CN103183607B - A kind of production method mixing fragrant dioctyl phthalate - Google Patents
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Abstract
The present invention relates to a kind of production method mixing fragrant dioctyl phthalate, specifically to a kind of method that mixed xylenes cooxidation produces mixing aromatic dicarboxilic acid, it belongs to aromatic carboxylic acids production field; In polyester slice production process, need to prepare a certain proportion of PTA and PIA, the addition of PIA is primarily to the pliability and the degree of cross linking of improving polyester slice, and the mixing that the serious technological problems that existing polyester production process exists is PTA and PIA is extremely difficult to highly uniform degree. And adopt PX and MX conjugated oxidation to produce mixed carboxylic acid, obtained PTA and PIA is simultaneously generated in the oxidation reaction, blending ingredients constitutes between different types of molecule perfect crystal formation in a fixed order, high degree of dispersion between molecule, being sufficiently mixed, this just effectively prevent the product quality problem brought due to PTA and PIA mixing inequality. The mixing aromatic dicarboxilic acid produced by the present invention, when being polymerized with ethylene glycol in PET Process, it is possible to arranges out desirable polymer copolymerization configuration, makes the performance of polyester slice be improved.
Description
Technical field
The present invention relates to a kind of production method mixing fragrant dioctyl phthalate, specifically to a kind of method that mixed xylenes cooxidation produces mixing aromatic dicarboxilic acid, it belongs to aromatic carboxylic acids production field.
Background technology
Aromatic carboxylic acids is important organic compound and the raw material producing multiple chemical products, and that wherein market demand is maximum is p-phthalic acid (PTA), and for the production of terylene, the yield of global p-phthalic acid (TA) has reached 40,000,000 tons/year; Next to that M-phthalic acid (PIA), for polyester slice, yield is 100～2,000,000 tons/year. The production method of PTA and PIA is closely similar, all adopts dimethylbenzene liquid-phase air oxidation to produce, xylol (PX) oxidation obtain p-phthalic acid, meta-xylene (MX) oxidation obtain M-phthalic acid. Its Technology origin is the patented technology US2833816 of Mid-Century company application in 1958, this patented technology is characterized by using low-molecular-weight carboxylic acid (such as acetic acid) as reaction dissolvent, with the cobalt of solubility, manganese, bromine compounds for catalyst system and catalyzing, preparing aromatic carboxylic acids with air oxidation in liquid phase, dimethylbenzene liquid phase catalytic oxidation is that the yield of carboxylic acid is up to 95%. Reaction condition prepared by PTA and PIA is also about the same, and general temperature is 150～220 DEG C, and pressure is that 0.5 ~ 2.5MP, specific embodiment and condition are discussed in detail in many patents and literature of the chemical engineering.
At present, the production of PTA and PIA all adopts highly purified raw material monomer (more than 99.5%) to obtain corresponding benzene dicarboxylic acid by oxidation respectively. Dimethylbenzene aromatic monomer, mainly by carbon 8 aromatics production, be carbon 8 aroamtic hydrocarbon raw material that initiation material obtains from oil and coal is a kind of mixture reaching chemical equilibrium, and meta-xylene is maximum, accounts for 1/2, and xylol and o-Dimethylbenzene respectively account for 1/4.Owing to the isomer character of these three carbon 8 aromatic hydrocarbons is close, separation difficulty, in order to obtain highly purified single-component substance, the cost of separation is just relatively high. Such as, existing carbon 8 aroamtic hydrocarbon raw material production technology is all carry out Crystallization Separation or adsorbing separation by after BTX aromatics gas-condensate liquid, separate xylol, then will between, adjacent mixture heating and gasifying, at high temperature carry out isomerization reaction, it is partially converted into xylol (conversion per pass about 20%), then is easily separated, so moved in circles. On the other hand, although adopting highly purified meta-xylene is that raw material is to produce M-phthalic acid, but the copolymerization that is mainly used for together with p-phthalic acid carrying out of substantial amounts of M-phthalic acid produces polyester slice, and so, during use, product M-phthalic acid mixes with p-phthalic acid again. If able to directly adopt mixed xylenes raw material rather than its high-purity single-component substance to aoxidize, the mixed dicarboxylic acid obtained no longer separates and directly copolymerization use, then production technology just can simplify, and production cost can significantly reduce.
It addition, the required angle produced from polyester slice, mixed carboxylic acid is used to be more beneficial for eliminating due to the uneven product quality problem brought of PTA and PIA mixing. This is because, PX and MX conjugated oxidation is adopted to produce mixed carboxylic acid, obtained PTA and PIA is simultaneously generated in the oxidation reaction, they form cocrystallization, the perfect cystal constituted in a fixed order between different types of molecule, high degree of dispersion between molecule, is sufficiently mixed, when therefore it is polymerized with ethylene glycol in PET Process, desirable polymer copolymerization configuration can be arranged out, make the performance of polyester slice be improved. And tradition uses the blended method for making polyester for raw material of the pure material of PTA and PIA, owing to PTA and PIA tends not to be sufficiently mixed, obtained polyester macromolecule product is often the simple mixing of PETP and ethylene m-phthalate polymer, without the degree reaching copolymerization. Therefore, developing PTA and PIA cooxidation technology, not only become present aspect lucrative at conservation, itself is a kind of new material preparing high-performance polyester section especially.
Summary of the invention
In view of prior art exists in problem, the invention aims to propose a kind of extract with xylol and C8 aromatic hydrocarbons separated after product be raw material, in parallel two-stage oxidation reaction, the method producing mixing fragrant dioctyl phthalate.
To achieve these goals, the technical solution adopted in the present invention is a kind of production method mixing fragrant dioctyl phthalate, product after adopting the extract of xylol and C8 aromatic hydrocarbons separated is reaction raw materials, by two-stage oxidation reaction, prepares mixing aromatic dicarboxilic acid; Sharing solvent, catalyst, the energy of tail gas and solvent dehydration, mother liquor purification, catalyst recovery system in described course of reaction, and adopt the slurry handling process of level Four crystallization, its step is as follows:
1) oxidation reaction: xylol passes into the first oxidation reactor, the C8 Aromatics Extractive Project thing that the concentration containing meta-xylene is higher delivers to the second oxidation reactor, passes in the second oxidation reactor by xylene feedstock, acetate solvate and catalyst by pipeline; Acetate solvate and catalyst are passed in the first oxidation reactor by pipeline, air or oxygen rich gas pass into the first oxidation reactor and the second oxidation reactor after compression through air inlet pipe, and dimethylbenzene and air catalytic oxidation under the effect of catalyst generates pure mixed phthalic acid;The condition of described first oxidation reactor and the second oxidation reactor is: pressure is 0.5～2.5Mpa, temperature is 150～220 DEG C, water content 5 ~ 15%(mass content), tail oxygen concentration is 3% ~ 6%(molar content), response time is 30 ~ 100min, and described catalyst is cobalt manganese bromine catalyst, wherein cobalt, manganese, three kinds of ions of bromine total mass concentration be 500～3000ppm, cobalt manganese atom ratio is 30～0.3, and the atomic ratio of cobalt and manganese total concentration and bromide ion is 0.5～2.5; The energy that oxidation produces is changed into the latent heat of solvent and is taken away by tail gas, and the slurry of product solid is extracted out from reaction bottom, to slurry processing unit;
2) slurry processes: it includes solid-liquid separation, hydrofinishing and Crystallization Separation;
The slurry of the first oxidation reactor and the second oxidation reactor is passed through oxidizing and crystallizing device level Four crystallization by described solid-liquid separation; Oxidizing and crystallizing device is made up of the complete continuously mixed crystallizer of 4 series windings, the temperature of first order crystallizer is 190～200 DEG C, the temperature of second level crystallizer is 160～170 DEG C, and the temperature of third level crystallizer is 90～120 DEG C, and the temperature of fourth stage crystallizer is 50～70 DEG C; Described first order mould temperature is higher than the first oxidation reaction actuator temperature 10 ~ 15 DEG C, and main purpose is to promote liquid phase dissolved in M-phthalic acid, reduces the foreign pigment in M-phthalic acid by secondary oxidation; Solvent flash distillation in the crystallizer of the second level, the recycling design latent heat of vaporization; Third level crystallizer controls to reduce system temperature to normal pressure; Fourth stage crystallizer passes through vacuum evaporation, is reduced to lower temperature, to ensure that the M-phthalic acid that dissolubility is higher can precipitate out from liquid phase crystallization fully; The dissolubility data that the selection of crystallization temperature provides with reference to table 1;
4th crystallizer outlet slurry is by filter element, and a liquid part is drawn to catalyst and residue treatment unit, and a part returns the first oxidation reactor; Solid, then by dried, sends into refinement;
Mixing dioctyl phthalate is dissolved in the water by described hydrofinishing, with hydrogen generation catalytic reduction reaction in fixed bed reactors, 85 ~ 90% aldehyde is converted into ar-Toluic acid soluble in water; Hydrogenation reaction temperature is 250～300 DEG C of temperature, 5～10Mpa pressure, and catalyst is palladium carbon, and being totally submerged the slurry time of staying in the reactor in the solution is 3～10min; By hydrogenation process, the carboxyl benzaldehyde of mass fraction 99% is removed;
Slurry after hydrofinishing is passed into refining crystallization device by described Crystallization Separation, crystallizer outlet slurry is easily separated by solid-liquid separation system, solid-liquid separation operates with deionized water rinsing, product after purification, by dry, prepares high purity terephthalic acid (TA) and the product mix of M-phthalic acid (IA) binary composition;
3) energy regenerating: the first oxidation reactor, the second oxidation reactor, the tail gas of the first crystallizer and the tail gas of the second crystallizer are passed into energy-recuperation system, and the recovery system of energy includes: multi-stage condensing cooling device, high pressure absorber and decompressor; Described multi-stage condensing cooling device produces middle pressure steam, and middle pressure steam is as the thermal source of dehydration column reboiler or stripper, drying machine; Described high pressure absorber utilizes pickling and washing to reclaim organic substance; Described decompressor pressure recovery can drive compressor compresses air; A part of condensed fluid returns to first order oxidation reactor and the second oxidation state reactor, and a part of condensed fluid is drawn out of and is passed into solvent dehydration system, and water reaction produced is extracted out;
4) solvent dehydration and catalyst recovery system: the condensed fluid extracted out from energy-recuperation system is passed into solvent dehydration system, the acetic acid steam that the second crystallizer top is extracted out is passed into solvent dehydration system; The source of the solvent that the high concentration acetic acid after dehydration produces as the second oxidation reactor or high pressure absorber and slurry process the cleaning mixture of system; A part of mother solution that slurry process system obtains returns to the first oxidation reactor as circulating solvent; A part of liquor abstraction carries out mother liquor purification and catalyst reclaims, to reduce the content recovery section catalyst simultaneously of impurity in circulating mother liquor; In mother solution, the recovery of acetic acid adopts and evaporates steam stripped method, and recovered solvent and catalyst return to the first oxidation reactor.
Described reaction raw materials derive from C8 Aromatics Extractive Project thing separated after product, or pass through mass fraction > xylol of 99.5% and meta-xylene be in proportion for 20:1～3:1 preparation; Preferred ratio is 10:1～5:1.
Described catalyst adopts the mixture of cobaltous acetate, manganese acetate and hydrogen bromide; Described oxidation reactor adopts and selects the tank reactor with stirring paddle or the bubbling column reactor with gas distributor; Being preferably stirred tank reactor, reaction time is 50～120 minutes.
Described oxidizing and crystallizing device is made up of the stirred tank of four series connection, and first order mould temperature is 180～190 DEG C, passes into partial oxidation and carries out deep oxidation to the first crystallizer; The temperature of second level crystallizer is 110～150 DEG C; The temperature of third level crystallizer is reduced to 20～50 DEG C.
Described hydrogenation reactor is continuous laminar flow fixed bed reactors, arranges a charging aperture, and hydrogen enters the first oxidation reactor from spout, and the bottom catalyst of the first oxidation reactor is supported by spiral drainage screen.
Feasibility and the advantage of the present invention are in that: in polyester slice production process, need to prepare a certain proportion of PTA and PIA, the addition of PIA is primarily to the pliability and the degree of cross linking of improving polyester slice, and the mixing that the serious technological problems that existing polyester production process exists is PTA and PIA is extremely difficult to highly uniform degree. And adopt PX and MX conjugated oxidation to produce mixed carboxylic acid, obtained PTA and PIA is simultaneously generated in the oxidation reaction, blending ingredients constitutes between different types of molecule perfect crystal formation in a fixed order, high degree of dispersion between molecule, being sufficiently mixed, this just effectively prevent the product quality problem brought due to PTA and PIA mixing inequality. The mixing aromatic dicarboxilic acid produced by the present invention, when being polymerized with ethylene glycol in PET Process, it is possible to arranges out desirable polymer copolymerization configuration, makes the performance of polyester slice be improved.
The beneficial effects of the present invention is: adopt the inventive method can be directly produced the benzene dicarboxylic acid being applied to polyester industrial by the cheap mixed xylenes raw material of applied cost, reduce xylene feedstock separation costs, obtain the mixing aromatic dicarboxilic acid of high dispersive simultaneously, improve the quality of product, improve the benzene dicarboxylic acid competitiveness of product in market.
Accompanying drawing explanation
Fig. 1 is unit module and the process task figure that pure mixed phthalic acid generates process;
Fig. 2 is the process chart of the present invention;
In figure: 100, the first oxidation reactor, the 200, second oxidation reactor, 300, crystallizer and solid-liquid separation system, 400, energy-recuperation system, 500, dehydration and catalyst recovery system, 301, first order crystallizer, 302, second level crystallizer, 303, third level crystallizer, the 304, the 4th crystallizer, 305, filter, 401, the first condenser, 402, the second condenser, 501, dehydrating tower, 520, catalyst and residue treatment unit.
Detailed description of the invention
In order to further appreciate that the production method of this mixing fragrant dioctyl phthalate, accompanying drawings is as follows. It should be noted that method provided by the invention is not limited in detailed description of the invention and embodiment the flow process configuration and the process conditions that provide, any local improvement to these methods is without changing inventive feature.
The pure mixed phthalic acid that the present invention provides generates unit module and the process task figure of process, and production process includes five formants: first oxidation reactor the 100, second oxidation reactor 200, crystallizer and solid-liquid separation system 300, energy-recuperation system 400, dehydration and catalyst recovery system 500. Mother solution, catalyst and air that xylol produces with slurry processing procedure add the first oxidation reactor 100 by charge pipe; The fresh acetic acid, catalyst and the air that obtain bottom product (mainly containing xylol and meta-xylene) after the extract of C8 aromatic hydrocarbons is separated and dehydrating tower add the second oxidation reactor 200 by charge pipe; First oxidation reactor 100 and the second oxidation reactor 200 tail gas merge, exported by offgas duct, most of reactor that refluxes back after condenser condenses, capacity of returns is allocated by the oxidation load of the first oxidation reactor 100 and the second oxidation reactor 200, condensed tail gas is sent into subsequent cell and is processed, and a little condensed fluid is delivered to dehydrating tower 501 rectification and separated. Merge in introducing crystallizer outlet line from the first oxidation reactor 100 and the second reactor 200 slurry out; First order crystallizer 301 temperature is higher than the first oxidation reaction actuator temperature 10 ~ 15 DEG C, and main purpose is to promote liquid phase dissolved in M-phthalic acid, reduces the foreign pigment in M-phthalic acid by secondary oxidation. The temperature and pressure of follow-up level Four crystallizer reduces step by step to make, two kinds dicarboxylic acids sufficient crystallisings are precipitated out. The slurry of crystallizer output prepares fragrant dioctyl phthalate by filtering, drying. The mother solution filtered returns the first oxidation reactor 100. In the mixing dioctyl phthalate that said process obtains, M-phthalic acid content is 5%～30%, and the content of optimization is 10%～15%.
The technological process that the present invention provides is as follows:
Charge pipe provides raw material dimethylbenzene to the first oxidation reactor 100, and para-xylene concentration (mass concentration) is higher than 99%. Meanwhile, pipeline provides circulating mother liquor, contains the M-phthalic acid of a small amount of non-crystallization and substantial amounts of solvent acetic acid in mother solution. Atmospheric air is compressed to 1.2～2.0MPa(0.2MPa higher than the pressure in the first oxidation reactor 100 by air compressor), pass in the first oxidation reactor 100 through pipeline, the oxygen in pressure-air is as the oxidant of reaction. Reaction temperature controls 185～200oC, pressure is 1.0～1.8MPa. Dimethylbenzene generates solids mixing fragrance phthalic acid through liquid phase oxidation in the reactor, and slurry residence time is 30～80 minutes. Catalyst cobalt, manganese metal and bromine catalyst are sent into by pipeline, catalyst adopts the industrial cobalt manganese bromine catalyst system commonly used, the mass concentration of cobalt is 100 ~ 900ppm, and manganese cobalt mass ratio is 0.5 ~ 1.5, and the mass ratio of promoter bromine and cobalt manganese is 0.6 ~ 1.2. In the pure mixed phthalic acid solid of gained, the content of ar-Toluic acid is 2000 ~ 4000ppm, and particle diameter is 90 ~ 150 μm. The slurry containing mixed carboxylic acid's solid of gained is extracted out bottom the first oxidation reactor 100, and the substantial amounts of energy that p xylene oxidation produces is changed into the latent heat of solvent and taken away by tail gas, enters energy-recuperation system through pipeline.
Product after the extract of C8 aromatic hydrocarbons is separated enters the second oxidation reactor 200 by pipeline, and partial tail gas condensed fluid is passed into the second oxidation reactor 200 by pipeline simultaneously. Pressure-air or oxygen rich gas are sent to the first oxidation reactor 100 by pipeline, as the oxidant of mixed arenes oxidation. Catalyst adopts the industrial cobalt manganese bromine catalyst system commonly used, and the mass concentration of cobalt is 100 ~ 900ppm, and manganese cobalt mass ratio is 0.5 ~ 1.5, and the mass ratio of promoter bromine and cobalt manganese is 0.6 ~ 1.2. The peak optimization reaction temperature of the second oxidation reactor 200 is 190 ~ 200 DEG C, and pressure is 1200 ~ 1600kPa, water content 5 ~ 10%(mass content), tail oxygen concentration is 3% ~ 6%(molar content), the time of staying is 50 ~ 100min. Mixed xylenes occurs liquid phase oxidation to generate pure mixed phthalic acid solid in the first oxidation reactor 100, and in the solid product of gained, the content of M-phthalic acid is 60 ~ 70%, and particle diameter is 60 ~ 80 μm. Gained slurry of solids is extracted out bottom the second oxidation reactor 200, and the substantial amounts of energy that oxidation produces is changed into the latent heat of solvent and taken away by tail gas, merges with the tail gas of the first oxidation reactor 100, enters energy-recuperation system 400 through pipeline.
The slurry extracted out bottom the first oxidation reactor 100 and the second oxidation reactor 200 combines, and sends into level Four crystallizer through pipeline. First order crystallizer 301 temperature is higher 10 ~ 15 DEG C than the first oxidation reactor 100 temperature, it is provided that the high temperature acetic acid steam of heat is sent to first order crystallizer 301 by pipeline, high temperature acetic acid steam can be obtained by the high concentration acetic acid of solvent dehydration system is heated, pressure-air or oxygen rich gas enter first order crystallizer 301 through air inlet pipe, and deep oxidation at high temperature occurs mixing aromatic carboxylic acids solid particle. The pressure of first order crystallizer 301 is 1300 ~ 2000kPa, and temperature is 190～220 DEG C, and the time of staying is 20 ~ 40min. It is sent to second level crystallizer 302 through pipeline from the first crystallizer 301 slurry out. Second crystallizer 302 reduces pressure cooling further, the steam produced is sent into bottom dehydrating tower 501 by pipeline, portion of energy needed for dehydration is provided, in the second crystallizer 302, most TA and most IA precipitates out from liquid phase crystallization, the temperature of the second crystallizer 302 is 160 ~ 170 DEG C, pressure is 400 ~ 600kPa, and the time of staying is 20 ~ 40min. Third level crystallizer 303 reduces pressure further to normal pressure, and temperature controls at 90～120 DEG C. Fourth stage crystallizer passes through vacuum evaporation, and pressure is gauge pressure-0.05MPa, is reduced to temperature 50～70 DEG C, to ensure that the M-phthalic acid that dissolubility is higher can precipitate out from liquid phase crystallization fully.
The slurry that 4th crystallizer 304 flows out is delivered to filter 305 by pipeline and is separated mother solution and solid, meanwhile, acetic acid moiety refining bottom dehydrating tower 501 is transported to oxidation reaction filter 305 and solid is washed. Oxidation reaction filter mother liquor fraction (90～95%) is back to the first oxidation reactor 100 by pipeline, partly (5～10%) are extracted out and are carried out mother liquor purification and catalyst recovery, the acetic acid reclaimed is back to the first oxidation reactor 100, solid after filtration washing delivers to drying machine through pipeline, obtains mixing aromatic dicarboxilic acid product after drying.
The tail gas of first oxidation reactor the 100, second oxidation reactor 200 and first order crystallizer 301 is passed into energy-recuperation system 400, the recycling of energy adopts multi-stage condensing cooling device to produce middle pressure steam, middle pressure steam is as the thermal source of dehydration column reboiler or stripper, drying machine, it is achieved recycle.The condensed fluid of part returns to the first oxidation reactor 100 and the second oxidation reactor 200 through pipeline and pipeline, and a part of condensed fluid is passed into solvent dehydration system through pipeline, and the acetic acid steam extracted out from crystallizer top is also passed into solvent dehydration system through pipeline. High concentration acetic acid after dehydration is as the solvent source of the second oxidation reactor 200, or the source as high temperature acetic acid steam, filter process cleaning mixture and residue treatment unit cleaning mixture. The steam lease making pipeline extracted out from solvent dehydration system drains into sewage disposal system.
The Extract of the first condenser 401 and the second condenser 402 delivers to dehydrating tower through pipeline, carries out rectifying and dewatering. Meanwhile, the second crystallizer 302 steam produced enters bottom dehydrating tower 501, it is provided that portion of energy needed for dehydration, and its complementary energy is provided by dehydrating tower 501 reboiler heat exchanger. Dehydrating tower 501 adopts azeotropic distillation to strengthen, and entrainer is butyl acetate or propyl acetate. Entrainer adds from tower top with water, and the vapor phase product after rectification, rich in water and entrainer, flows out from tower top, and condensed device condenses, and is separated into aqueous phase and oil phase in oil water separator. Oil phase is back to rectifying column, and aqueous phase then discharges system. Separate via oil water separator, make entrainer be recycled. Tower top discharges the acetate concentration mass fraction of water less than 0.3%, and the acid concentration of the acetic acid of the low concentration of tower is more than 90%.
Embodiment 1
The method and apparatus that the present invention provides is adopted to carry out the mixing fragrant dioctyl phthalate flow process producing 600000 tons per year and device design, 7600 hours production times of year, the process conditions of unit equipment are determined according to material consumption and energy consumption minimized principle, and the energy match between each stream stock is optimized according to the principle that system capacity is integrated. Gained related process parameters is enumerated as follows according to sequence of unit:
Under these conditions, oxidation reactor 100 exports the index of slurry and is listed in table 3.
Note: PX p-phthalic acid, MX M-phthalic acid; 3-CBA 3-carboxyl benzaldehyde, 4-CBA 4-carboxyl benzaldehyde.
Under these conditions, oxidation reactor 200 exports the index of slurry and is listed in table 5.
Crystallizer parameter is enumerated as follows
Material and the energy balance data of the mixing fragrant dioctyl phthalate production procedure of 600000 tons are listed in table 10.
Claims (10)
1. mixing a production method for fragrant dioctyl phthalate, the separated afterproduct of extract adopting xylol and C8 aromatic hydrocarbons is reaction raw materials, by two-stage oxidation reaction, prepares mixing aromatic dicarboxilic acid; Its step is as follows:
1) oxidation reaction: xylol passes into the first oxidation reactor, the C8 Aromatics Extractive Project thing that the concentration containing meta-xylene is higher delivers to the second oxidation reactor, passes in the second oxidation reactor by xylene feedstock, acetate solvate and catalyst by pipeline; Acetate solvate and catalyst are passed in the first oxidation reactor by pipeline, air or oxygen rich gas pass into the first oxidation reactor and the second oxidation reactor after compression through air inlet pipe, and dimethylbenzene and air catalytic oxidation under the effect of catalyst generates pure mixed phthalic acid; The energy that oxidation produces is changed into the latent heat of solvent and is taken away by tail gas, and the slurry of product solid is extracted out from reaction bottom, to slurry processing unit;
2) slurry processes: it includes solid-liquid separation, hydrofinishing and Crystallization Separation;
The slurry of oxidation reactor is passed through oxidizing and crystallizing device level Four crystallization by described solid-liquid separation; Oxidizing and crystallizing device is made up of the complete continuously mixed crystallizer of 4 series windings, the temperature of first order crystallizer is 190～200 DEG C, the temperature of second level crystallizer is 160～170 DEG C, and the temperature of third level crystallizer is 90～120 DEG C, and the temperature of fourth stage crystallizer is 50～70 DEG C;4th crystallizer outlet slurry is by filter element, and liquid portion is drawn to catalyst and residue treatment unit, and part returns the first oxidation reactor (100); Solid, then by dried, sends into refinement;
Mixing dioctyl phthalate is dissolved in the water by described hydrofinishing, and with hydrogen generation catalytic reduction reaction in fixed bed reactors, the aldehyde by 90 ~ 95% is converted into ar-Toluic acid soluble in water; Hydrogenation reaction temperature is 250～300 DEG C of temperature, 5～10Mpa pressure, and catalyst is palladium carbon, and being totally submerged the slurry time of staying in the reactor in the solution is 3～10min; By hydrogenation process, the carboxyl benzaldehyde of mass fraction 99% is removed;
Slurry after hydrofinishing is passed into refining crystallization device by described Crystallization Separation, crystallizer is discharged slurry and is easily separated by solid-liquid separation system, solid-liquid separation operates with deionized water rinsing, product after purification, by dry, prepares p-phthalic acid and the product mix of M-phthalic acid binary composition;
3) energy regenerating: the tail gas of the first oxidation reactor, the second oxidation reactor, the first crystallizer and the second crystallizer is passed into energy-recuperation system, and energy-recuperation system includes: multi-stage condensing cooling device, high pressure absorber and decompressor; Described multi-stage condensing cooling device produces middle pressure steam, and middle pressure steam is as the thermal source of dehydration column reboiler or stripper, drying machine; Described high pressure absorber utilizes pickling and washing to reclaim organic substance; Described decompressor pressure recovery can drive compressor compresses air; The condensed fluid of a part returns to the first oxidation reactor and the second oxidation reactor, and a part of condensed fluid is drawn out of and is passed into solvent dehydration system, and water reaction produced is extracted out;
4) solvent dehydration and catalyst recovery system: the condensed fluid extracted out from energy-recuperation system is passed into solvent dehydration system, the acetic acid steam that the second crystallizer top is extracted out is passed into solvent dehydration system; High concentration acetic acid after dehydration is the solvent source that produces of reactor or high pressure absorber and slurry process system cleaning mixture; The partial mother liquid that slurry process system obtains returns to reactor as circulating solvent; Partial mother liquid is extracted out and is carried out mother liquor purification and catalyst recovery; In mother solution, the recovery of acetic acid adopts and evaporates steam stripped method, and recovered solvent and catalyst return to reactor.
2. the production method of mixing fragrant dioctyl phthalate according to claim 1, it is characterized in that: described reaction raw materials derive from C8 Aromatics Extractive Project thing separated after product, or pass through mass fraction > xylol of 99.5% and meta-xylene be in proportion for 20:1～3:1 preparation.
3. the production method of mixing fragrant dioctyl phthalate according to claim 1, it is characterised in that: described reaction is by raw materials quality mark > xylol of 99.5% and meta-xylene be 10:1～5:1 preparation in proportion.
4. the production method of mixing fragrant dioctyl phthalate according to claim 1, it is characterized in that: the condition of described first oxidation reactor and the second oxidation reactor is: pressure is 0.5～2.5Mpa, temperature is 150～220 DEG C, water content 5 ~ 15%(mass content), tail oxygen concentration is 3% ~ 6%(molar content), the response time is 30 ~ 100min.
5. the production method of mixing fragrant dioctyl phthalate according to claim 1, it is characterized in that: the catalyst in described step 1) is cobalt manganese bromine catalyst, catalyst cobalt, manganese, three kinds of ions of bromine total mass concentration be 500～3000ppm, cobalt manganese atom ratio is 30～0.3, and the atomic ratio of cobalt and manganese total concentration and bromide ion is 0.5～2.5.
6. the production method of mixing fragrant dioctyl phthalate according to claim 1, it is characterised in that: first order mould temperature is higher 10 ~ 15 DEG C than oxidation reaction actuator temperature, a large amount of flash distillation of solvent in the crystallizer of the second level, the recycling design latent heat of vaporization; Third level crystallizer controls to reduce system temperature to normal pressure; Fourth stage crystallizer passes through vacuum evaporation.
7. the production method of mixing fragrant dioctyl phthalate according to claim 1, it is characterised in that: the catalyst in described step 1) adopts the mixture of cobaltous acetate, manganese acetate and hydrogen bromide; Described oxidation reactor adopts and selects the tank reactor with stirring paddle or the bubbling column reactor with gas distributor; Reaction time is 50～120 minutes.
8. the production method of mixing fragrant dioctyl phthalate according to claim 7, it is characterised in that: described oxidation reactor adopts stirred tank reactor.
9. the production method of mixing fragrant dioctyl phthalate according to claim 1, it is characterized in that: described oxidizing and crystallizing device is made up of the stirred tank of four series connection, first order mould temperature is 180～190 DEG C, passes into partial oxidation and carries out deep oxidation to the first crystallizer; The temperature of second level crystallizer is 110～150 DEG C; The temperature of third level crystallizer is reduced to 20～50 DEG C.
10. the production method of mixing fragrant dioctyl phthalate according to claim 1, it is characterized in that: described hydrogenation reactor is continuous laminar flow fixed bed reactors, having individual charging aperture, hydrogen enters reactor from a spout, and the bottom catalyst of reactor is supported by spiral drainage screen.
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| CN106565457B (en) * | 2015-10-09 | 2020-09-08 | 中国石化仪征化纤有限责任公司 | Method for preparing two products of polymer-grade terephthalic acid and isophthalic acid by taking mixed aromatic hydrocarbon as raw material |
| CN107963964A (en) * | 2017-11-02 | 2018-04-27 | 华东理工大学 | The preparation method of M-phthalic acid |
| CN108003006A (en) * | 2017-11-17 | 2018-05-08 | 杭州多向流化学科技有限公司 | A kind of method that terephthalic acid (TPA) and M-phthalic acid are produced using C8 aronmatic as raw material |
| CN108299182A (en) * | 2018-02-02 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of method that meta-xylene and paraxylene mixed oxidization prepare phthalic acid |
| CN111389314B (en) * | 2020-03-31 | 2020-12-11 | 南京延长反应技术研究院有限公司 | Built-in micro-interface unit enhanced reaction system and process for producing PTA (purified terephthalic acid) by PX (para-xylene) |
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| US2853514A (en) * | 1955-07-22 | 1958-09-23 | Olin Mathieson | Process for the preparation of aromatic carboxylic acids |
| CN1665770A (en) * | 2002-06-27 | 2005-09-07 | 欧洲技术承包与工程股份公司 | Method for separating water generated in production of aromatic polycarboxylic acid by aromatic hydrocarbon catalytic oxidation |
| CN1962598A (en) * | 2006-11-23 | 2007-05-16 | 浙江大学 | Method for producing benzene dicarboxylic acid by mixed dimethylbenzene cooxidation |
| CN101318890A (en) * | 2008-07-15 | 2008-12-10 | 中国石油化工股份有限公司 | Method for preparation of mixed benzol dimethanoic acid and benzene acetic acid |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2853514A (en) * | 1955-07-22 | 1958-09-23 | Olin Mathieson | Process for the preparation of aromatic carboxylic acids |
| CN1665770A (en) * | 2002-06-27 | 2005-09-07 | 欧洲技术承包与工程股份公司 | Method for separating water generated in production of aromatic polycarboxylic acid by aromatic hydrocarbon catalytic oxidation |
| CN1962598A (en) * | 2006-11-23 | 2007-05-16 | 浙江大学 | Method for producing benzene dicarboxylic acid by mixed dimethylbenzene cooxidation |
| CN101318890A (en) * | 2008-07-15 | 2008-12-10 | 中国石油化工股份有限公司 | Method for preparation of mixed benzol dimethanoic acid and benzene acetic acid |
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