CN101257975B - Method for treating wastes from terephthalic acid process - Google Patents
Method for treating wastes from terephthalic acid process Download PDFInfo
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- CN101257975B CN101257975B CN2006800329629A CN200680032962A CN101257975B CN 101257975 B CN101257975 B CN 101257975B CN 2006800329629 A CN2006800329629 A CN 2006800329629A CN 200680032962 A CN200680032962 A CN 200680032962A CN 101257975 B CN101257975 B CN 101257975B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
- B01J31/403—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/68—Liquid treating or treating in liquid phase, e.g. dissolved or suspended including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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Abstract
Disclosed herein is a method for treating waste byproducts from terephthalic acid processes, by homogeneously mixing the waste byproducts with water and an anti- corrosion agent to prepare a waste water, decomposing organic compounds of the waste water through oxidation reaction with an oxidant under the condition that the waste water is kept in a liquid state, and recovering catalyst particles from the liquid component. The method is of high industrial applicability as it allows organics to be decomposed with the waste byproducts maintained in a liquid state and can recover catalysts with high yield availability.
Description
Technical field
The present invention relates to a kind of method that is used for handling the waste by-product that comes from terephthalic acid (TPA) (terephthalic acid) processing procedure.Specifically the present invention is the method that is used for handling the waste by-product that comes from terephthalic acid (TPA) (terephthalic acid) processing procedure, by simultaneously water and corrosion inhibitor being mixed with waste by-product and making its reaction in discarded water, being added into oxidant under the high-temperature and high-pressure conditions, be used for decomposing organic matter and follow to utilize and come reducing catalyst as cobalt and manganese, above-mentioned waste by-product is a liquid condition.
Background technology
In general, the preparation of terephthalic acid (TPA) can utilize in the presence of transition metal such as cobalt and manganese and make the paraxylene partial oxidation, is accompanied by production of by-products such as benzoic acid, p-tolualdehyde, paratolunitrile, 4-carboxyl benzaldehyde, 4-hydroxymethyl-benzoic acid etc.Behind synthetic terephthalic acid (TPA), reclaim and to stay accessory substance behind prepared phthalic acid and the acetate solvate and become discarded object, as the metallic catalyst of cobalt and manganese and co-catalyst hydrobromic acid etc.
It is very difficult will reclaiming these expensive catalysts cobalts and manganese from synthesize the left waste by-product of terephthalic acid (TPA), is solid-state aromatic compound because the main composition of these waste by-product at room temperature is close to.When acetic acid is recovered since these discarded objects to be close to be at solid state, therefore he to be decomposed be unusual difficulty.Usually these discarded objects are to handle via incinerating into ash.When these waste by-product were incinerated into ash, these catalyst such as cobalt, manganese etc. emitted along with the ash after these incinerations from incinerator, and the ash after then incinerating from these reclaims these catalyst.(U.S.Pat.Nos.4,786,621 and 4,876,386) however be difficult to solid waste is inserted incinerator continuously.For this reason, the organic waste by-product that stays behind these recovery solvent acetic acid will be mixed with fuel oil to prevent that it from filling up material mouthful (Korean Pat.No.0371231, a Japanese Pat.No.63040157).But, also run into from these incineration technology and be difficult to reclaim solid metallic and can produce the new waste by-product and the difficulty of waste water when reclaiming.In addition; these catalyst particles are quite small; therefore the regular meeting when reclaiming of metallic catalyst particulate partly is accompanied by waste gas and emits the quite difficulty that makes that recovery becomes, and but then, is imperative but will prevent the pollution of the environment as air pollution.
Another technology that reclaims catalyst from the waste by-product that terephthalic acid process is left over is disclosed (Chinese Pat.No.1117163), wherein the product that produces from terephthalic acid process basically by the alkaline discard solution behind the ethene processing procedure with the pH-value 7.5 or higher that neutralizes, then can use moisture sodium hydroxide solution to adjust the pH-value scope is between 8.5 to 9.5, adds cobalt and polyacrylamide again and makes it form coagulating sedimentation.Even these advantages that reclaim waste by-product from the ethene processing procedure can be utilized again and again, but such technology then is defective at the organic matter from the waste by-product of terephthalic acid process, all not by the decomposition of chemical sense, produce high concentration and a large amount of discarded organic by-products as benzoic acid, terephthalic acid (TPA), toluic acid etc. and just emit as original form.And organic discard solution of manufacturing comprises many CODs (COD) value and reaches hundreds thousand of high organic matters in reclaiming the process of catalyst.Therefore, the biological treatment of these organic discarded water is unusual difficulties, and builds the treatment plant that these discarded water reclaim and need zone greatly.
Summary of the invention
Technical problem
The main purpose of the present invention research by synthetic terephthalic acid process the processing of residual waste by-product, carried out by main inventor, solve towards the problem direction that formerly technology met with, cause discovery using resist simultaneously temperature and pressure to be maintained waste by-product as under the liquid condition, not only can make decomposition that waste by-product continues but also the catalyst recovery yield that can increase waste by-product.
Therefore, main purpose of the present invention provides a kind of method of handling the terephthalic acid process waste by-product, and the method is quite effective for organic oxidation Decomposition and from waste by-product recovery catalyst.
Solution
Can reach a kind of method of from terephthalic acid process, handling waste by-product that provides according to purpose of the present invention, comprise (a) and utilize water evenly to mix waste by-product and be prepared into discarded water, and described waste by-product contains and is useful on the synthetic catalyst of terephthalic acid (TPA) with resist (anti-corrosion agent); (b) under described discarded water is situation at liquid, in the pressure described discarded water of heating down; (c) utilize the above-mentioned discarded water that has heated of oxidant reaction decomposing the organic matter that it is included, and catalyst is transformed into metal oxide; (d) cooling heat treated water in step (c); (e) this water of cold treatment that reduces pressure, and the water of reduced pressure treatment has been separated into gaseous state effluent and the liquid effluent that comprises catalyst particles, to discharge its gaseous state effluent; And (f) from its liquid effluent, reclaim catalyst particles, described catalyst particles contains cobalt (cobalt) and manganese (Manganese), wherein said resist be selected from by NaOH, sodium acid carbonate, sodium carbonate, potassium hydroxide, potash with and composition thereof the group that formed.
The advantage that can reach
Remove acetate solvate and can cause described waste by-product at room temperature to be close to and lose flowability, make to handle and go up the difficulty that becomes in solid state.Even utilize incinerator to handle these waste by-product continuously, organic solvent still can produce other problem in processing procedure.In incineration course, the small cobalt of part and Mn catalyst particulate will be accompanied by waste gas and emit so cause the rate of recovery to descend.And the grey removal process after incinerating, the dissolving of these strong acid and strong bases and neutralization, purpose is but to cause having produced new waste water and problem of environmental pollution in order to increase the rate of recovery.
Yet the method that the present invention can decompose described waste by-product does not have the problem that meets with described in traditional incineration course, and shows the high-recovery of catalyst, makes that terephthalic acid process can more efficient implementation.
Description of drawings
Fig. 1 illustrates for the flow process that expression one embodiment of the invention is provided for handling terephthalic acid process;
Fig. 2 illustrates for the flow process that expression another embodiment of the present invention is provided for handling terephthalic acid process, and it is applicable to a large amount of gases with high-enriched organics;
Fig. 3 is for being provided at the particle size distribution curve map of the metallic catalyst particulate of manufacturing in the synthetic terephthalic acid process according to one embodiment of the invention.
10: the discarded object 11 of terephthalic acid process: water
12: resist 13: oxidant
14: mixing channel 21: waste water pump
22: heat exchanger 23: heater
24: reactor 25: cooler
26: reducing transformer 27: dropping valve
31: gas-solid separator 32: solid-liquid separator
33: the water 34 of discharging: the catalyst of recovery
35: the gas 126 of discharging: gas purger
127: LLCV
The specific embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent, be that example describes in detail with reference to accompanying drawing below according to the method that is used for handling the waste by-product come from terephthalic acid (TPA) (terephthalic acid) processing procedure of the present invention, especially exemplified by preferred embodiment, wherein components identical will be illustrated with the components identical symbol.
As mentioned above, come from the described waste by-product of terephthalic acid process, form, can't be very fast soluble in water but form pulpous state by organic acid with very big molecular weight.Hydrobromic acid, the co-catalyst as synthetic terephthalic acid (TPA) has highly corrosive, and therefore resist must be used for preventing the hydrobromic acid etching apparatus in organic oxidizing process.So in the process that is increased in these waste by-product of processing of described organic matter solubility is useful, and the interpolation of an amount of alkaline components is for preventing that hydrobromic corrosion from being necessary.
According to purpose of the present invention, the discarded object of described terephthalic acid process add in the entry with a debita spissitudo and increase water-soluble, then in order to prevent that hydrobromic corrosion from adding resist.
Use high-pressure pump to make discard solution be pressurized to 41.5 to 250 atmospheric pressure (bar) but between so that make discard solution under reaction temperature, maintain solution state continuous feed to treatment facility.Utilize a heat exchanger and heater to heat described discard solution, and add oxidant (as oxygen, air or the like) organic matter is resolved into carbon dioxide and water between 250 ℃ to 370 ℃ of the range of reaction temperature.Wherein, the described discarded object preferred proportion of mixing with water is between the 0.1wt% to 30wt%.
In the process of oxidation, when catalyst such as cobalt and manganese etc. were converted into the burning particulate that forms pulpous state, organic composition was broken down into carbon dioxide and water.When decomposing organic compounds arrived required degree, this comprised the mixture of catalyst particles vacuum cooled, and the metallic catalyst particulate also can be separated and can reclaim simultaneously.
Consult Fig. 1, below will illustrate that processing of the present invention comes from an embodiment of the waste by-product of terephthalic acid process with Fig. 1.
In Fig. 1, the discarded object 10 that produces in the process by synthetic terephthalic acid (TPA) at room temperature is solid state, and not only comprising expendable terephthalic acid (TPA) also includes side reaction and produces and at room temperature lack under the condition of acetate solvate and be the aromatic compound of solid-state tool heavy molecular weight, as benzoic acid, p-tolualdehyde, paratolunitrile, 4-carboxyl benzaldehyde, 4-hydroxymethyl-benzoic acid etc.In order to make effective oxidation, so organic waste must be distributed in the water uniformly.Yet the uniform state of discarded object in water be very inaccessible be because most organic compound in water, have low solubility.Fortunately, because the composition of discarded object major part is an organic acid, and the waste products that produces in the process of synthetic terephthalic acid (TPA) is convertible into organic salt after by the mixed-alkali composition and therefore is increased in solubility in the water.
As shown in Figure 1, the discarded object 10 that will come from terephthalic acid process mixes to form a slurry with water 11.In order discarded object to be dissolved in the water and with the neutralization of co-catalyst hydrobromic acid, to add resist 12 in described slurry, the waste water with the even attitude of tool is stored in the mixing channel 14 at last.
In one embodiment, the function of described resist for the solubility that increases described discarded object and in and hydrobromic acid form a salt include NaOH (NaOH), sodium carbonate (Na2CO3), sodium acid carbonate (NaHCO3), potassium hydroxide (KOH), potash with and composition thereof the group that formed.Lacking under the condition of resist, hydrobromic acid will cause serious extent of corrosion.On the other hand, if add too much resist, the pH-value of described discard solution will increase and cause caustic corrosion.Therefore add described resist be preferably keep discarded water the pH value in 4～7.
Described mixing channel 14 utilizes pump 21 as being used for the moisture discarded aqueous solution that pressurizes in the processing procedure through after mixing fully.According to purpose of the present invention, the pressure that increases processing procedure that is to say that described pressure is higher than the vapour pressure of maximum temperature, so that reactant can not evaporate again to the treatment temperature that does not have steam to produce.When the pressure of reactant was lower than vapour pressure, the reactant of mixing will flash to steam condition.If produce too many steam, hammering will take place, and can cause scrambling and unstability on the process operation.Consequent steam, the violent decline of density of liquid meeting makes the required time interval of reaction to determine, the difficulty that suitable decomposing organic matter is become.Therefore, during described wastewater feed preferable operating pressure to 250 crust (bar), and oxidizing reaction temperature changes scope between 250 ℃ to 370 ℃ between 41.5 crust (bar).
Utilize pump 21 pressurizations, carry out wastewater treatment by heat exchanger 22.Heat exchanger 22 is quite helpful for the positive energy exchange in the process, because it can utilize the heat energy that flows out hot water in the process from reactor 24 after oxidation reaction.Particularly, the COD (COD) when waste water reaches 80000mg O
2During/L, the energy that exothermic reaction during oxidation of organic compounds produced is big to enough heating described waste water, makes its inflow heat exchanger reach reaction temperature.
Mainly heated described waste water is to be allowed to enter heater 23 in the process by heat exchanger 22, and wherein heater 23 is that the described waste water of last heating is to oxidation temperature.Be heated to reaction temperature between 250 ℃ to 370 ℃ at heater 23, described waste water then imports reactor 24.When the temperature of waste water when heat exchanger 22 is heated to same or is higher than reaction temperature, heater 23 just need not provide extra heat energy again, but can be allowed inflow reactor 24 immediately.In the presence of oxidant 13, the organic matter in the waste water is oxidized to carbon dioxide and water in reactor 24.
According to purpose of the present invention, oxidant be a kind of wrap oxygen containing liquid be selected from oxygen, oxygen containing admixture of gas, ozone, hydrogenperoxide steam generator, dissolved oxygen water with and composition thereof the group that formed.The consumption of described oxidant is with complete decomposing organic compounds than high 1 molar percentage to 50 molar percentage (mo1%) of theoretical value.Specifically, when waste water has the concentration of higher organic compound, will carefully select oxidant in order to avoid temperature of reactor surpasses 374 ℃, the water of supercritical temperature will produce under this temperature.Preferably, water meeting and combination with oxygen can be used to cooling reactor with as oxidant, use as the oxidative decomposition heating of organic compound.In addition, described oxidant can be added in the feeding mouth or reactor of reactor.
Preferably, described waste water can rest on interior 2 minutes to 30 minutes of reactor so that organic compound can be sufficiently oxidized to till the decomposition.
Though heat energy when inflow heat exchanger 22 through exchange, still can be overheated when outflow reactor 24 and can't flow out.Therefore, the liquid that overheated desire flows out in these reactors directly cools off with cooler 25, and wherein temperature decline scope is 25 ℃ to 100 ℃, to the scope that is fit to discharge.When by reducing transformer 26 and dropping valve 27, the described waste water that is cooled will be by step-down.
Main reducing transformer 26 is devices that are used for reducing described cooling waste water pressure, and its pressure state is equal or is higher than vapour pressure.The decomposition generation water of described waste water and gaseous state composition such as carbon dioxide and oxygen are accompanied by the precipitation of catalyst such as cobalt and manganese.If gaseous state, liquid state and solid state component all are blended in the process of step-down, therefore the loss dropping valve 27 that its mixture can be serious reduces its service life.Therefore, the loss that reducing transformer can prevent described valve 27 is set before dropping valve 27.A capillary pressure lowering means provides a pipe with minute diameter, can be used as an embodiment of reducing transformer 26.
According to purpose of the present invention, when cooling waste water was flowed through reducing transformer 26, its pressure dropped to atmospheric pressure 20 crust (bar), the therefore loss that has slowed down dropping valve 27 by scope between 41.5 crust (bar) to 250 crust (bar).Behind the dropping valve 27 of flowing through, its mixture is imported into gas-liquid separator 31, comprises carbon dioxide and the oxygen of excessive importing etc. of generation in the decomposable process of organic compound in the gas phase composition 35 that wherein is discharged out.Simultaneously, liquid phase is formed and to be comprised catalyst particles 34 and will be imported into solid-liquid separator 32 wherein when treated water is discharged away, and the catalyst particles 34 that exists with the kenel of metal oxide can be recovered.
Be used for removing in the method for the particulate in the mixture that comprises water and catalyst particles, solid-liquid separator 32 can be operated by precipitation, method centrifugal or that filter.Because particle is small when diameter is micrometre (um), come separation of cobalt and Mn catalyst particulate to need the plenty of time via precipitation.Therefore, the preferable system of separator is equipped with sedimentator and filter.
When waste water has the organic compound of high concentration, need excessive oxidant can increase the output of oxygen and carbon dioxide.Under these circumstances, unsettled operation can occur in the process that reduces pressure in the reducing transformer.In this process, so the process that descends of pressure is preferably and then in the process that removes of gas composition.
See also Fig. 2, illustrate that another embodiment of the present invention is provided for handling the flow process of terephthalic acid process, it is applicable to handle to have the waste water process of high-enriched organics, and wherein the process that removes of gas composition is early than the process of pressure decline.In reactor 24, decompose the carbon dioxide produced by organic compound and be partially dissolved in and reach equilibrium concentration in the water and part exists with gas phase.In addition, the excessive oxygen that provides, between 1 molar concentration to 50 molar concentration, those responseless oxygen will be discharged into outside the reactor 24 in the value scope that surpasses COD.A large amount of gas compositions exists under these circumstances, and the direct importing of waste water such as the capillary reducing transformer 26 of Fig. 1 will cause the plug flow of pulpous state gas to form, and plug flow can make the fluctuation of pressure acutely change, so the excessive loss of build-up of pressure control valve.
In the presence of a large amount of gases, so the waste water inflow heat exchanger 22 interior heats exchange from reactor 24 flows out then enters in the gas-liquid separator 31 in 25 li coolings of cooler, wherein gas is separated with the liquid that includes catalyst particles.The gas dropping valve 26 that utilization is arranged on gas outlet end is adjusted the pressure of gas-liquid separator 31, adjusts the pressure of entire process process thus.After isolating these gases, when liquid level reaches critical point, open the liquid level that automatic liquid level control valve 127 is controlled slurry by liquid-level controller, catalyst particles and water mixes slurry and can emit from gas-liquid separator 31 under high pressure conditions.
In order to prevent that valve (for example dropping valve 27) is depleted, provide a reducing transformer 26 to be arranged at automatic valve 127 after.Via the reducing transformer 26 that passes through as shown in Figure 1, the pressure of the liquid of high pressure drops to atmospheric pressure 20 crust (bar), the therefore proportion of goods damageds of having slowed down dropping valve 27 by scope between 41.5 crust (bar) to 250 crust (bar).Taking off and passing through dropping valve 27, mixture is directed to solid-liquid separator 32, is recyclable catalyst particles 34 after treated water flows out wherein.
As mentioned above, but the invention provides one and not only can effectively retrieve in the waste by-product of synthetic terephthalic acid process the also method of decomposing organic matter of burning particle catalyst composition.
Of the present invention only is illustrative with as preferable understanding, but not is restricted person.Anyly do not break away from spirit of the present invention and category, and, all should be contained in the accompanying Claim book its equivalent modifications of carrying out or change.
Embodiment one
Discarded object from terephthalic acid process is formed
Behind separating acetic acid solvent and water completely, the waste by-product that comes from terephthalic acid process analyzes organic compound and catalyst is formed.The main component of discarded object is as follows at table 1 when synthesizing terephthalic acid (TPA).
In the discarded object from terephthalic acid process, as shown in table 1, terephthalic acid (TPA) and benzoic acid have accounted for the 85wt% that major part reaches gross weight.M-phthalic acid and paratolunitrile have also accounted for the sub-fraction composition, have also comprised impurity.
Table 1
The discarded object that comes from the terephthalic acid process is formed
Embodiment two
Decomposition from the terephthalic acid process discarded object
As mentioned above, the discarded object that produces in synthetic terephthalic acid (TPA) process is the mixture that organic matter and catalyst are formed.Described discarded object is mixed with water, mix with NaOH, carry out handling procedure with the undissolved particulate of part again to increase solubility.
In the process of the inflow of waste water, be found to and have COD (COD) value reaches 82300mgO
2/ L, and adjust pH-value to 6.0 by the NaOH (NaOH) that adds 1.786wt%.The reactor that uses in processing procedure is a tubulose, and to be set at initial oxidizing reaction temperature temperature when when inlet, 298 ℃ of temperature increased to outlet gradually be 361 ℃.In reactor, keeping pressure is that 250 crust (bar) and reaction time are 4.3 minutes.The oxygen that surpasses COD 20% is provided.After the oxidative decomposition, the pH-value of the waste water after the processing is 7.2, and this value is higher than the pH-value of original waste water, and the value of COD is 3570mg O
2/ L, the resolution ratio that is reached is 95.7%.
Embodiment three
Organic resolution ratio in reaction time
The discarded object that will come from terephthalic acid process mixes the back chemical oxygen demand value that produces main waste water and reaches 84000mg O with water and NaOH
2/ L and its pH-value is adjusted to 5.5.Pressure in the whole process before step-down maintains 250 crust (bar), and the amount of oxygen that is provided surpasses 20% of COD.The COD of treated water and resolution ratio are shown in table 2 according to reaction condition and result after measuring as follows.
As shown in table 2, the preferably keeps being at least 250 ℃ for the temperature of waste water inflow reactor.Higher reaction temperature or long reaction time can both guarantee higher organic matter decomposition rate.If the wastewater temperature of inflow reactor is lower than 250 ℃, the initial reaction rate is will be too slow so that can't reach enough organic matter decomposition rate, though this be because when oxidation reaction begins the reaction time growing, temperature is difficult to reach 250 ℃.
Table 2
Wastewater treatment
Embodiment four
The change of treated water tenor after adding resist
It is acid that the discarded object that comes from terephthalic acid process is in water, and it mainly consists of hydrobromic acid and organic acid such as terephthalic acid (TPA), benzoic acid, paratolunitrile etc.Because the separation of organic acid low degree, what discarded object can't be good is dissolved in the water, so form slurry.In order to prevent that hydrobromic corrosion from forming slurry with solving separating of organic acid low degree, a kind of alkaline matter be selected from by NaOH, sodium acid carbonate, sodium carbonate, potassium hydroxide, potash with and composition thereof the group that formed to be added in the discarded object as resist.When adding described alkaline matter in the entry, but the degree that described discarded object is dissolved to output waste water wherein the part particulate remain on not dissolved state.Described waste water can be very fast the importing processing procedure have corrosion resistance in addition to carry out oxidation Decomposition.
Analyze the corrosion resistance that adds different resist waste water.This analysis is to utilize a tubular reactor, and its outlet temperature is 360 ℃ and to set the reaction time be 250 crust (bar) at 4.5 minutes to 5 minutes pressure.The amount of oxygen that is provided surpasses COD, 84000mg O
220% of/L.
Discarded object is decomposed via adding entry and alkaline solution such as NaOH, sodium acid carbonate, sodium carbonate, potassium hydroxide or potash, and the waste water of handling has the content of four kinds of metallic irons, nickel, chromium and molybdenums after by analysis, and coming from the main component of making reactor and testing arrangement is nickel alloy I-625.The metal ingredient of high-load means the corrosion of experience such as used device such as reactor, heat exchanger higher degree in the process in the waste water.
Data by table three may be obvious that, and when obvious corrosion occurring lacking resist, keep waste water pH-value 4～7 and use resist will reduce the extent of corrosion of device significantly.
Table three
The tenor that waste water adds behind the resist changes
Embodiment five
The catalyst particle that reclaims distributes
The waste by-product that will come from terephthalic acid process is mixed the back and is then carried out oxidation reaction under 360 ℃ of temperature with water, NaOH and sodium acid carbonate.The treated water that comprises catalyst particles after by analysis distribution of particles and the result as shown in Figure 3.With volume, particulate has d (0.1)=1.175 μ m through measuring size, d (0.5)=3.005 μ m and d (0.9)=18.324 μ m.
Embodiment six
Catalyst recovery
When the combination of NaOH and sodium acid carbonate is used as resist, and the oxidative decomposition of accessory substance carries out that pressure is 250 crust (bar) when 360 ℃ of temperature, is used for controlling the pH-value of waste water.The content of catalyst cobalt and manganese analysis and utilization ICP-MS quantitatively is to calculate the use amount of catalyst in waste water.In order to reclaim catalyst, with waste water process precipitation and filtration.It is as follows that the use amount of catalyst and yield are summarized in table 4.Together relatively after, the digital proof of table 4 the method according to this invention be more excellent in the performance of catalyst recovery yield.
Table 4
Catalyst recovery yield
Claims (11)
1. method that is used to handle the waste by-product that comes from terephthalic acid process comprises:
A) utilize water evenly to mix waste by-product and be prepared into discarded water, and described waste by-product contain and is useful on the synthetic catalyst of terephthalic acid (TPA) with resist;
B) under described discarded water is situation at liquid, in the pressure described discarded water of heating down;
C) utilize the above-mentioned discarded water that has heated of oxidant reaction decomposing the organic matter that it is included, and catalyst is transformed into metal oxide;
D) cool off water heat treated in step c);
E) this water of cold treatment that reduces pressure, and the water of reduced pressure treatment has been separated into gaseous state effluent and the liquid effluent that comprises catalyst particles, to discharge its gaseous state effluent; And
F) reclaim catalyst particles from its liquid effluent, described catalyst particles contains cobalt and manganese,
Wherein said resist be selected from by NaOH, sodium acid carbonate, sodium carbonate, potassium hydroxide, potash with and composition thereof the group that formed.
2. method according to claim 1, wherein organic content is 0.1～30 percentage by weight in the discarded water of step a).
3. method according to claim 1, more comprise separate its cooling processing water to gaseous state and liquid effluent, and the step of its effluent that has separated that reduces pressure, and step of replacing e).
4. method according to claim 1, wherein resist is to be used to keep the pH value of discarded water in 4～7.
5. method according to claim 1, wherein step b) and c) be under the pressure, 250～370 ℃ of 41.5 to 250 crust, to carry out.
6. method according to claim 1, wherein oxidant be selected from oxygen, oxygen containing admixture of gas, ozone, hydrogenperoxide steam generator, dissolved oxygen water with and composition thereof the group that formed.
7. method according to claim 1, wherein the used in amounts of oxidant than high 1 molar percentage to 50 molar percentage of theoretical value with complete decomposing organic compounds.
8. method according to claim 1, wherein the discarded water of step c) is to be cooled to 25～100 ℃.
9. according to claim 1 or 3 described methods, wherein the discarded water of step e) is to be decompressed between atmospheric pressure to 20 crust.
10. according to claim 1 or 3 described methods, wherein step e) is to carry out in capillary.
11. method according to claim 1, wherein step f) is to carry out in a solid-state-liquid separation equipment, and its equipment has and is selected from the device that settling vessel, centrifuge, filter and its combination are formed.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020050083293 | 2005-09-07 | ||
| KR10-2005-0083293 | 2005-09-07 | ||
| KR1020050083293A KR100662146B1 (en) | 2005-09-07 | 2005-09-07 | Method for treating wastes from terephthalic acid process |
| PCT/KR2006/003515 WO2007029956A1 (en) | 2005-09-07 | 2006-09-05 | Method for treating wastes from terephthalic acid process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101257975A CN101257975A (en) | 2008-09-03 |
| CN101257975B true CN101257975B (en) | 2010-12-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800329629A Expired - Fee Related CN101257975B (en) | 2005-09-07 | 2006-09-05 | Method for treating wastes from terephthalic acid process |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4763789B2 (en) |
| KR (1) | KR100662146B1 (en) |
| CN (1) | CN101257975B (en) |
| WO (1) | WO2007029956A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101013489B1 (en) * | 2008-10-29 | 2011-02-11 | 아신기술 주식회사 | Recovery of catalysts and aromatic acids from the wastes aromatic acid production plants |
| US9388110B2 (en) | 2013-12-12 | 2016-07-12 | Saudi Arabian Oil Company | Liquid phase oxidation of aromatic feedstocks with manganate recycling to produce carboxylic acids |
| CN112830597A (en) * | 2020-12-31 | 2021-05-25 | 何蕾 | Polyester wastewater treatment method |
| CN116265044B (en) * | 2021-12-16 | 2024-06-18 | 中国科学院大连化学物理研究所 | Method for treating paraxylene liquid phase oxidation residues |
| CN114712959B (en) * | 2022-05-21 | 2023-04-18 | 山东凯希威智能装备有限公司 | Waste gas treatment method for polymerizing waste by using oxygen-enriched water |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4250330A (en) * | 1977-04-13 | 1981-02-10 | Montedison S.P.A. | Process for the recovery of the solvent and of the by-produced methylacetate in the synthesis of terephthalic acid |
| US4410449A (en) * | 1979-12-14 | 1983-10-18 | Dynamit Nobel Aktiengesellschaft | Recovery and reuse of heavy-metal oxidation catalyst from the Witten DMT process |
| US4939297A (en) * | 1989-06-05 | 1990-07-03 | Eastman Kodak Company | Extraction process for removal of impurities from terephthalic acid filtrate |
| CN1226550A (en) * | 1998-02-16 | 1999-08-25 | 中国石化辽阳石油化纤公司 | Process for recovering cobalt and manganese catalysts from production of terephthalic acid |
| US20040245176A1 (en) * | 2003-06-05 | 2004-12-09 | Parker Kenny Randolph | Process for removal of impurities from mother liquor in the synthesis of carboxylic acid using pressure filtration |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49106401A (en) * | 1973-02-16 | 1974-10-09 | ||
| KR790000412B1 (en) * | 1974-04-03 | 1979-05-14 | Matsuyama Petrochemicals Inc | Method for recovering oxidation catalyst |
| JPH1015390A (en) * | 1996-07-02 | 1998-01-20 | Mitsubishi Gas Chem Co Inc | Method for recovering catalyst from liquid phase oxidation reaction mother liquor |
| JPH11165079A (en) | 1997-12-05 | 1999-06-22 | Toray Ind Inc | Method for recovering acetic acid in liquid-phase air oxidation reaction and method for recovering catalyst |
| GB0010241D0 (en) * | 2000-04-28 | 2000-06-14 | Johnson Matthey Plc | Improvements in precious metal refining |
-
2005
- 2005-09-07 KR KR1020050083293A patent/KR100662146B1/en active IP Right Grant
-
2006
- 2006-09-05 WO PCT/KR2006/003515 patent/WO2007029956A1/en active Application Filing
- 2006-09-05 CN CN2006800329629A patent/CN101257975B/en not_active Expired - Fee Related
- 2006-09-05 JP JP2008529916A patent/JP4763789B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4250330A (en) * | 1977-04-13 | 1981-02-10 | Montedison S.P.A. | Process for the recovery of the solvent and of the by-produced methylacetate in the synthesis of terephthalic acid |
| US4410449A (en) * | 1979-12-14 | 1983-10-18 | Dynamit Nobel Aktiengesellschaft | Recovery and reuse of heavy-metal oxidation catalyst from the Witten DMT process |
| US4939297A (en) * | 1989-06-05 | 1990-07-03 | Eastman Kodak Company | Extraction process for removal of impurities from terephthalic acid filtrate |
| CN1226550A (en) * | 1998-02-16 | 1999-08-25 | 中国石化辽阳石油化纤公司 | Process for recovering cobalt and manganese catalysts from production of terephthalic acid |
| US20040245176A1 (en) * | 2003-06-05 | 2004-12-09 | Parker Kenny Randolph | Process for removal of impurities from mother liquor in the synthesis of carboxylic acid using pressure filtration |
Non-Patent Citations (2)
| Title |
|---|
| JP特开平10-15390A 1998.01.20 |
| JP特开平11-165079A 1999.06.22 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101257975A (en) | 2008-09-03 |
| KR100662146B1 (en) | 2006-12-27 |
| WO2007029956A1 (en) | 2007-03-15 |
| JP2009506888A (en) | 2009-02-19 |
| JP4763789B2 (en) | 2011-08-31 |
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