CN101318890A - Method for preparation of mixed benzol dimethanoic acid and benzene acetic acid - Google Patents
Method for preparation of mixed benzol dimethanoic acid and benzene acetic acid Download PDFInfo
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- CN101318890A CN101318890A CNA2008100224736A CN200810022473A CN101318890A CN 101318890 A CN101318890 A CN 101318890A CN A2008100224736 A CNA2008100224736 A CN A2008100224736A CN 200810022473 A CN200810022473 A CN 200810022473A CN 101318890 A CN101318890 A CN 101318890A
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Abstract
The invention discloses a method for making mixed benzene dicarbonic acids and a phenyl acetic acid, comprising the following steps of: performing an oxidization reaction by using mixed xylenes as a raw material, oxygen or oxygen in compressed air as an auxiliary raw material, an acetic acid as a solvent, cobalt acetate and manganese acetate as catalysts, a hydrobromic acid as an auxiliary catalyst, at a temperature of between 100 and 250 DEG C and a pressure of between 0.5 and 2.5 MPa for 50 to 180 minutes to obtain a mixture of mixed benzene dicarbonic acids of p-phthalic acid, m-phthalic acid and o-phthalic acid and a phenyl acetic acid; separating the phenyl acetic acid and the mixed benzene dicarbonic acids. The novel method for producing the phenyl acetic acid of the invention is a technical innovation with high economic value. The oxidization of phenylethane and the separation and refining of an oxide of the phenylethane are applied throughout the technological process for making mixed benzene dicarbonic acids from four components of the mixed xylenes, which is a technical problem in the field. The method creatively solves the technical problem.
Description
Technical field
The present invention relates to a kind of manufacture method of Chemicals, be specifically related to the manufacture method of a kind of pure mixed phthalic acid and toluylic acid.Pure mixed phthalic acid wherein (PMA) is a kind of new product, and its main component is m-phthalic acid, terephthalic acid and phthalic acid (phthalic anhydride).Pure mixed phthalic acid (PMA) can be used as the new polyester resin---the raw material of poly-pure mixed phthalic acid glycol ester, also can mix use with pure terephthalic acid (PTA) according to various ratios, and make the vibrin of different use propertieies and purposes.
Toluylic acid is the fine chemical material of having many uses, and can be used for medicine, spices, dyestuff, sterilant and plant-growth regulator etc.
Background technology
Present polyester industrial chain product and technological line are: aromatic hydrocarbons extracting → xylol (MX) → p-Xylol (PX) → pure terephthalic acid (PTA) → polyester (PET) does not comprise that the polyester downstream industry is four product chain links.The polyester here (PET) is a polyethylene terephthalate.
Xylol is a kind of industrialized market product.The main component of xylol is m-xylene, p-Xylol, o-Xylol, and the ethylbenzene about 6～7%.The primary structure feature of xylol is to contain the hydrocarbon polymer that 8 carbons contain 1 phenyl ring simultaneously, because the singularity of structure, the boiling point of 4 main ingredients of xylol is close, and rectifying separation or extracting and separating be difficulty very.Present industrialized separation method mainly is to adopt adsorption separating method.When p-Xylol or m-xylene are separated, other 3 integral parts are transformed into the structure of target product by disproportionation, isomerization process.
The boiling point of p-Xylol, m-xylene, o-Xylol and ethylbenzene and the content parameter in Mixed XYLENE are referring to table 1:
The boiling point of table 1 p-Xylol, m-xylene, o-Xylol and ethylbenzene and the content in Mixed XYLENE
| Dimethylbenzene (mixing) MX | P-Xylol PX | M-xylene M ' X | O-Xylol OX | Ethylbenzene | |
| Boiling point (℃) | 135～145 | 138.5 | 139.1 | 144.4 | 136.2 |
| Content (%) roughly | 100 | 20～24 | 40～48 | 20～24 | 6～7 |
P-Xylol (PX) is used for oxidation and generates terephthalic acid (TA), obtains pure terephthalic acid (PTA) product through hydrofining technology again.M-xylene (M ' X) be used for oxidation generation m-phthalic acid, obtain smart m-phthalic acid (PIA) product through hydrofining technology again.
In order to improve the use properties of polyester as the drink bottle raw material, increase barrier, reduce crystallization velocity and degree of crystallinity, method commonly used now is to add an amount of m-phthalic acid (PIA) in pure terephthalic acid (PTA) raw material, as the 3rd monomer together with ethylene glycol (EG) esterification, produce the polyester for bottle resin through polycondensation again.
In terephthalic acid (PTA), add an amount of m-phthalic acid (PIA) and phthalic acid simultaneously, has similar effect to an amount of m-phthalic acid of interpolation (PIA) in terephthalic acid (PTA), can reduce the compound with regular structure of polyester macromolecule chain, reduce the crystallization velocity and the crystallizing power of polyester, can increase transparency and gas barrier property as polyester bottles.
The inventor notices: since terephthalic acid and m-phthalic acid are that raw material production obtains with xylol (MX) all, and to consume a large amount of energy separating and be transformed in the process of p-Xylol or m-xylene structure, increase great deal of investment, so direct production part pure mixed phthalic acid (PMA) product is that to have market rational, has practicality.200610154821.6 number Chinese patent application discloses a kind of " the xylol co-oxidation is produced the method for phthalic acid ": the xylol raw material is added in the oxidation reactor with acetate solvate and cobalt, manganese, bromine three-way catalyst, be blown into air or oxygen-containing gas, 150～220 ℃ of temperature, 0.5 carry out oxidizing reaction 30～150min under the～2.5MPa pressure, obtain containing the pure mixed phthalic acid slurry ... separate obtaining the benzene dicarboxylic acid product.Yet at the application's invention task, the associated viscera of the document and the content of prior art are basic identical.For example, as far back as the seventies in 20th century, China is domestic just to be begun to have in a large number about the Studies on Oxidation of Xylol report, for example: 1, " between xylol oxidation system, terephthalic acid " (petrochemical complex, Petrochemical Technology, 1970 01 phases); 2, " between xylol oxidation system, terephthalic acid " (fine-chemical intermediate, Fine Chemical Intermediates, 1971 04 phases); 3, " Studies on Oxidation of Xylol " (Lin Mei and, Five City University's journal (social science version), Journal ofWuyi University, Z1 phase in 1989); 4, " terephthalic acid between the xylol preparation " (Li Zhongyi, etc., Dalian University of Technology's journal, 1989 04 phases); 5, " catalysis of dimethylbenzene oxidation and catalysis restraining effect " (Chen Zhenghua, etc., chemistry of fuel journal, 04 phase of nineteen eighty-three); 6, " selective oxidation of Hydroxylamine HCL cobalt complex catalytic mixing dimethylbenzene " (Chen Junru, etc., chemical research and application, 178-181 page or leaf, 1970 01 phases).Above research report and data have introduced the use m-xylene respectively and p xylene oxidation is produced m-phthalic acid, method of terephthalic acid, has introduced the method for utilizing xylol (mixture of m-xylene, p-Xylol, o-Xylol) to produce pure mixed phthalic acid (m-phthalic acid, terephthalic acid, phthalic acid).More than disclosed research report different with No. 200610154821.6 patent applications be: open source literature that all have retrieved and patent (application) all do not relate to such situation, be in the resulting xylol product of suitability for industrialized production, except p-Xylol, m-xylene, o-Xylol, also has ethylbenzene.Existing technology can not be separated ethylbenzene fully with other three components.The oxidation of ethylbenzene and the separation of oxide compound thereof and refining will be applied in xylol of the present invention (four components) oxidation and produce the pure mixed phthalic acid technological process of production all the time become the technical barrier of this area.
The production method that toluylic acid is commonly used has two kinds: the one, and be raw material with toluene, generate benzyl chloride with the chlorine reaction, generate benzyl cyanide through cyaniding, obtain toluylic acid through hydrolysis, acidifying again.The 2nd, be raw material with toluene, generate benzyl chloride with the chlorine reaction, in the presence of the high reactivity complex catalyst, carry out carbonylation reaction with benzyl chloride and CO and make toluylic acid.Toluylic acid is used for the ultimate production that the penicillin production process improves penicillin G, also as the raw material of producing spices, sterilant and plant-growth regulator etc.Domestic about 82% toluylic acid product is used to produce penicillin at present.
Summary of the invention
The manufacture method that the purpose of this invention is to provide a kind of pure mixed phthalic acid and toluylic acid, this method are studied pure mixed phthalic acid and are utilized as target product, and are to utilize the xylol of C8 as raw material, wherein contain ethylbenzene.
Technical scheme of the present invention is: the manufacture method of a kind of pure mixed phthalic acid and toluylic acid the steps include:
Adopt xylol (MX) to make raw material, with the oxygen in oxygen or the pressurized air is auxiliary material, with acetic acid is solvent, with Cobaltous diacetate, manganese acetate is that catalyzer, Hydrogen bromide are cocatalyst, 100～250 ℃ of temperature, carry out oxidizing reaction under pressure 0.5～2.5MPa condition, by the reaction times of 50～180min, final pure mixed phthalic acid (MA) and the toluylic acid slurry mix that contains terephthalic acid, m-phthalic acid, phthalic acid composition that generate of oxidizing reaction;
Toluylic acid is separated with pure mixed phthalic acid.
Described separating step, the characteristics that can utilize the physical properties of monoprotic acid and diprotic acid to differ greatly, Separation of Benzene acetate and pure mixed phthalic acid.
Say that more specifically and more optimally the manufacture method of pure mixed phthalic acid of the present invention and toluylic acid is characterized in that, step is as follows:
(1), oxidized portion
(1)-and a, be main raw material with the xylol that contains ethylbenzene, be auxiliary material with the oxygen in oxygen or the pressurized air, with acetic acid solvent; Catalyst cobalt, manganese, three kinds of ionic total mass concentrations of bromine are 100-4000ppm, and cobalt, manganese mass ratio are 0.5～25, and the atomic ratio of metal ion ionic concn and bromide anion is 0.1～4.5.100～250 ℃ of temperature, carry out oxidizing reaction under pressure 0.5～2.5MPa condition, by carrying out oxidizing reaction under the reaction times of 50～180min, generate pure mixed phthalic acid (MA) and toluylic acid.
(1)-b, the slurry pure mixed phthalic acid (MA) of oxidizing reaction is further made trickle grain growth in the liquid by multistep crystalline form, crystallisation step adopts 3～5 grades of crystallization modes, preferred level Four crystallization, first step crystalline temperature is lower than 0～50 ℃ of oxidizing temperature, second stage Tc is at 150～170 ℃, third stage Tc is at 80～150 ℃, and fourth stage Tc is at 15～80 ℃.The solid suspension that crystallization forms is in oxidation liquid, and toluylic acid then is dissolved in the oxidation liquid, discharges the solid-liquid mixed slurry from reactor lower part;
(1)-the further desuperheat of material, decompression behind the c, crystallization.Temperature of charge is reduced to 5～20 ℃, pressure is at 100～150KPa, pure mixed phthalic acid (MA) and toluylic acid that reaction is generated all crystallize out, by filtering or the method for centrifugation realizes solid-liquid separation, pass through dehumidification system again solvent contained in the solid-state pure mixed phthalic acid (MA) and in the mixture of solid-state pure mixed phthalic acid and toluylic acid etc. is removed;
At crystal system, what at first crystallize out is the pure mixed phthalic acid solid.Along with the reduction of slurry temperature, when temperature reached the fusing point of toluylic acid, the crystalline solid that follow-up crystallizer obtains was the mixture of pure mixed phthalic acid and toluylic acid.The normal pressure fusing point of toluylic acid is 77 ℃.
The oxidation reactor liquidus temperature is a scope, and is similar with the production technique of m-phthalic acid (PIA) to present pure terephthalic acid (PTA), is divided into two kinds of low-temperature oxidation, high temperature oxidations, and its technical characterstic lays particular emphasis on respectively to reduce and consumes and the increase speed of response.Oxidizing reaction temperature is controlled at about 180 ℃ in general.
Oxidation reactor can use agitator, increases compressed-air actuated dispersiveness and reaction uniformity.Pressurized air enters the reactor liquid phase by sparger.
(2), toluylic acid separates and the toluylic acid FF
(2)-and a, because the boiling point of phenylacetic aldehyde is 195 ℃, distill earlier and collect at the 195 ℃ of left and right sides phenylacetic aldehydes when material enters the fluidized-bed pre-heating stage and send oxidation reactor further oxidation through condensation.
(2)-and b, for the mixture of pure mixed phthalic acid and toluylic acid, adopt fluidized-bed heating distillatory way, at 265.5 ℃ or toluylic acid is separated a little more than 265.5 ℃.The toluylic acid atmospheric boiling point is 265.5 ℃.When the fluidised bed material temperature reached and surpass the boiling point of toluylic acid, toluylic acid was with rapid evaporation.
(2)-c, with the toluylic acid vapor condensation, collect for refining and use, reclaim heat simultaneously.
Perhaps, described step (2)-b adopts following operation with (2)-c:
(2)-bc, adopt the method Separation of Benzene acetate and the pure mixed phthalic acid of underpressure distillation, distillation temperature is at 100～270 ℃, working pressure is 60～100KPa, optimum temps is 180 ℃, optimum operation pressure is 20KPa, to reduce the fluidized bed process temperature, avoid the phthalic anhydride distillation to enter the toluylic acid system simultaneously.
(3), pure mixed phthalic acid FF
(3)-a, hydrogenating reduction are refining
The dried pure mixed phthalic acid of desolventizing (MA) solid, and isolate pure mixed phthalic acid (MA) solid that obtains after the toluylic acid and be dissolved in 150～300 ℃ of hot water, this moment, reactor pressure was 0.5～9.0MPa, the solubleness of pure mixed phthalic acid (MA) in water is 25～30%, and the aqueous solution that is dissolved with pure mixed phthalic acid is according to 0.001～0.0025Nm
3/ h MA adds hydrogen, adopt palladium carbon catalyst (" palladium carbon catalyst " is the public technology of this area), by hydrogenation reaction a small amount of formaldehyde group (contraposition carboxyl benzaldehyde, a position carboxyl benzaldehyde, ortho position carboxyl benzaldehyde) that generates because of oxidation is reduced into methyl group, easily is dissolved in contraposition tolyl acid, a position tolyl acid, the ortho position tolyl acid of water.Residence time of material is 20～60min in the reactor, and the more excellent residence time is 45min.More excellent temperature and pressure condition is 286 ℃ and 7.5MPa respectively.
Perhaps, described step (3)-a adopts following operation:
The aqueous solution hydrogenation reaction of pure mixed phthalic acid (MA) is made catalyzer (" amorphous nickel catalyzer " can with reference to " catalyzer that cyclohexane oxidation is used ") with amorphous nickel, carries out hydrogenation reduction in magnetic stablizing bed catalyst system.It is stable to adopt magnetic stablizing bed technology to keep the suspension of catalyzer, dispersion and relative position.In order to increase reaction time, can design and make reaction medium cycle through magnetic stablizing bed catalyst system.Magnetic stablizing bed technology and amorphous nickel catalyst technology have Chinese patent: " a kind of magnetic stablizing bed hydrogenating alkyl anthraquinone method " can be for reference, the number of applying for a patent: 200410037675.X.
Perhaps, described step (3)-a adopts following operation:
Pure mixed phthalic acid (MA) is made with extra care and is obtained pure mixed phthalic acid through hydrogen peroxide oxidation, passes through dewatering means such as crystallization, filtration or centrifugation again, send the drying machine drying, obtains the high purity pure mixed phthalic acid, promptly smart pure mixed phthalic acid (PMA) product.
Concrete operations are: the dried pure mixed phthalic acid of desolventizing (MA) solid, and isolate pure mixed phthalic acid (MA) solid that obtains after the toluylic acid and be dissolved in 150～300 ℃ of hot water, this moment, reactor pressure was 0.5～9.0MPa, the solubleness of pure mixed phthalic acid (MA) in water is 25～30%, adding concentration to the aqueous solution that is dissolved with pure mixed phthalic acid is 10～25% hydrogen peroxide, utilize the oxidation susceptibility of hydrogen peroxide, with carboxyl benzaldehyde (CBA) (contraposition carboxyl benzaldehyde, between the position carboxyl benzaldehyde, the ortho position carboxyl benzaldehyde) is oxidized to phthalic acid, with tolyl acid (contraposition tolyl acid, between the position tolyl acid, the ortho position tolyl acid) is oxidized to phthalic acid.The addition of hydrogen peroxide obtains according to the cubage of CBA among the MA and tolyl acid.For example, when the content (weight) of CBA was 5000ppm, when tolyl acid content (weight) was 400ppm, interpolation concentration was hydrogen peroxide 2000～3300ppm of 20%.Residence time of material is 10～60min in the reactor, and the more excellent residence time is 25min.More excellent temperature and pressure condition is 286 ℃ and 7.5MPa respectively.The hydrogen peroxide concentration and the addition that add to reactor have determined the concentration of hydrogen peroxide in the reactor, and the concentration of hydrogen peroxide then determines the residence time of reaction mass in the reactor.More excellent hydrogen peroxide material concentration is 15%.
The hydrogen peroxide oxidation purification techniques is compared with the hydrofining technology, avoided from the aqueous solution, extracting the operation of tolyl acid reuse, water dissolution, recrystallization operation have for the second time been omitted, omitted expensive palladium-carbon catalyst, reduced equipment investment cost, save energy consumption and reduction production run cost.
Pure mixed phthalic acid purified content is that patent CN200610154821.6 does not address, and also is to produce to meet the quality problems that polyester industrial uses the essential solution of product institute of standard.Patent application CN200610154821.6 (specification sheets, the 6th page, row last) only be " slurry is sent into first crystallizer 8 through after heating up; first crystallizer 8 is also sent into the part air simultaneously and carried out supplemental; ... " be the tolyl acid of (CBA) of 4000～6000ppm content and 400～500ppm content to be transformed into " impurity to carboxyl benzaldehyde (4-CBA) content less than 200ppm ", and " impurity 4-CBA content is less than 200ppm ".Patent (application) CN200610154821.6 then says: " can further purify by recrystallization method if will obtain more highly purified single component carboxylic acid ", this also is impossible.If possible, the process for refining of pure terephthalic acid's product (PTA) of industrial mass production is actually impracticable as long as adopt " recrystallization method purification " just passable now.
(3)-and b, through after the hydrogenation reaction, most of carboxaldehyde radicals phenylformic acid is converted into tolyl acid.The pure mixed phthalic acid aqueous solution is sent to the crystallizer crystallization, separates out the pure mixed phthalic acid solid.Be dissolved in the water the mixed methyl phenylformic acid through gas carry, thin-film evaporator, perhaps pass through the membrane separation technique after separating, send oxidation reactor back to.The pure mixed phthalic acid that crystallization is separated out obtains the higher pure mixed phthalic acid solid of purity through filtering or centrifugation.Dissolve the pure mixed phthalic acid solid once more with deionized water, crystallization once more, filtration or centrifugation again through super-dry, obtain high purity pure mixed phthalic acid product, are called smart pure mixed phthalic acid (PMA) again.
(4), phthalic anhydride and two pure mixed phthalic acid separates
(PMA) further processes to the high purity pure mixed phthalic acid, adopt the isolating method of similar toluylic acid and pure mixed phthalic acid, under 200～280 ℃ of conditions, with fluidized-bed heating distillatory way phthalic acid (phthalic anhydride) fractionation by distillation is come out, collect through condensation, can obtain phthalic anhydride (phthalic acid) product and smart two respectively and mix phthalic acid (PITA) product.Smart two mix in the phthalic acid (PITA), and m-phthalic acid content accounts for 66.67%, and terephthaldehyde's acid content accounts for 33.33%.
Equally also can adopt the method for fluidized-bed underpressure distillation, reduce the fluidized bed process temperature.
The pure mixed phthalic acid (MA) that obtains from oxidation reactor is still containing organic impurity with the toluylic acid after separating, removes impurity through refining step, can obtain smart pure mixed phthalic acid (PMA) product.
Toluylic acid can obtain purified toluylic acid product after removing impurity.
The present invention has following prioritization scheme:
1, increase has following steps in oxidation step (1):
(1)-d, oxidation reactor gas phase reclaim heat by interchanger, reenter oxidation reactor after the condensations such as acetic acid, xylol (MX), less water.Acetic acid in the part non-condensable gas send solvent recovering system to reclaim, and reduces the loss, and removes moisture and organic impurity simultaneously.
(1)-and e, can adopt in crystallizer the method that adds little air, make reaction intermediate further transform to product.
2, increase between hydrogenating reduction purification step (3)-b and step (3)-d following steps arranged:
(3)-c, secondary oxidation are refining
The solid-liquid mixed slurry that contains the solid pure mixed phthalic acid of discharging from the oxidation reactor bottom enters crystal system and carries out pressure and temperature reducing, and the pure mixed phthalic acid (MA) and the toluylic acid that make reaction generate all crystallize out.In crystallizer, add small amount of hot air, make that the further oxidation conversion of part aldehyde radical is a carboxyl.This moment slurry temperature than higher, catalyzer also exists, and can also bring into play katalysis, can so that oxidizing reaction further carry out.So further improving is that not only bubbling air in first crystallizer along with the reduction of thermograde, also can feed warm air in second, third crystallizer.By secondary oxidation, make carboxaldehyde radicals phenylformic acid (perhaps being called carboxyl benzaldehyde) further be converted into phthalic acid, reduce impurity, increase target product output.
(3)-d, three oxidations (hydrogen peroxide oxidation) are refining
Carry out oxide purification with hydrogen peroxide (hydrogen peroxide) as oxygenant.After oxidizing reaction, through crystallization (secondary oxidation), the dried pure mixed phthalic acid of desolventizing (MA) solid is dissolved in the certain density hydrogen peroxide, perhaps earlier pure mixed phthalic acid (MA) solid is dissolved in the water, in pure mixed phthalic acid (MA) aqueous solution, add hydrogen peroxide, both ratios are 1: 0.1～1: 1 (wt%), utilize the oxidation susceptibility of hydrogen peroxide, a small amount of carboxaldehyde radicals phenylformic acid (the contraposition carboxyl benzaldehyde in the pure mixed phthalic acid (MA), between the position carboxyl benzaldehyde, the ortho position carboxyl benzaldehyde) aldehyde radical is oxidized to carboxyl, is converted into phthalic acid.
According to different target levels of product quality, the pure mixed phthalic acid product can be without hydrofining or hydrogen peroxide oxidation refining step and is dispatched from the factory, though the content of carboxaldehyde radicals phenylformic acid (carboxyl benzaldehyde) also meets quality standard than higher in the product.
Above step (2)-b, (the 2)-c or the working order of (2)-bc and step (3), also can do following change:
Refining to pure mixed phthalic acid with the mixture of toluylic acid, remove impurity and again toluylic acid is separated with pure mixed phthalic acid afterwards, obtain pure mixed phthalic acid (PMA) product and toluylic acid product respectively.
(PMA) further processes to the high purity pure mixed phthalic acid, and phthalic acid (phthalic anhydride) is separated, and can obtain phthalic anhydride (phthalic acid) product and smart two and mix phthalic acid (PITA) product.Smart two mix the middle m-phthalic acid content of phthalic acid (PITA) accounts for 66.67%, and terephthaldehyde's acid content accounts for 33.33%.
Data shows, 77 ℃ of the fusing points of toluylic acid, 265.5 ℃ of boiling points; Terephthalic acid can not fusion, 300 ℃ of distillations; 345-347 ℃ of m-phthalic acid fusing point can distil; 131.6 ℃ of phthalic anhydride (the dehydration form of phthalic acid) fusing points, 295 ℃ of boiling points (distillation).
The composition of three kinds of isomer roughly is in smart pure mixed phthalic acid (PMA) product: m-phthalic acid 50%, terephthalic acid 25%, phthalic acid 25%.
The present invention adopts xylol direct oxidation production pure mixed phthalic acid (PMA), and as the raw material of polyester, compare with present production technique, new product chain has been skipped p-Xylol (PX) product chain link, can be so that the production cost of a part of polyester product reduces significantly.Because the performance of this part polyester product is special, fusing point is relatively low, and the polymolecularity of macromolecular structure increases, and being expected to increases the market Application Areas of vibrin as the plastic prod raw material.Therefore the present invention can promote the overall market competitive capacity of polyester product chain.The oxidation of ethylbenzene and the separation of oxide compound thereof and refining will be applied in xylol (four components) oxidation and produce the pure mixed phthalic acid technological process of production all the time become the technical barrier of this area.The present invention for the first time, has creatively solved this technical barrier.
In order to be different from xylol (MX), the present invention adopts (M ' X) English code name as m-xylene.
At present m-phthalic acid (PIA) also is to be raw material with xylol (MX), adopt fractionation by adsorption and disproportionation, isomerized method to obtain m-xylene (M ' X) earlier, through peroxidation, refining and make, because scale is smaller, production cost is more taller than terephthalic acid (PTA) again.A part adopts an amount of m-phthalic acid (PIA) to be mixed into the polyester product of producing with ethylene glycol (EG) esterification and polycondensation among the pure terephthalic acid (PTA), can adopt an amount of pure mixed phthalic acid (PMA) to substitute m-phthalic acid (PIA).Composition can be slightly different, but performance can be suitable, and cost reduces a lot.
Data shows that the fusing point of polyethylene glycol isophthalate is 65 ℃; The fusing point of the polymkeric substance that obtains with ethylene glycol esterification, polycondensation after PTA mixes with PIA one to is 120 ℃.The fusing point of the polymkeric substance behind expectation PITA (ratio of PIA and PTA is two-to-one) and ethylene glycol esterification, the polycondensation ester will be between 65～120 ℃.
Pure mixed phthalic acid (PMA) is used according to the different ratios blending with terephthalic acid (PTA), can obtain use properties and the similar polyester product of present bottle grade polyester resin, and the different novel polyester products of multiple performance.
Because it is very big to separate the difficulty of ethylbenzene from xylol, and almost can not realize separating fully of ethylbenzene and dimethylbenzene, so the present invention takes separation processes flow process behind the initial oxidation, the characteristics of utilizing diprotic acid and monoprotic acid physical properties to differ greatly, the realization toluylic acid separates with phthalic acid.
The present invention also is the method for a new production toluylic acid product, is a technological innovation that higher economic worth is arranged.
Embodiment
Embodiment 1, the manufacture method of pure mixed phthalic acid and toluylic acid, and technical process mainly is divided into four parts, i.e. and oxidation, toluylic acid separate and toluylic acid is refining, pure mixed phthalic acid is refining, and the separating of phthalic anhydride and two pure mixed phthalic acid.Specification of quality according to product is different with standard, and process for refining can be given up or simplify.
(1), oxidized portion
With the xylol is main raw material, with the oxygen in the pressurized air is auxiliary material, is solvent with acetic acid, is that catalyzer, Hydrogen bromide are cocatalyst with Cobaltous diacetate, manganese acetate, under gentle relatively temperature condition, carry out oxidizing reaction, generate pure mixed phthalic acid (MA) and toluylic acid.Described " Wen He temperature condition relatively " is: about 180 ℃ of temperature, pressure 0.5～2.5Mpa, the reaction times of 50～180min.
Pure mixed phthalic acid (MA) partial crystallization forms solid, is suspended in the oxidation liquid.Toluylic acid then is dissolved in the oxidation liquid.Discharge the solid-liquid mixed slurry from reactor lower part, to react the pure mixed phthalic acid (MA) and the toluylic acid that generate at crystal system by the measure of pressure and temperature reducing all crystallizes out, by filtering or the method for centrifugation realizes solid-liquid separation, pass through dehumidification system again solvent contained in the solid-state pure mixed phthalic acid (MA) and in the mixture of solid-state pure mixed phthalic acid and toluylic acid etc. is removed.Oxidation reactor can use agitator, increases compressed-air actuated dispersiveness and reaction uniformity.Pressurized air enters the reactor liquid phase by sparger.
(2), toluylic acid separates and the toluylic acid FF
For the mixture of pure mixed phthalic acid and toluylic acid, we adopt fluidized-bed heating distillatory way that toluylic acid is separated.The toluylic acid atmospheric boiling point is 265.5 ℃.When the fluidised bed material temperature reached and surpass the boiling point of toluylic acid, toluylic acid was with rapid evaporation.With the toluylic acid vapor condensation, collect for refining and use, reclaim heat simultaneously.
Because the boiling point of phenylacetic aldehyde is 195 ℃, material enters that the fluidized-bed pre-heating stage distills and collects through condensation and send oxidation reactor further oxidation.
(3), pure mixed phthalic acid FF
(3)-a, hydrogenating reduction are refining
The dried pure mixed phthalic acid of desolventizing (MA) solid, and isolate pure mixed phthalic acid (MA) solid that obtains after the toluylic acid and be dissolved in the hot water, in the aqueous solution of pure mixed phthalic acid (MA), add compression hydrogen, adopt palladium carbon catalyst, by hydrogenation reaction a small amount of formaldehyde group (contraposition carboxyl benzaldehyde, a position carboxyl benzaldehyde, ortho position carboxyl benzaldehyde) that generates because of oxidation is reduced into methyl group, easily is dissolved in contraposition tolyl acid, a position tolyl acid, the ortho position tolyl acid of water.
Through after the hydrogenation reaction, most of carboxaldehyde radicals phenylformic acid is converted into tolyl acid.The pure mixed phthalic acid aqueous solution is sent to the crystallizer crystallization, separates out the pure mixed phthalic acid solid.Be dissolved in the water the mixed methyl phenylformic acid through gas carry, thin-film evaporator, perhaps pass through the membrane separation technique after separating, send oxidation reactor back to.The pure mixed phthalic acid that crystallization is separated out obtains the higher pure mixed phthalic acid solid of purity through filtering or centrifugation.Dissolve the pure mixed phthalic acid solid once more with deionized water, crystallization once more, filtration or centrifugation again through super-dry, obtain high purity pure mixed phthalic acid product, are called smart pure mixed phthalic acid (PMA) again.
(3)-b, secondary oxidation are refining
The solid-liquid mixed slurry that contains the solid pure mixed phthalic acid of discharging from the oxidation reactor bottom enters crystal system and carries out pressure and temperature reducing, and the pure mixed phthalic acid (MA) and the toluylic acid that make reaction generate all crystallize out.In crystallizer, add small amount of hot air, make that the further oxidation conversion of part aldehyde radical is a carboxyl.This moment slurry temperature than higher, catalyzer also exists, and can also bring into play katalysis, can so that oxidizing reaction further carry out.So not only bubbling air in first crystallizer along with the reduction of thermograde, also can feed warm air in second, third crystallizer.By secondary oxidation, make carboxaldehyde radicals phenylformic acid (perhaps being called carboxyl benzaldehyde) further be converted into phthalic acid, reduce impurity, increase target product output.
(3)-c, three oxidations (hydrogen peroxide oxidation) are refining
Carry out oxide purification with hydrogen peroxide (hydrogen peroxide) as oxygenant.After oxidizing reaction, be dissolved in the certain density hydrogen peroxide through crystallization (secondary oxidation), the dried pure mixed phthalic acid of desolventizing (MA) solid, perhaps earlier pure mixed phthalic acid (MA) solid is dissolved in the water, in pure mixed phthalic acid (MA) aqueous solution, add certain density hydrogen peroxide, utilize the oxidation susceptibility of hydrogen peroxide, the aldehyde radical of a small amount of carboxaldehyde radicals phenylformic acid in the pure mixed phthalic acid (MA) (contraposition carboxyl benzaldehyde, a position carboxyl benzaldehyde, ortho position carboxyl benzaldehyde) is oxidized to carboxyl, is converted into phthalic acid.
The consumption of hydrogen peroxide can be in analytical test pure mixed phthalic acid (MA) on the basis of carboxaldehyde radicals benzoic acid content, considers concentration, oxidation efficiency and the rate of loss of hydrogen peroxide, calculates gross data, and concrete processing parameter can be proofreaied and correct in practice.
Through dewatering means such as crystallization, filtration or centrifugations, send the drying machine drying through hydrogen peroxide oxidation purified pure mixed phthalic acid, obtain the high purity pure mixed phthalic acid, promptly smart pure mixed phthalic acid (PMA) product.
The hydrogen peroxide oxidation purification techniques is compared with the hydrofining technology, avoided from the aqueous solution, extracting the operation of tolyl acid reuse, water dissolution, recrystallization operation have for the second time been omitted, omitted expensive palladium-carbon catalyst, reduced equipment investment cost, save energy consumption and reduction production run cost.
According to different target levels of product quality, the pure mixed phthalic acid product can be without hydrofining or hydrogen peroxide oxidation refining step and is dispatched from the factory, though the content of carboxaldehyde radicals phenylformic acid (carboxyl benzaldehyde) also meets quality standard than higher in the product.
(4), phthalic anhydride and two pure mixed phthalic acid separates
(PMA) further processes to the high purity pure mixed phthalic acid, adopt the isolating method of similar toluylic acid and pure mixed phthalic acid, with fluidized-bed heating distillatory way phthalic acid (phthalic anhydride) fractionation by distillation is come out, collect through condensation, can obtain phthalic anhydride (phthalic acid) product and smart two respectively and mix phthalic acid (PITA) product.Smart two mix in the phthalic acid (PITA), and m-phthalic acid content accounts for 66.67%, and terephthaldehyde's acid content accounts for 33.33%.
Equally also can adopt the method for fluidized-bed underpressure distillation, reduce the fluidized bed process temperature.
Embodiment 2, and is substantially the same manner as Example 1, but following change is arranged:
The temperature of step (1) oxidized portion is at 100～160 ℃;
Separating and the toluylic acid FF at step (2) toluylic acid, is method Separation of Benzene acetate and the pure mixed phthalic acid that adopts underpressure distillation, to reduce the fluidized bed process temperature, avoids the phthalic anhydride distillation to enter the toluylic acid system simultaneously;
At step (3) pure mixed phthalic acid FF, when hydrogenating reduction was made with extra care, the aqueous solution hydrogenation reaction of pure mixed phthalic acid (MA) also can be made catalyzer with amorphous nickel, carries out in magnetic stablizing bed catalyst system.It is stable to adopt magnetic stablizing bed technology to keep the suspension of catalyzer, dispersion and relative position.In order to increase reaction time, can design and make reaction medium cycle through magnetic stablizing bed catalyst system.
Embodiment 3, and is substantially the same manner as Example 1, but following change is arranged:
The temperature of step (1) oxidized portion is at 190～250 ℃;
Be omitted in following two steps between hydrogenating reduction purification step (3)-b and step (the 3)-d:
(3)-c, secondary oxidation are refining
(3)-d, three oxidations (hydrogen peroxide oxidation) are refining.
Embodiment 4, and is substantially the same manner as Example 1, but following change is arranged: after the secondary oxidation step, do not carry out three oxidations.
Embodiment 5, and is substantially the same manner as Example 1, but following change is arranged: described step (2) adopts following operation:
(2)-and bc, adopting the method Separation of Benzene acetate and the pure mixed phthalic acid of underpressure distillation, distillation temperature is at 100～120 ℃, and working pressure is 60～70KPa, to reduce the fluidized bed process temperature, avoids the phthalic anhydride distillation to enter the toluylic acid system simultaneously.
Embodiment 6, and is substantially the same manner as Example 5, but distillation temperature is 260～270 ℃, and working pressure is 90～100KPa.
Embodiment 7, and is substantially the same manner as Example 5, but distillation temperature is 180 ℃, and working pressure is 80KPa.
Embodiment 8, substantially the same manner as Example 1, but following change is arranged: described step (2) increases following operation before: distill earlier and collect through condensation at the 195 ℃ of left and right sides phenylacetic aldehydes when material enters the fluidized-bed pre-heating stage and send oxidation reactor further oxidation.
Embodiment 9, and is substantially the same manner as Example 1, but following change is arranged:
Described multistep crystallization is the level Four crystallization, and first step crystalline temperature is lower than 0～50 ℃ of oxidizing temperature, and second stage Tc is at 150～170 ℃, and third stage Tc is at 80～150 ℃, and fourth stage Tc is at 15～80 ℃.
Claims (10)
1, the manufacture method of a kind of pure mixed phthalic acid and toluylic acid the steps include:
Adopt xylol to make raw material, with the oxygen in oxygen or the pressurized air is auxiliary material, with acetic acid is solvent, with Cobaltous diacetate, manganese acetate is that catalyzer, Hydrogen bromide are cocatalyst, 100～250 ℃ of temperature, carry out oxidizing reaction under pressure 0.5～2.5MPa condition, by the reaction times of 50～180min, final pure mixed phthalic acid and the toluylic acid slurry mix that contains terephthalic acid, m-phthalic acid, phthalic acid composition that generate of oxidizing reaction;
Toluylic acid is separated with pure mixed phthalic acid.
2, the manufacture method of pure mixed phthalic acid according to claim 1 and toluylic acid is characterized in that, concrete steps are:
(1), oxidized portion
(1)-and a, be main raw material with the xylol that contains ethylbenzene, be auxiliary material with the oxygen in oxygen or the pressurized air, with acetic acid solvent; Catalyst cobalt, manganese, three kinds of ionic total mass concentrations of bromine are 100～4000ppm, and cobalt, manganese mass ratio are 0.5～25, and the atomic ratio of metal ion ionic concn and bromide anion is 0.1～4.5.100～250 ℃ of temperature, carry out oxidizing reaction under pressure 0.5～2.5MPa condition, by carrying out oxidizing reaction under the reaction times of 50～180min, generate pure mixed phthalic acid and toluylic acid;
(1)-b, the slurry pure mixed phthalic acid of oxidizing reaction is further made trickle grain growth in the liquid by multistep crystalline form, crystallisation step adopts 3～5 grades of crystallization modes, the solid suspension that crystallization forms is in oxidation liquid, toluylic acid then is dissolved in the oxidation liquid, discharges the solid-liquid mixed slurry from reactor lower part;
(1)-the further desuperheat of material, decompression behind the c, crystallization.Temperature of charge is reduced to 5～20 ℃, pressure is at 100～150KPa, pure mixed phthalic acid and toluylic acid that reaction is generated all crystallize out, by filtering or the method for centrifugation realizes solid-liquid separation, through dehumidification system solvent contained in the solid-state pure mixed phthalic acid and in the mixture of solid-state pure mixed phthalic acid and toluylic acid etc. is removed again;
(2), toluylic acid separates and the toluylic acid FF
(2)-and a, because the boiling point of phenylacetic aldehyde is 195 ℃, distill earlier and collect at the 195 ℃ of left and right sides phenylacetic aldehydes when material enters the fluidized-bed pre-heating stage and send oxidation reactor further oxidation through condensation;
(2)-and b, for the mixture of pure mixed phthalic acid and toluylic acid, adopt fluidized-bed heating distillatory way, at 265.5 ℃ or toluylic acid is separated a little more than 265.5 ℃; When the fluidised bed material temperature reached and surpass the boiling point of toluylic acid, toluylic acid was with rapid evaporation;
(2)-c, with the toluylic acid vapor condensation, collect for refining and use, reclaim heat simultaneously;
Perhaps, described step (2)-b adopts following operation with (2)-c:
(2)-and bc, adopting the method Separation of Benzene acetate and the pure mixed phthalic acid of underpressure distillation, distillation temperature is at 100～270 ℃, and working pressure is 60～100KPa, to reduce the fluidized bed process temperature, avoids the phthalic anhydride distillation to enter the toluylic acid system simultaneously;
(3), pure mixed phthalic acid FF
(3)-a, hydrogenating reduction are refining
The dried pure mixed phthalic acid solid of desolventizing, and isolate the pure mixed phthalic acid solid that obtains after the toluylic acid and be dissolved in 150～300 ℃ of hot water, this moment, reactor pressure was 0.5～9.0MPa, the solubleness of pure mixed phthalic acid in water is 25～30%, and the aqueous solution that is dissolved with pure mixed phthalic acid is according to 0.001～0.0025Nm
3/ h MA adds hydrogen, adopts palladium carbon catalyst, by hydrogenation reaction a small amount of formaldehyde group that generates because of oxidation is reduced into methyl group, easily is dissolved in contraposition tolyl acid, a position tolyl acid, the ortho position tolyl acid of water; Residence time of material is 20～60min in the reactor;
Perhaps, described step (3)-a adopts following operation:
The aqueous solution hydrogenation reaction of pure mixed phthalic acid is made catalyzer with amorphous nickel, carries out hydrogenation reduction in magnetic stablizing bed catalyst system; It is stable to adopt magnetic stablizing bed technology to keep the suspension of catalyzer, dispersion and relative position;
Perhaps, described step (3)-a adopts following operation:
Pure mixed phthalic acid is made with extra care and is obtained pure mixed phthalic acid through hydrogen peroxide oxidation, passes through dewatering means such as crystallization, filtration or centrifugation again, send the drying machine drying, obtains the high purity pure mixed phthalic acid, promptly smart pure mixed phthalic acid product;
(3)-and b, through after the hydrogenation reaction, most of carboxaldehyde radicals phenylformic acid is converted into tolyl acid; The pure mixed phthalic acid aqueous solution is sent to the crystallizer crystallization, separates out the pure mixed phthalic acid solid; Be dissolved in the water the mixed methyl phenylformic acid through gas carry, thin-film evaporator, perhaps pass through the membrane separation technique after separating, send oxidation reactor back to; The pure mixed phthalic acid that crystallization is separated out obtains the higher pure mixed phthalic acid solid of purity through filtering or centrifugation; Dissolve the pure mixed phthalic acid solid once more with deionized water, crystallization once more, filtration or centrifugation again through super-dry, obtain high purity pure mixed phthalic acid product;
(4), phthalic anhydride and two pure mixed phthalic acid separates
The high purity pure mixed phthalic acid is further processed, under 200～280 ℃ of conditions, the phthalic acid fractionation by distillation is come out, collect, obtain phthalic anhydride product and smart two respectively and mix the phthalic acid product through condensation with fluidized-bed heating distillatory way;
Smart two mix in the phthalic acid, and m-phthalic acid content accounts for 66.67%, and terephthaldehyde's acid content accounts for 33.33%.
3, the manufacture method of pure mixed phthalic acid according to claim 2 and toluylic acid is characterized in that,
In described (2)-bc step, when the method Separation of Benzene acetate of employing underpressure distillation and pure mixed phthalic acid, distillation temperature is 180 ℃, and working pressure is 20KPa;
In described (3)-a step, when hydrogenating reduction was made with extra care, residence time of material was 45min in the reactor; The temperature and pressure condition is 286 ℃ and 7.5MPa respectively.
4, the manufacture method of pure mixed phthalic acid according to claim 2 and toluylic acid, it is characterized in that, concrete operations when described step (3)-a adopts the hydrogen peroxide oxidation operation are: the dried pure mixed phthalic acid solid of desolventizing, and isolate the pure mixed phthalic acid solid that obtains after the toluylic acid and be dissolved in 150～300 ℃ of hot water, this moment, reactor pressure was 0.5～9.0MPa, the solubleness of pure mixed phthalic acid in water is 25～30%, adding concentration to the aqueous solution that is dissolved with pure mixed phthalic acid is 10～25% hydrogen peroxide, utilize the oxidation susceptibility of hydrogen peroxide, carboxyl benzaldehyde is oxidized to phthalic acid, tolyl acid is oxidized to phthalic acid; Residence time of material is 10～60min in the reactor.
5, the manufacture method of pure mixed phthalic acid according to claim 4 and toluylic acid is characterized in that, residence time of material is 25min in the reactor; The temperature and pressure condition is 286 ℃ and 7.5Mpa respectively; The hydrogen peroxide material concentration is 15%.
6, the manufacture method of pure mixed phthalic acid according to claim 2 and toluylic acid is characterized in that, increasing in oxidation step (1) has following steps:
(1)-d, oxidation reactor gas phase reclaim heat by interchanger, reenter oxidation reactor after acetic acid, xylol, the less water condensation; Acetic acid in the part non-condensable gas send solvent recovering system to reclaim, and reduces the loss, and removes moisture and organic impurity simultaneously;
(1)-and e, adopt the method that in crystallizer, adds little air, make reaction intermediate further transform to product.
7, the manufacture method of pure mixed phthalic acid according to claim 2 and toluylic acid is characterized in that, increasing between hydrogenating reduction purification step (3)-b and step (3)-d has following steps:
(3)-c, secondary oxidation are refining
The solid-liquid mixed slurry that contains the solid pure mixed phthalic acid of discharging from the oxidation reactor bottom enters crystal system and carries out pressure and temperature reducing, and the pure mixed phthalic acid and the toluylic acid that make reaction generate all crystallize out; In crystallizer, add small amount of hot air, make that the further oxidation conversion of part aldehyde radical is a carboxyl;
(3)-d, three oxide purifications
Carry out oxide purification with hydrogen peroxide as oxidant: after oxidizing reaction, through crystallization, secondary oxidation, the dried pure mixed phthalic acid solid of desolventizing are dissolved in the certain density hydrogen peroxide, perhaps earlier the pure mixed phthalic acid solid is dissolved in the water, add hydrogen peroxide in the pure mixed phthalic acid aqueous solution, both weight ratios are 1: 0.1～1: 1; Utilize the oxidation susceptibility of hydrogen peroxide, the benzoic aldehyde radical of a small amount of carboxaldehyde radicals in the pure mixed phthalic acid is oxidized to carboxyl, be converted into phthalic acid.
8, the manufacture method of pure mixed phthalic acid according to claim 4 and toluylic acid is characterized in that, the working order of described step (2)-b, (2)-c or (2)-bc and step (3) is done following the change:
Refining to pure mixed phthalic acid with the mixture of toluylic acid, remove impurity and again toluylic acid is separated with pure mixed phthalic acid afterwards, obtain pure mixed phthalic acid product and toluylic acid product respectively;
The high purity pure mixed phthalic acid is further processed, phthalic acid is separated, can obtain phthalic anhydride product and smart two and mix the phthalic acid product; M-phthalic acid content accounts for 66.67% in the smart two mixed phthalic acids, and terephthaldehyde's acid content accounts for 33.33%.
9, the manufacture method of pure mixed phthalic acid according to claim 2 and toluylic acid, it is characterized in that, described step (1)-b adopts the level Four crystallization, first step crystalline temperature is lower than 0～50 ℃ of oxidizing temperature, second stage Tc is at 150～170 ℃, third stage Tc is at 80～150 ℃, and fourth stage Tc is at 15～80 ℃.
10, the manufacture method of pure mixed phthalic acid according to claim 2 and toluylic acid is characterized in that, uses agitator in the oxidation reactor of described step (1) oxidized portion, increases compressed-air actuated dispersiveness and reaction uniformity; Pressurized air enters the reactor liquid phase by sparger.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103012120A (en) * | 2011-09-27 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing terephthalic acid by oxidation refining process |
| CN103183607A (en) * | 2012-01-18 | 2013-07-03 | 逸盛大化石化有限公司 | Method for producing mixed aromatic dioctyl phthalate |
| CN106167451A (en) * | 2016-07-25 | 2016-11-30 | 浙江大学 | The method that meta-xylene produces aromatic carboxylic acids with ethylbenzene multistep cooxidation |
| CN106220489A (en) * | 2016-07-25 | 2016-12-14 | 浙江大学 | The method being raw material production M-phthalic acid with xylol raffinate |
| CN111362793A (en) * | 2020-03-05 | 2020-07-03 | 大连凯信石化科技有限公司 | Method for co-producing p-methyl benzoic acid in production of purified terephthalic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103012120A (en) * | 2011-09-27 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing terephthalic acid by oxidation refining process |
| CN103183607A (en) * | 2012-01-18 | 2013-07-03 | 逸盛大化石化有限公司 | Method for producing mixed aromatic dioctyl phthalate |
| CN103183607B (en) * | 2012-01-18 | 2016-06-15 | 逸盛大化石化有限公司 | A kind of production method mixing fragrant dioctyl phthalate |
| CN106167451A (en) * | 2016-07-25 | 2016-11-30 | 浙江大学 | The method that meta-xylene produces aromatic carboxylic acids with ethylbenzene multistep cooxidation |
| CN106220489A (en) * | 2016-07-25 | 2016-12-14 | 浙江大学 | The method being raw material production M-phthalic acid with xylol raffinate |
| CN106220489B (en) * | 2016-07-25 | 2018-12-18 | 浙江大学 | The method for producing M-phthalic acid as raw material using paraxylene raffinate |
| CN106167451B (en) * | 2016-07-25 | 2018-12-18 | 浙江大学 | The method of meta-xylene and ethylbenzene multistep cooxidation production aromatic carboxylic acids |
| CN111362793A (en) * | 2020-03-05 | 2020-07-03 | 大连凯信石化科技有限公司 | Method for co-producing p-methyl benzoic acid in production of purified terephthalic acid |
| CN111517940A (en) * | 2020-05-27 | 2020-08-11 | 大连凯信石化科技有限公司 | Method for co-producing m-methylbenzoic acid in production of isophthalic acid |
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