: described solvent comprises the aliphatic carboxylic acid of 1～6 carbon atom or contains the aliphatic carboxylic acid solution of 2～25% quality than water.
9, according to the described method of producing aromatic carboxylic acid with nitrogen oxide as catalytic additive of claim 1 or 2, it is characterized in that: the gas of described oxygen-containing molecules comprises air, oxygen-rich air and pure oxygen.
10, according to claim 1 or 2 described methods of producing aromatic carboxylic acid with nitrogen oxide as catalytic additive, it is characterized in that: described methyl aromatic hydrocarbon is selected from p-Xylol, m-xylene, o-Xylol, 1,2, the 4-Three methyl Benzene, (1,3,5-trimethylbenzene, 1,2,4,5-tetramethyl-benzene, pentamethylbenzene, hexamethyl-benzene, dimethylnaphthalene, 4,4 '-dimethyl diphenyl and toluene.
11, the method for producing aromatic carboxylic acid with nitrogen oxide as catalytic additive according to claim 1 or 2 described liquid, it is characterized in that: the methyl aromatic hydrocarbon intermediate oxidation product of described partial oxidation is selected from p-methylbenzoic acid, m-methyl benzoic acid, o-toluic acid, p-tolyl aldehyde, a tolyl aldehyde, o-methyl-benzene formaldehyde, 4-carboxyl benzaldehyde, 3-carboxyl benzaldehyde and 2-carboxyl benzaldehyde.
12, according to claim 1 or 2 described methods of producing aromatic carboxylic acid with nitrogen oxide as catalytic additive, it is characterized in that: described aromatic carboxylic acid is selected from terephthalic acid, m-phthalic acid, phthalic acid, Tetra hydro Phthalic anhydride, naphthalic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic anhydride, 1,3,5-benzenetricarboxylic acid, pyromellitic dianhydride, benzene pentacarbonic acid, benzene hexacarboxylic acid, 4,4 '-biphenyl carboxylic acids two and phenylformic acid.
13, according to claim 1 or 2 described methods of producing aromatic carboxylic acid with nitrogen oxide as catalytic additive, it is characterized in that: described rare earth metal, transition metal, basic metal and alkaline-earth metal ions are selected from cerium, samarium, zirconium, hafnium, molybdenum, chromium, nickel, tungsten, potassium, sodium and calcium.
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