CN102026952A - Method for treating separated mother liquor from terephthalic acid refinement - Google Patents
Method for treating separated mother liquor from terephthalic acid refinement Download PDFInfo
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Abstract
Provided is a method for treating the separated mother liquor from terephthalic acid refinement whereby recovered water with little impurity is obtained cheaply and in large quantity from the primary mother liquor separated at the time of primary crystallization. The method of treating the mother liquor (primary mother liquor) wherein the refined terephthalic acid crystals (primary crystals) and mother liquor (primary mother liquor) are separated from the crystal slurry involves an evaporation process wherein the aforementioned mother liquor is evaporated in the presence of terephthalic acid crystals by heating and flash evaporation at a pressure below atmospheric pressure and separated into vapor and a mother liquor suspension of terephthalic acid crystals; a process whereby terephthalic-acid-containing crystals are separated from the aforementioned mother liquor suspension; and a process whereby the aforementioned vapor is condensed and condensed water is produced.
Description
Technical field
The present invention relates to when making the high purity terephthalic acid, the crystallization slurry by purified terephthalic is separated into the method that a mother liquor of crystallization and mother liquor is handled.The present invention is in high purity terephthalic acid's manufacturing, to handling effectively of a large amount of discharges from purified terephthalic crystalline separation mother liquor (mother liquor), thereby be used for utilizing again, carrying capacity of environment is little, save the technology of resource, wherein said high purity terephthalic acid's manufacturing comprises: in acetate solvate, in the presence of oxide catalyst liquid phase carry out p-Xylol oxidizing reaction and after making crude terephthalic acid, this crude terephthalic acid is dissolved in high temperature, in the highly compressed water, in the presence of noble metal catalyst, carry out hydrofinishing and obtain the aqueous solution, by carrying out that this aqueous solution is carried out multi-segment flash evaporation, cooling and separate out crystallization, generate slurry, reclaim the purified terephthalic crystallization.
The present invention especially is used for the method for purified aqueous solvent for following processing: under the pressure below the normal atmosphere, this separation mother liquor (mother liquor) is carried out flash distillation and heating, evaporation, it is concentrated, crystallization, be recovered in dissolved aromatic carboxylic acid effective constituent in this separation mother liquor (mother liquor), supply with, be effective to the manufacturing raw material of crude terephthalic acid, condensation simultaneously, reclaim vaporized steam, it can be effective to circularly the refining required water of crude terephthalic acid.
Background technology
In the past, high purity terephthalic acid's manufacturing is to be raw material with the p-Xylol, in acetate solvate, make crude terephthalic acid by liquid phase oxidation reaction, after the terephthalic acid that this is rough is dissolved in high temperature, the highly compressed water, carries out hydro-reduction and handle and obtain purified terephthalic.In this high purity terephthalic acid's manufacturing, the 4-carboxyl benzaldehyde (4-CBA) that is considered to representative impurity that crude terephthalic acid is contained carries out hydro-reduction, and be translated into be relatively easy to p-methylbenzoic acid (p-tA) separating of terephthalic acid after, carry out method such as release of pressure cooling (flash distillation, cooling or dodge cold) and generate terephthalic acid crystallization slurry by this having been dissolved terephthaldehyde's aqueous acid, carry out solid-liquid separation and reclaim, make the poor purified terephthalic crystallization of p-methylbenzoic acid (p-tA 150ppm is following).
With form the strong 4-carboxyl benzaldehyde (4-CBA) of chemical affinities such as eutectic or absorption with terephthaldehyde's acid crystal and compare, by being reduced into the p-methylbenzoic acid (p-tA) more weak with terephthalic acid crystal chemistry affinity, this will be the method that the performance and the crystalline separation and purification of terephthalic acid are easy to advantage.
Therefore, from the purified terephthalic Crystallization Separation separation mother liquor (mother liquor) be dissolved with the p-methylbenzoic acid of the approaching amount of the amount that generates by reduction and with state of saturation dissolved terephthalic acid amount with the 4-carboxyl benzaldehyde, be dissolved with in addition the trace that in crude terephthalic acid, contains metallic impurity (come from oxide catalyst cobalt, come from the iron of corrosion of equipment) etc.
In high purity terephthalic acid's manufacturing process, (with respect to crude terephthalic acid be 2～10 times amount) uses high purity water (pure water) such as ion exchange treatment as the aqueous solvent that is used to dissolve crude terephthalic acid because a large amount of, it is big that an above-mentioned mother liquor might as well, might as well carrying capacity of environment on matter on amount, and directly the depleted words become the disadvantage on the environment.In addition, the supply of refining needed a large amount of aqueous solvent (pure water) of crude terephthalic acid also has problems, and carries out various groping in order to address this problem.
Following method has been proposed: the solubleness of dissolved aromatic carboxylic acid organic composition is reduced in the patent documentation 1 (special public clear 56-35174 communique) by refrigerated separation mother liquor (mother liquor) further, make crystallization separated out the dissolved p-methylbenzoic acid purity drop terephthaldehyde's acid crystal carry out secondary crystal and separate out and reclaim, make its oxidizing reaction that circulates, coexists as described p-Xylol, improve the yield of terephthalic acid manufacturing process integral body thus.Though instructed the mother liquor (secondary mother liquid) that separated secondary crystal the reduction of essence to be arranged in the method as the processing load of draining, to the processing of this waste water then without any mentioning.
In addition, proposed following treatment process in the patent documentation 2 (spy opens flat 5-58948 communique): the secondary crystal that above-mentioned purity is low is mixed in described oxidation reaction medium and seeks the raising of terephthalic acid yield, and uses as the water of dissolving crude terephthalic acid with at least a portion of secondary mother liquid direct former state ground or after processing.Treatment process as this secondary mother liquid has proposed following treatment process in addition: carry out fractionation, rinse water that will be when distillatory water is used for Separation and Recovery purified terephthalic crystallization (primary crystallization).
This method as previously mentioned, owing to contain p-methylbenzoic acid (the p-tA content 300～1500ppm) that in secondary mother liquid, contains in large quantities, contain metallic impurity etc. in addition, not treated at this secondary mother liquid, as the water of dissolving crude terephthalic acid when directly re-using, can not use in large quantities, be limited to limited amount seldom.
In addition, consider to evaporate as the method for handling this secondary mother liquid, for minimization for evaporative water together with the pollution substance of following (p-tA etc.), proposed to have sufficient reflux ratio and implement carry out fractionated treatment process, but owing to handle in (25～12 sections of reflux ratio 2～10, number of theoretical platess) in fractionation, with the big water (vaporization heat 539kcal/kg, 100 ℃) of sufficient reflux ratio distillation vaporization heat, the distillation load is big.
Further, in patent documentation 3 (spy opens the 2006-8671 communique), as the method for separating out proterties and filterableness of improving secondary crystal, proposed to make a mother liquor multistage to dodge cold method, processing for isolating secondary mother liquid, it is contacted with synthetic sorbing materials such as vinylbenzene-divinyl benzene series and reduce the impurity level (p-tA etc.) that contains, recycling dissolution process in crude terephthalic acid etc.
Patent documentation 1: Japanese Patent Publication 56-35174 communique
Patent documentation 2: Japanese kokai publication hei 5-58948 communique
Patent documentation 3: TOHKEMY 2006-8671 communique
Summary of the invention
Yet, the disclosed technology of described patent documentation is from separating, having reclaimed the secondary mother liquid behind the secondary crystal and removed the impurity that contains, especially p-methylbenzoic acid, reclaim as treating water, re-use in the technology of the manufacturing of purified terephthalic, owing to treating water regenerated handling secondary mother liquid for the back of separating out at secondary crystal, so operation multiprocessing cost height.Therefore, be difficult to re-use in a large number the recycle-water that generates by this processing.
In addition, be to set out in high purity terephthalic acid's the manufacture method of raw material with p-Xylol, as to Separation and Recovery the method handled of purified terephthalic crystalline mother liquor (mother liquor), to separate out by this mother liquor being carried out flash distillation, cooling, Separation and Recovery the crystalline secondary crystal supply with as a part to the base feed of the oxidizing reaction of p-Xylol, be the preferred method that improves the terephthalic acid yield, but crystallization is more efficiently separated out this secondary crystal and improve filterableness when being separated this crystallization and become problem.
Further, reclaiming the impurity that is contained from the mother liquor that constitutes by the aqueous solvent that is used to dissolve crude terephthalic acid, especially in the manufacturing to the purified terephthalic of the poor water of Phenylbenzoic acid, be used for dissolved water again or cleaning purified terephthalic crystalline water etc., the cheapness that can re-use in large quantities, easy treatment process become problem.
The objective of the invention is to, be provided at when making purified terephthalic, an isolating mother liquor is separated out the operation of secondary crystal from the separating out of primary crystallization the time, obtains the treatment process that the purified terephthalic of the few recycle-water of impurity is separated mother liquor in a large number, at an easy rate.
The inventor furthers investigate these problems, consequently, by the mother liquor that terephthaldehyde's acid crystal is pre-existing in being carried out flash distillation and heating, evaporation it is concentrated, the steam that is produced by mother liquor is as water of condensation and Separation and Recovery, by reducing absolute magnitude as the mother liquor of secondary mother liquid, make as terephthaldehyde's acid crystal of secondary crystal and separate out, the crystallization content of secondary crystal is increased, make it recyclable.And it is few to generate foreign matter content from the steam that produces, especially the poor water of condensation of p-methylbenzoic acid.Therefore, reduce as load and the treatment process of the processing load of significantly reduction amount and it can be made up from the matter of the isolating secondary mother liquid of secondary crystal.
What be used to address the above problem the invention is characterized in, comprise: be dissolved in high temperature, highly compressed water solvent in the crude terephthalic acid that will generate by the liquid phase oxidation reaction of p-Xylol, after in the presence of noble metal catalyst, carrying out hydro-reduction, cooling, crystallization, generate terephthalic acid crystallization slurry, from the crystallization (primary crystallization) of this crystallization slurry Separation and Recovery purified terephthalic and the one separation process of mother liquor (mother liquor); In the presence of the terephthalic acid crystalline, under the pressure below the normal atmosphere,, make it be separated into solvent vapo(u)r and the evaporization process that contains the outstanding turbid mother liquor of terephthalic acid crystalline by isolating mother liquor (mother liquor) is carried out at least one section flash distillation and heating; The secondary separation operation that contains the crystallization (secondary crystal) of terephthalic acid from this outstanding turbid mother liquor Separation and Recovery; The solvent vapo(u)r of the described generation of condensation and generate the condensation operation of water of condensation.
In addition, it is characterized in that, in described evaporization process, have at least be dissolved in terephthalic acid in the mother liquor suitable the crystallization of terephthalic acid of amount.In addition, it is characterized in that, in described evaporization process, the crystallization of terephthalic acid is existed by adding terephthaldehyde's acid crystal.In addition, it is characterized in that, in described evaporization process, under the pressure below the normal atmosphere, produce solvent vapo(u)r, do not reflux or reflux on a small quantity (reflux ratio≤1) by flash distillation and the heating that comprises at least one section.
In addition, it is characterized in that, the secondary crystal that reclaims in the described secondary separation operation is supplied at least a portion of the base feed of described liquid phase oxidation reaction.In addition, it is characterized in that the water of condensation that described condensation operation is generated re-uses as the part of the water solvent of the described crude terephthalic acid of dissolving or as the part of the rinse water of cleaning purified terephthalic crystallization (primary crystallization) (one separation process).In addition, it is characterized in that, in described evaporization process, under reduced pressure under 40～80 ℃ temperature, produce solvent vapo(u)r by one section flash distillation and heating.In addition, it is characterized in that, in described evaporization process, under atmospheric pressure, under reduced pressure under 40～80 ℃ temperature, produce solvent vapo(u)r by flash distillation and heating by behind the flash distillation generation solvent vapo(u)r.In addition, it is characterized in that, in described evaporization process, use about heating medium below 110 ℃ to produce solvent vapo(u)r.
According to the present invention, to separate out the operation of secondary crystal at an isolating mother liquor when primary crystallization is separated out, the steam that condensation is simultaneously evaporated by flash distillation that mother liquor is carried out and heat treated reclaims the few water of condensation of foreign matter content in a large number, at an easy rate.This phlegma can re-use refining in crude terephthalic acid, can significantly reduce the supply of pure water.
In addition, by retrieving evaporation condensed water, because the reduction of the amount of the secondary mother liquid that remaining separation is discharged and the reduction of solute (impurity) realize the significantly reduction of carrying capacity of environment from a mother liquor.
Further, because by retrieving the evaporation condensed water from a mother liquor, residual outstanding turbid mother liquor amount reduces significantly, therefore improve outstanding turbid crystalline filterableness and disengaging time and shorten, the efficient during the improvement solid-liquid separation.Therefore, the secondary crystal amount of Separation and Recovery increases (meltage that is converted into terephthalic acid is about 5 weight %), also improves yield and cost that the high purity terephthalic acid makes.
This mother liquor to a large amount of that replaces the aftertreatment of conduct secondary mother liquid in the past and need carries out fractionated distillation (backflow) load, in handling according to a mother liquor of the inventive method, by keeping with the waste thermal energy of lower temperature (about below 110 ℃) and carrying out evaporative condenser, the pure water of the refining usefulness of recyclable crude terephthalic acid can be sought the significantly reduction of processing costs.
Description of drawings
Fig. 1 is the treatment scheme of an example of enforcement the inventive method.
Fig. 2 is the sketch chart that is used to carry out the tests of simulating device of embodiments of the invention.
Fig. 3 is the graph of a relation of ratio of the yield of the content of p-methylbenzoic acid of water of condensation of simulation test gained and water of condensation.
Embodiment
For a mother liquor of the processed object of conduct in the embodiment of the invention, because at 130～160 ℃ of (about 2～5.5Kg/cm
2G) separate generation down, therefore in mother liquor as the saturated solution of the terephthalic acid of this temperature, usually dissolve the terephthalic acid of about 0.1～0.3 weight %, the ratio with about 0.03～0.15 weight % is dissolved with the p-methylbenzoic acid that is formed by the 4-carboxyl benzaldehyde transformation that is contained in the crude terephthalic acid in addition.The terephthalic acid crystalline solids that spill from solid-liquid separating machine when in addition, a mother liquor reclaims exist with the amount below about 0.02 weight % usually.
For implementing terephthalic acid crystalline amount essential to the invention, the inventor finds, as long as make it so that be equivalent to the amount of dissolved terephthalic acid amount (about 0.1～0.3 weight %) in mother liquor less and exist just enough.
For this reason, with regard in the practicality, making the amount from the dissolved a great deal of of a mother liquor to the several times of this a great deal of or exist with respect to terephthaldehyde's acid crystal that mother liquor reaches the amount of about 1 weight %, is preferable methods.Making the terephthaldehyde's acid crystal existence more than about 1 weight % is effectively to the p-methylbenzoic acid content in the water of condensation that reduces the steam that generates, but the purpose that re-uses for the water of condensation that reclaims the steam that generates is then not necessarily measured.The method of supplying with the crystallization of new terephthalic acid and adjust its amount before the flash distillation of a mother liquor and heat treated is reliably, also can use separating machine (the separating machine increase is to the crystallization content that spills of a mother liquor) etc. to adjust when purified terephthalic crystalline solid-liquid separation.
Here, for the crystallization of the terephthalic acid of new supply, being preferably does not increase purified terephthalic crystallization (PTA) impurity level (p-tA etc.), that make as the high purity terephthalic acid.
Therefore, few in order to reclaim foreign matter content from secondary mother liquid, especially the water of condensation that lowers of p-methylbenzoic acid content, need fractionation up to now always, but in the method for present embodiment, found to make the crystallization of terephthalic acid to preexist in mother liquor one time, make the aqueous solvent evaporation by flash distillation and heating, need not to reflux and (get back to container for evaporation.) or reclaim the especially method of the poor water of condensation of p-methylbenzoic acid of impurity by a small amount of reflux (reflux ratio is below 1).
And find, by under the pressure below the normal atmosphere, comprising at least one section pressure flash distillation (pressing カ Off ラ Star シ ユ),, make its condensation in 40～80 ℃ of heating down of outlet temperature, evaporation, can obtain the poor water of condensation of p-methylbenzoic acid thus.Therefore in the present embodiment, because condensation by heating, evaporation, reduce significantly thus from residual spissated outstanding turbid mother liquor the amount of isolating secondary mother liquid, therefore increase the terephthalic acid of separating out and the crystallization content of p-methylbenzoic acid, crystallization (secondary crystal) yield is compared with existing method and is increased and reclaim.
Therefore, even if when it separates, by the terephthaldehyde's acid crystal that is pre-existing in a mother liquor, fractional crystallization amount (secondary crystal) also increases, and it can also be seen that the filtration velocity of having improved the outstanding turbid mother liquor that generates.Promptly, think for the separation of this outstanding turbid mother liquor, though with the clarification filtration is purpose, the terephthalic acid crystalline exists the main body charging (ボ デ イ one Off イ one De), the filtration velocity that become pre-coated filter aid agent (プ レ コ one ト) material (promoting filtering filtration adjuvant) to be enhanced.Therefore, add the reduction of secondary mother liquid amount, the needed time of the separation of secondary crystal significantly shortens.
In addition, the recovery that in the evaporation process of secondary mother liquid, in the solvent vapo(u)r evaporation, was attended by p-methylbenzoic acid steam, needs to distill (backflow) purified water of condensation in the past, even if so, according to the present embodiment that in a mother liquor, terephthalic acid is pre-existing in, by impurity absorption to the terephthalic acid crystalline particle that adds, exists, thus thought immobilization more p-methylbenzoic acid suppress the generation of p-methylbenzoic acid steam.Therefore, in the present embodiment, in the heating by a mother liquor, when evaporation concentrates, the evaporation of the backflow by need not evaporation condensed water, or by a small amount of backflow, the poor water of condensation of promptly recyclable p-methylbenzoic acid.
Therefore, by the flash distillation of a mother liquor and the evaporation that causes by heating, p-methylbenzoic acid content in the recovery water of condensation is because the existence of terephthalic acid crystalline, need not the backflow (by evaporation) of water of condensation and reduce (about 1/5～1/10) significantly, though its content is also according to the evaporation ratio of this aqueous solvent and difference, but about 90 weight % that can reach a mother liquor reclaim in large quantities as water of condensation, can effectively utilize basically.
By a small amount of (amount of reflux ratio below 1) water of condensation that refluxes, significantly reduce p-methylbenzoic acid content further in addition, recyclable, utilize most aqueous solvent again.Therefore, reduce the amount of secondary mother liquid and the amount of separating out of increase secondary crystal, the carrying capacity of environment of handling isolating secondary mother liquid is also significantly low to be reduced.
Further, as below normal atmosphere to its flash distillation and heating, make the heating medium of its evaporation, especially under reduced pressure in order to make 40～80 ℃ outstanding turbid mother liquor heating evaporation, known exhaust steam (the about 0.05Kg/cm that discharges in large quantities that can effectively be used to from high purity terephthalic acid's manufacturing process and other petrochemical processes
2G, about 110 ℃ of steam) etc. waste thermal energy.Therefore laborsavingization that need not to make new heating medium, can realize energy as the heating medium that makes it to evaporate.
As mentioned above, according to making terephthaldehyde's acid crystal be present in the method for a mother liquor, flash distillation by following evaporation or a small amount of reflux (reflux ratio=0～1) or its heating evaporation is concentrated, the organism crystallization that contained (terephthalic acid, p-tA) of Separation and Recovery separation performance through improving more at high speed effectively utilizes, so the recyclable foreign matter content water of condensation that more reduces of the content of p-methylbenzoic acid especially.Therefore, it is the method for new usage quantity of the refining required pure water that can reduce crude terephthalic acid significantly.Therefore, can realize significantly reducing the closed system of environmental treatment load owing to the secondary mother liquid amount.
When implementing present embodiment, crude terephthalic acid is dissolved in high temperature, highly compressed water, carrying out hydro-reduction in the presence of noble metal catalyst handles, described crude terephthalic acid from originate in acetate solvate, the manufacturing process of the crude terephthalic acid of the operation of liquid-phase oxidation p-Xylol in the presence of oxide catalyst, through be cooled to the operation (not shown) that 130～160 ℃ temperature generates the crystallization slurry of purified terephthalic by multi-segment flash evaporation, this slurry is supplied in solid-liquid separating machine (solid-liquid separating machine 1 of Fig. 1) afterwards.
In the treatment scheme of enforcement method of the present invention shown in Figure 1, shown that the operation to separate the crystallization slurry of above-mentioned purified terephthalic with solid-liquid separating machine 1 is a starting point, from making the flow process of purified terephthalic crystallization (powder) as the primary crystallization of a separating obtained side's purified terephthalic and handling as the flow process of the present embodiment method of isolating the opposing party's separation mother liquor (mother liquor) simultaneously.
At first, for for 130～160 ℃ crystallization slurry of unshowned operation, at about 2～5.5Kg/cm
2The adding to depress with solid-liquid separating machine 1 of G, carried out solid-liquid separation, will carry out being transferred to slurry after crystallization is cleaned at slurry preparation vessel 2 and supply with groove 3 as an isolating side's crystallization with the rinse water slurryization again of heating that be heated to uniform temp (well heater E-1).Then, carry out following method: separate with solid-liquid separating machine 4 once more, obtain the moistening crystallization (primary crystallization) of purified terephthalic after, carry out drying and make high purity terephthalic acid (purified terephthalic PTA) with drying machine 5.
On the other hand, discharge from solid-liquid separating machine 1 and to separate mother liquor (mother liquor), greatly under separation temperature (130～160 ℃), be stored in earlier in mother liquor tank 6, become the mother liquor that sets out of the treatment process of present embodiment.Here, as previously mentioned, usually dissolve the have an appointment terephthalic acid of 0.1～0.3 weight % and the p-methylbenzoic acid of about 0.03～0.15 weight in the mother liquor, as the solids component (terephthalic acid composition) that spills from solid-liquid separation, there is the following amount of about 0.02 weight % usually in throw out in addition.
When handling this mother liquor, in slurry preparation vessel 8, modulate the water-based slurry of terephthalic acid in advance.For synthetic ratio, be the concentration of the terephthalic acid of 10～30 weight %, become the paste consistency that can transfer swimmingly.The terephthalic acid that modulation forms is unqualified for proterties, particle diameter, but preferably uses purified high purity terephthalic acid (PTA).
Then, will be at pressurization (about 2～5.5Kg/cm
2A mother liquor of a mother liquor tank 6 G) is supplied in the flash drum 7 of (ATM) under the normal pressure, and mother liquor of flash distillation makes aqueous solvent evaporation and is cooled to about 100 ℃.Simultaneously, supply with modulation crystallization slurry, in the flash distillation of a mother liquor, make the coexistence of terephthaldehyde's acid crystal from crystal preparation vessel 8.The amount of terephthalic acid was assumed to the amount of the several times of amount～this a great deal of that dissolved terephthalic acid amount (0.1～0.3 weight %) is suitable at least in mother liquor and supplied with this moment, supplied with the terephthaldehyde's acid crystal that reaches about 1 weight % with respect to mother liquor.
But,, can not supply with synthetic terephthalic acid slurry and implement above-mentioned flash distillation as long as the terephthalic acid of the solids component that spills during solid-liquid separation exists with the amount more than the dissolved a great deal of.In addition, directly be supplied in flash drum 7 swimmingly with powder, just there is no need to supply with the slurry state especially so long as the terephthalic acid crystalline is supplied with.
The solvent vapo(u)r of evaporation is stored in the water of condensation storagetank 10 as reclaiming water of condensation through condenser E-3 condensation in flash drum 7.The part of the rinse water when this reclaims water of condensation as the dissolving water of crude terephthalic acid, as the purified terephthalic solid-liquid separation is effectively used as the refining water of crude terephthalic acid.
Then, with the outstanding turbid mother liquor of flash drum 7 (normal pressure, 100 ℃) by drawdown pump be supplied in be communicated with condensate draining 11 and be adjusted into decompression down (700～-400mmHg) flash drum 9, to its flash distillation and make its cooling (about 40～80 ℃).Simultaneously by the outstanding turbid mother liquor under the well heater E-5 heating decompression, evaporating solvent water and concentrating.The heating that should hang turbid mother liquor also can be undertaken by the well heater that is arranged at the handover pipeline that starts from flash drum 7.As heating medium, use the medium of about temperature below 110 ℃, the well heater E-5 that the temperature head of the outstanding turbid mother liquor (40～80 ℃) of preferred use and flash drum 7 is big heats.
Steam condensation in condenser E-4 of evaporation captures in condensate draining 11 in the flash drum 9.Can make fractional distillating tube E-6 operation (feeding water coolant) this moment, makes the part of evaporated vapor be back to evaporator tank 9, is preferred for the reduction of impurity (p-methylbenzoic acid) content in the water of condensation that generates.Therefore, it is preferred adopting the method for evaporation of multi-efficiency formula to concentrate.
The water of condensation that captures in condensate draining 11 is transferred to water of condensation storagetank 10, mixes with water of condensation from flash drum 7, recycles making with extra care in crude terephthalic acid as recycle-water.Here, this is used for purified recirculated water, and in order to use as the rinse water of purified terephthalic crystalline solid-liquid separation, the content of preferred p-methylbenzoic acid is for below about 10ppm, below more preferably about 5ppm.In addition, as the dissolving water of crude terephthalic acid, the content of preferred p-methylbenzoic acid is for below about 20ppm, below more preferably about 10ppm.
Recovery for water of condensation, promptly a mother liquor concentrates, though by improving its degree of enrichment, there is the tendency that increases the content that reclaims the p-methylbenzoic acid in the water of condensation, even but be concentrated into about 10% in the present embodiment, the content of the p-methylbenzoic acid of condensed water does not significantly increase yet, and can concentrate.Therefore, about 90 weight % of the aqueous solvent of a recyclable mother liquor.Reduce the content of p-methylbenzoic acid by the backflow of the water of condensation that generated by partial condensation, the water of condensation that reclaims about 90 weight % is certain.
Here, also can omit (bypass) flash drum 7, only by 9 one sections of flash drums under reduced pressure (700～-400mmHg) make its flash distillation, under 40～80 ℃ temperature, carry out heating evaporation simultaneously.Certainly to supply with terephthalic acid slurry from slurry preparation vessel 8.In addition in the present embodiment, the importing of the evaporated vapor that causes by flash distillation and heating is preferably carried out in the subsurface mode that is directed in flash drum 7 and 9.
Then, in flash drum 9, concentrate and the outstanding turbid mother liquor that significantly reduces passes through strainer 12 and solid-liquid separation is separated into secondary crystal and secondary mother liquid.The outstanding absurd creature (crystallization) of separating out respectively in flash drum 7 and 9 is because p-methylbenzoic acid content is many and for microgranular, therefore isolating secondary crystal is the filter cake with adhesive difficult filterableness.Therefore, the clarifying filter that uses adding pressure type in filtration is preferred, preferably uses pressure filter, Fundabac filter (mill heavy industry (strain) system is broadcast on the Ishikawa island), Cricket filter strainers such as (month island machinery (strain) systems).
In addition, isolating secondary mother liquid is arranged into secondary mother liquid groove 13, carries out wastewater treatment, and by evaporation, concentrated, its amount is significantly low to be reduced, and also reduces by the cooling under reducing pressure (40～80 ℃) dissolved impurity amount.For example the meltage of terephthalic acid is below about 0.03 weight %, and the meltage of p-methylbenzoic acid is the following amount of about 0.04 weight %, and carrying capacity of the environment reduces significantly, when waste treatment, amount on might as well, on the matter might as well, reduced processing significantly and loaded.
For the method for illustration present embodiment more specifically, tests of simulating result is as follows.Here, the method for present embodiment is not defined as following analogy method.The experimental installation that uses as the method that is used for simulation process purification of terephthalic acid mother liquor is shown in the sketch chart of Fig. 2.
Be arranged in the Water Tank with Temp.-controlled (about 100 ℃) 31 as dodging the autoclave that has stirrer (flash distillation and the thickener) A of cold trap 20L, top pipe arrangement 24 is communicated with condensate cooler C1, C2, valve V3, phlegma Receiving bin D and water droplet collector E, is connected to vacuum pump F by pipe arrangement 25,26,28.The interior pressure of high-pressure valve A (the pressure warning unit PI of phlegma Receiving bin D) control is carried out pressure adjustment (normal atmosphere and decompression) by the control valve V4 that is installed on collector E.
The supply of a mother liquor by under meter M and pipe arrangement 21, is adjusted flow by valve V1 from a mother liquor tank (not shown) of high purity terephthalic acid's manufacturing installation, is supplied in high-pressure valve A and is flashed.Then, the terephthalic acid crystalline water-based slurry of synthetic about 20 weight % injects a certain amount of by quantitative injector H by pipe arrangement 29 compartment of terrains in having the slurry preparation vessel G of stirrer.Quantitatively injector H is for operating, inject with the pneumatic transport of gas under pressure compartment of terrain the mode of the slurry of a constant volume (about 6ml) by the valve that is installed on quantitation tube.
For the residual cooling suspension liquid in the autoclave A that is formed by flash cooling, by valve V2 (standard-sized sheet), the liquid level in the autoclave A is according to the horizontal adjustment of pipe arrangement 22, be discharged among the suspension liquid storagetank B that has stirrer by pipe arrangement 22.In time discharge outstanding turbid mother liquor by pipe arrangement 23, the valve V6 that is arranged at its bottom.Here, when flashing pressure is implemented down at normal atmosphere (ATM), the production well of suspension liquid storagetank B and pipe arrangement 22 (vent) is a normal atmosphere, when flashing pressure is decompression, these production wells are connected in collector E by pipe arrangement 30 (dotted line), make suspension liquid storagetank B and pipe arrangement 22 be and the flashing pressure equipressure.
On the other hand, in flash distillation and heating, concentrating, when the water of condensation of refluxed evaporator steam not, evaporated vapor is accommodated into phlegma Receiving bin D and metering by condensate cooler C1, condensate cooler C2 (water flowing) and the pipe arrangement 25 (valve V3 standard-sized sheet) of pipe arrangement 24, logical water coolant as evaporation condensed water.In addition, when reflux condensation mode water, regulate the water-flowing amount of condensate cooler C1, use as fractional distillating tube, water of condensation is accommodated into phlegma Receiving bin D and metering.Therefore, calculate to measure certain heating down take in the time calculating reflux ratio to the water of condensation of phlegma Receiving bin D.
Here, pipe arrangement 25 is equipped with sample tube S, by the valve of sending into to the sample tube S operation that causes by closing of valve V3, extract flash distillation or concentrate in water of condensation (about 100ml), be used to analyze the content of p-methylbenzoic acid.For the outstanding turbid mother liquor in the autoclave A that has concentrated, use the B equipment (not shown) that has 110 φ that are incubated groove, under pressure 390mmHg, carry out decompress filter, the analysis of carrying out the calculating measurement of filtration velocity and filter cake is to be used for comparison.
High temperature, high pressure (about 145 ℃, about 3Kg/cm that will come from a mother liquor tank of high purity terephthalic acid's manufacturing installation
2G) a mother liquor is adjusted into the ratio (under meter M) of about 500ml/min by valve V1, directly imports in the liquid of autoclave A, and under atmospheric pressure (ATM) makes its flash distillation.Simultaneously with quantitative injector H with 1 minute interval by pipe arrangement 29 will about 6ml the slurry of terephthalic acid of 20% weight be injected into a mother liquor send into pipe arrangement 21.
Made its flash distillation about 1 hour (do not have reflux), the result obtains water of condensation (is 8.2 weight % with respect to a mother liquor) from the ratio that phlegma Receiving bin D can about 41ml/min.The content of the p-methylbenzoic acid in this evaporation condensed water (para-toluylic acid) is 2.1ppm.Here, terephthalic acid (the solubleness 0.17gr/100gr water of terephthalic acid) with respect to dissolving 0.17 weight % in a mother liquor of 145 ℃, the supply (6ml/min) of the water-based slurry of the terephthalic acid of 20 weight % makes terephthaldehyde's acid crystal exist with 0.26 weight %.Therefore, terephthaldehyde's acid crystal of about 1.5 times of amounts of dissolved terephthalic acid a great deal of is existed.
Comparative example 1
In the method for embodiment 1, stop to come the injection (V7 closes) of the water-based slurry of the terephthalic acid of injector H self-quantitatively, similarly to Example 1, obtain evaporation condensed water.The content of the p-methylbenzoic acid in this water of condensation is 9.5ppm.
The injection of the importing of a mother liquor and terephthalic acid slurry is carried out similarly to Example 1, autoclave A internal pressure is maintained under the decompression of 150mmHg, with temperature maintenance at about 60 ℃, implements flash cooling similarly to Example 1.At this moment, obtain the evaporation condensed water (is 20.4 weight % with respect to a mother liquor) of the ratio of 102ml/min from phlegma Receiving bin D, the content of p-methylbenzoic acid is 2.7ppm.
Comparative example 2
Stop the terephthalic acid among the embodiment 2 the water-based slurry injection (V7 closes) and carry out.P-methylbenzoic acid content in the evaporation condensed water of this moment is 19ppm.
After the flash distillation of embodiment 2 is finished, close V1 and V2 (stopping the injection of a mother liquor and the discharge of outstanding turbid mother liquor), with autoclave A internal pressure maintain 150mmHg, with temperature maintenance at about 60 ℃, the evaporated vapor of the outstanding turbid mother liquor in the autoclave that do not reflux and evaporate, concentrated (the obstructed water coolant of condensate cooler C1).
The water of condensation of evaporation is accommodated in phlegma Receiving bin D and calculates and measure, and distillates the amount of 5.6L water of condensation after this concentrates beginning, extracts about 100ml water of condensation afterwards from sample tube S.The content of the p-methylbenzoic acid of sample condensation water is 4.3ppm.Here, because the capacity of residual outstanding turbid mother liquor begins to be about 15L from liquid level in the autoclave A of embodiment 2 flash distillations after finishing, so after flash distillation finishes, the about 63 weight % of simmer down to (obtaining the water of condensation of about 37 weight %).
Follow embodiment 3, further do not reflux, outstanding turbid mother liquor in evaporation, the concentrated autoclave A, concentrate beginning back (embodiment 2 flash distillations finish after) and distillate 11.2L evaporation condensed water (beginning to distillate 5.6L) from embodiment 3, extract the water of condensation (about 100ml) among the sample tube S afterwards, the content of the p-methylbenzoic acid in the sample condensation water is 9.7ppm.Here, after flash distillation is finished, the about 25 weight % of simmer down to (obtaining the water of condensation of about 75 weight %).
Follow embodiment 4, further do not reflux, outstanding turbid mother liquor in evaporation, the concentrated high-pressure valve A, concentrate beginning back (embodiment 2 flash distillations finish after) and distillate 13L evaporation condensed water (beginning to distillate 1.8L) from embodiment 4, extract water of condensation (about 100ml) afterwards from sample tube S, the content of the p-methylbenzoic acid in the water of condensation is 16ppm.Here, after flash distillation ended, the about 13 weight % of simmer down to (obtained the water of condensation of about 87 weight %.)。In addition, from the about 11 weight % of the import volume conversion simmer down to of mother liquor.
On the other hand, extract the residual mother liquor (suspension liquid) of the autoclave A of 200ml,, use filter paper (5C) to carry out filtration test by filter plant.The required time of filtration of this moment is 46 seconds.The terephthalic acid amount of the filter cake on the filter paper reaches this formic acid content of methyl is respectively 9.1 weight %, 2.4 weight % in addition.
Comparative example 3
After the flash distillation of comparative example 2 is finished, similarly to Example 3, concentrate the outstanding turbid mother liquor in the autoclave A, in phlegma Receiving bin D, distillate the water of condensation of 5.6L, afterwards similarly to Example 3, extract the water of condensation sample.P-methylbenzoic acid content in the sample condensation water is 31ppm.
Comparative example 4
Then comparative example 3 does not further reflux, and evaporation, concentrates the outstanding turbid mother liquor in the autoclave A, distillates 11.2L evaporation concentration water (flash distillation of comparative example 2 finish after), afterwards similarly to Example 3, and extraction sample (about 100ml).P-methylbenzoic acid content in the sample condensation water is 69ppm.
Comparative example 5
Then comparative example 4 does not further reflux, and evaporation, concentrates the outstanding turbid mother liquor in the autoclave A, distillates 13L evaporation concentration water (flash distillation of comparative example 2 finish after), afterwards similarly to Example 3, and extraction sample (about 100ml).P-methylbenzoic acid content in the sample condensation water is 146ppm.Extract the residual mother liquor (suspension liquid) of the autoclave A of 200ml, filter similarly to Example 5.The required time of filtration of this moment is 432 seconds.In addition, terephthaldehyde's acid content of filter cake and p-methylbenzoic acid content are respectively 5.5 weight %, 3.2 weight % on the filter paper.
Embodiment 6
The injection of the importing of a mother liquor and terephthalic acid slurry is carried out similarly to Example 1, with autoclave A internal pressure maintain 150mmHg, with temperature maintenance at about 60 ℃, implement flash cooling (reproduction of embodiment 2) similarly to Example 1.At this moment, the evaporation condensed water (is 20.2 weight % with respect to a mother liquor) that the ratio that phlegma Receiving bin D can 101ml/min obtains, the content of p-methylbenzoic acid is 2.5ppm.
Afterwards, close V1 and V2 (stopping the importing of a mother liquor and the discharge of outstanding turbid mother liquor), feed water coolant to condensate cooler C1, carry out the backflow of the water of condensation that causes by partial condensation, with the pressure in the autoclave A maintain 150mmHg, with temperature maintenance at about 60 ℃, carry out outstanding turbid mother liquor concentrated in the autoclave.After the 5.6L water of condensation is received into phlegma Receiving bin D, extract sample similarly to Example 3, the content of the p-methylbenzoic acid in the sample condensation water is 2.6ppm.Need 1.46 times the time of embodiment 3 this moment to the time that phlegma Receiving bin D takes in the 5.6L water of condensation.Therefore, in condensate cooler C1, carried out being equivalent to the partial condensation of 0.46 reflux ratio.
Embodiment 7
Follow embodiment 6, to the logical water coolant of condensate cooler C1, carry out the backflow of the water of condensation that causes by partial condensation, further concentrate, further make the 5.6L water of condensation to be accommodated in phlegma Receiving bin D to the outstanding turbid mother liquor in the autoclave A, afterwards similarly to Example 4, extract sample, the content of the p-methylbenzoic acid in the sample condensation water is 13.99ppm.Need 1.58 times the time of embodiment 4 this moment to the time that phlegma Receiving bin D takes in the 5.6L water of condensation.Therefore, in condensate cooler C1, carry out partial condensation with respect to 0.58 reflux ratio.
Follow embodiment 7, to the logical water coolant of condensate cooler C1, carry out the backflow of the water of condensation that causes by partial condensation, further concentrate, further make the 1.8L water of condensation to be accommodated in phlegma Receiving bin D to the outstanding turbid mother liquor in the autoclave A, afterwards similarly to Example 5, extract sample, the content of the p-methylbenzoic acid in the sample condensation water is 4.5ppm.Need 1.68 times the time of embodiment 5 this moment to the time that phlegma Receiving bin D takes in the 1.8L water of condensation.Therefore, in condensate cooler C1, carry out partial condensation with respect to 0.68 reflux ratio.Similarly to Example 5, carry out the filtration test of the residual mother liquor (outstanding turbid mother liquor) of 200ml autoclave A, filtering the needed time is 52 seconds.In addition, the content of the terephthalic acid of filter cake and p-methylbenzoic acid is 9.0 weight %, 2.6 weight %.
The content (ppm) of the p-methylbenzoic acid of the water of condensation of Fig. 3 display simulation test gained and the relation of water of condensation yield (wt%).When not refluxing pass through flash distillation and heating evaporation have terephthalic acid (PTA) crystalline filter cake (△ solid line) and filter cake (▲ dotted line) when not existing and condensation the part of the steam that the produces terephthalic acid crystalline filter cake (line of * single-point) that has when having implemented backflow (reflux ratio is below 1) compare.The p-methylbenzoic acid content of the water of condensation of flash distillation here and heating evaporation and the filter cake separately that forms illustrates with the yield of water of condensation.
Symbol description
1,4: solid-liquid separating machine; 2,8: the slurry adjustment tank; 3: slurry is supplied with groove; 5: drying machine; 6: mother liquor tanks; 7,9: flash tank; 10: the condensed water storagetank; 11: condensate draining; 12: filter; 13: the secondary mother liquid groove; E-1, E-5: heater; E-3, E-4: condenser; E-6: fractional distilling tube; A: autoclave (flash distillation and thickener), B: suspension storagetank; The C:(condensation) cooler; D: condensate liquid receiving slit; E: collector; F: vavuum pump; G: slurry adjustment tank; H: quantitative injector; M: flowmeter; S: coupon; V: valve; P1: pressure gauge; TI: thermometer.
Claims (9)
1. the treatment process that purified terephthalic is separated mother liquor is characterized in that, comprises:
Be dissolved in high temperature, highly compressed water solvent and after carrying out hydro-reduction in the presence of the noble metal catalyst in the crude terephthalic acid that will generate by the liquid phase oxidation reaction of p-Xylol, cooling, crystallization, generate terephthalic acid crystallization slurry, from the crystallization (primary crystallization) of this crystallization slurry Separation and Recovery purified terephthalic and the one separation process of mother liquor (mother liquor);
In the presence of the terephthalic acid crystalline, under the pressure below the normal atmosphere,, make it be separated into solvent vapo(u)r and the evaporization process that contains the outstanding turbid mother liquor of terephthalic acid crystalline by isolating mother liquor (mother liquor) is carried out at least one section flash distillation and heating;
The secondary separation operation that contains the crystallization (secondary crystal) of terephthalic acid from this outstanding turbid mother liquor Separation and Recovery;
The solvent vapo(u)r of the described generation of condensation and generate the condensation operation of water of condensation.
2. purified terephthalic as claimed in claim 1 is separated the treatment process of mother liquor, it is characterized in that, in described evaporization process, have at least be dissolved in terephthalic acid in the mother liquor suitable the crystallization of terephthalic acid of amount.
3. purified terephthalic as claimed in claim 1 or 2 is separated the treatment process of mother liquor, it is characterized in that, in described evaporization process, by adding terephthaldehyde's acid crystal the crystallization of terephthalic acid is existed.
4. the treatment process of separating mother liquor as each described purified terephthalic in the claim 1 to 3, it is characterized in that, in described evaporization process, under the pressure below the normal atmosphere, produce solvent vapo(u)r, do not reflux or reflux on a small quantity (reflux ratio≤1) by flash distillation and the heating that comprises at least one section.
5. the treatment process of separating mother liquor as each described purified terephthalic in the claim 1 to 4 is characterized in that, the secondary crystal that reclaims in the described secondary separation operation is supplied at least a portion of the base feed of described liquid phase oxidation reaction.
6. the treatment process of separating mother liquor as each described purified terephthalic in the claim 1 to 5, it is characterized in that the water of condensation that described condensation operation is generated re-uses as the part of the water solvent of the described crude terephthalic acid of dissolving or as the part of the rinse water of cleaning purified terephthaldehyde's acid crystal (primary crystallization) (one separation process).
7. the treatment process of separating mother liquor as each described purified terephthalic in the claim 1 to 6 is characterized in that, in described evaporization process, under reduced pressure produces solvent vapo(u)r by one section flash distillation and heating under 40～80 ℃ temperature.
8. the treatment process of separating mother liquor as each described purified terephthalic in the claim 1 to 6, it is characterized in that, in described evaporization process, under atmospheric pressure, under reduced pressure under 40～80 ℃ temperature, produce solvent vapo(u)r by flash distillation and heating by behind the flash distillation generation solvent vapo(u)r.
9. the treatment process of separating mother liquor as each described purified terephthalic in the claim 1 to 8 is characterized in that, in described evaporization process, uses about heating medium below 110 ℃ to produce solvent vapo(u)r.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008131786 | 2008-05-20 | ||
| JP2008-131786 | 2008-05-20 | ||
| PCT/JP2009/002040 WO2009141968A1 (en) | 2008-05-20 | 2009-05-11 | Method for treating separated mother liquor from terephthalic acid refinement |
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| CN102026952A true CN102026952A (en) | 2011-04-20 |
| CN102026952B CN102026952B (en) | 2014-05-07 |
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| CN200980117772.0A Expired - Fee Related CN102026952B (en) | 2008-05-20 | 2009-05-11 | Method for treating separated mother liquor from terephthalic acid refinement |
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| Country | Link |
|---|---|
| CN (1) | CN102026952B (en) |
| MX (1) | MX2010012094A (en) |
| WO (1) | WO2009141968A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304397A (en) * | 2012-03-09 | 2013-09-18 | 株式会社日立工业设备技术 | Refining method for roughhew aromatic dicarboxylic acid |
| CN113318471A (en) * | 2021-07-08 | 2021-08-31 | 山东友道化学有限公司 | Method and system for treating xylene oxidation reaction liquid |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5802115B2 (en) * | 2011-11-18 | 2015-10-28 | 株式会社日立製作所 | Method for purifying crude terephthalic acid |
| CN108623065B (en) * | 2017-03-22 | 2020-08-25 | 天华化工机械及自动化研究设计院有限公司 | Method for recycling mother liquor of PTA refining unit |
| CA3100582C (en) * | 2018-05-28 | 2023-08-08 | Pierson Capital Environmental (Beijing) Limited | Efficient methods and compositions for recovery of products from organic acid pretreatment of plant materials |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1150944A (en) * | 1991-02-05 | 1997-06-04 | 帝国化学工业公司 | Production of terephthalic acid |
| CN1651393A (en) * | 2003-12-19 | 2005-08-10 | 三井化学株式会社 | Method for mfg.terephthalic acid |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3058155B2 (en) * | 1998-12-03 | 2000-07-04 | 株式会社日立製作所 | Apparatus and method for producing high-purity terephthalic acid |
| JP2004231644A (en) * | 2003-01-08 | 2004-08-19 | Mitsubishi Chemicals Corp | Method for producing high purity terephthalic acid |
| JP4657674B2 (en) * | 2003-12-19 | 2011-03-23 | 三井化学株式会社 | Method for producing terephthalic acid |
| JP2006008671A (en) * | 2004-05-28 | 2006-01-12 | Mitsubishi Chemicals Corp | Method for producing high-purity terephthalic acid |
-
2009
- 2009-05-11 WO PCT/JP2009/002040 patent/WO2009141968A1/en active Application Filing
- 2009-05-11 CN CN200980117772.0A patent/CN102026952B/en not_active Expired - Fee Related
- 2009-05-11 MX MX2010012094A patent/MX2010012094A/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1150944A (en) * | 1991-02-05 | 1997-06-04 | 帝国化学工业公司 | Production of terephthalic acid |
| CN1651393A (en) * | 2003-12-19 | 2005-08-10 | 三井化学株式会社 | Method for mfg.terephthalic acid |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304397A (en) * | 2012-03-09 | 2013-09-18 | 株式会社日立工业设备技术 | Refining method for roughhew aromatic dicarboxylic acid |
| CN103304397B (en) * | 2012-03-09 | 2015-11-25 | 株式会社日立制作所 | The process for purification of crude aromatic dicarboxylic acids |
| CN113318471A (en) * | 2021-07-08 | 2021-08-31 | 山东友道化学有限公司 | Method and system for treating xylene oxidation reaction liquid |
| CN113318471B (en) * | 2021-07-08 | 2024-05-31 | 山东友道化学有限公司 | Treatment method and system for dimethylbenzene oxidation reaction liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| MX2010012094A (en) | 2010-12-07 |
| WO2009141968A1 (en) | 2009-11-26 |
| CN102026952B (en) | 2014-05-07 |
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