WO2010071599A1 - Procédé de traitement d’eaux usées produites dans un procédé de production d’acide aromatique - Google Patents

Procédé de traitement d’eaux usées produites dans un procédé de production d’acide aromatique Download PDF

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Publication number
WO2010071599A1
WO2010071599A1 PCT/SG2008/000486 SG2008000486W WO2010071599A1 WO 2010071599 A1 WO2010071599 A1 WO 2010071599A1 SG 2008000486 W SG2008000486 W SG 2008000486W WO 2010071599 A1 WO2010071599 A1 WO 2010071599A1
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WIPO (PCT)
Prior art keywords
waste water
process according
passing
ion exchange
exchange resin
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PCT/SG2008/000486
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English (en)
Inventor
Ooi Lin Lum
Wen Yue Ge
Tian He Guan
Wei Qi
Ling Gang Kong
Xiao Yan Wu
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Hydrochem (S) Pte Ltd
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Application filed by Hydrochem (S) Pte Ltd filed Critical Hydrochem (S) Pte Ltd
Priority to PCT/SG2008/000486 priority Critical patent/WO2010071599A1/fr
Priority to TW098143103A priority patent/TW201026613A/zh
Publication of WO2010071599A1 publication Critical patent/WO2010071599A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/04—Feed pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/06—Specific process operations in the permeate stream
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/38—Polymers

Definitions

  • This invention relates to the treatment of waste water generated from an aromatic acid production processes and to the recovery of useful components contained within the waste water.
  • Aromatic acids are commercially important chemicals for the production of plastic materials.
  • One particularly important aromatic acid is purified terephthalic acid (PTA) , which has seen increasing demand in recent years due to its use as a raw material in the production of various applications such as in coatings, composite materials based on unsaturated polyester resins, hot-melt adhesives and production in the production of polyester fibres.
  • PTA purified terephthalic acid
  • PET polyethylene terephthalate
  • PTA is a raw chemical compounds used in the production of PET.
  • PET is used to make fabrics for apparel and home furnishings such as bed sheets, bedspreads, curtains and draperies.
  • Polyester fibres can also be spun together with natural fibres, such as cotton, to produce a cloth with improved properties such as wrinkle resistance.
  • PTA production method involves the oxidation of paraxylene in the presence of oxidation catalysts such as cobalt (Co) and Manganese (Mn) to produce PTA. Thereafter, the PTA is purified by dissolution in a high temperature aqueous solution, followed by treatment with a hydrogenation catalyst and subsequently re-crystallized by cooling down the solution.
  • oxidation catalysts such as cobalt (Co) and Manganese (Mn)
  • the PTA is purified by dissolution in a high temperature aqueous solution, followed by treatment with a hydrogenation catalyst and subsequently re-crystallized by cooling down the solution.
  • Such a purification process generates large amounts of waste water and contained within this waste water are compounds such as, dissolved organic substances, heavy metal impurities and oxidation catalyst metals.
  • some PTA will be entrained in the waste water and the recovery of this entrained PTA is understandably desired. More importantly, however, is the recovery of the expensive and recyclable catalyst metals dissolved in
  • the PTA waste water stream from the PTA purification process is routed to a filter to recover the insoluble PTA.
  • the filtrate is thereafter passed through an ion exchange resin (IER) to adsorb thereon the catalysts and any other metal impurities present in the waste water.
  • IER ion exchange resin
  • RO reverse osmosis
  • the IER is regenerated using " a strong acid as the regenerant.
  • the regenerant solution containing a plethora of tramp metals and catalyst metals, is treated with alkaline solutions such as sodium hydroxide and sodium carbonate (Na 2 CO 3 ) , and in particular sodium hydroxide (NaOH) , in order to precipitate the metals as hydroxides, which can thereafter be separated from the regenerant solution.
  • alkaline solutions such as sodium hydroxide and sodium carbonate (Na 2 CO 3 ) , and in particular sodium hydroxide (NaOH)
  • the pH of the regenerant solution is first adjusted to the range of 4 to 5, whereby some metals are precipitated as hydroxides and removed as sludge. More NaOH is added to further increase the pH of the regenerant solution to 8.5 to 9.5.
  • the waste water stream that has passed through the IER column further undergoes alkaline addition to increase its pH to a value of 5 to 7, thereby maintaining the solubility of the organic substances.
  • the waste water is thereafter passed through a two-stage reverse osmosis unit to remove the organic salts, organic compounds and other trace amounts of metal ions.
  • the recycled water is the routed back for re-use in the PTA production process.
  • the known method is disadvantageous in that it requires a two-stage addition of alkaline solution (e.g. Na 2 CO 3 ) .
  • alkaline solution e.g. Na 2 CO 3
  • the precipitated catalyst metals are thereafter filtered from the waste water, washed with water, re-dissolved with acid and undergoes a further purification step before substantially pure catalysts can be recovered.
  • a two-stage alkaline addition method also results in the use of large amounts of alkaline such as NaOH / NaCO 3 , which renders the process uneconomical.
  • the metal catalysts namely Co and Mn
  • the metal catalysts are precipitated as sludge during the subsequent addition of NaOH to adjust the pH of the solution to about 9.
  • Such a method suffers from a lack of selectivity as the sludge removed will typically contain hydroxides of other metals, as well as that of Co and Mn. Consequently, this lack of selectivity in the catalyst recovery step results in the recovered catalyst possessing a low level of purity. This is particularly detrimental as the recovered catalyst is to be recycled back into the PTA purification process. Heavy metal impurities that may be present in the recycle catalyst stream can further lead to catalyst fouling and reduce the overall yield of PTA production.
  • metal impurities are precipitated and removed in a first alkaline addition.
  • the waste water subsequently passes through a chelating resin for adsorption of the catalyst metals.
  • inorganic acids e.g. HCl
  • the resin is regenerated and alkaline solution is further added to the regenerant to precipitate and recover the catalyst metals.
  • the waste water stream having passed through the chelating resin, undergoes alkaline addition to increase its pH to about 6 - 7.
  • a two stage RO unit is thereafter used to recover water from the waste water stream.
  • the disadvantages of this process is similar to that disclosed above, namely, high consumption of alkaline, a need to install a two-stage RO unit, thereby incurring high capital investment and operating costs associated with the above.
  • a treatment process for removing insoluble aromatic acids, oxidation catalysts, and metal impurities, from waste water generated in an aromatic acid production process comprising the steps of:
  • step (b) passing the filtrate of step (a) through an ion exchange resin to selectively remove at least one metal impurities;
  • step (c) passing the effluent of step (b) through an ion exchange resin capable of adsorbing said oxidation catalysts.
  • the at least one said metal impurities may be selected from the group comprising of chromium, nickel and iron.
  • the removed metal impurities will not be adsorbed onto the resin in step (c) .
  • This allows better adsorption of the oxidation catalysts on the resin in step (c) .
  • the recovered oxidation catalysts may be substantially free of metal impurities .
  • step (b) passing the filtrate of step (a) through an ion exchange resin to selectively remove at least one metal impurities;
  • step (c) passing the effluent of step (b) through an ion exchange resin capable of adsorbing said oxidation catalysts .
  • the process of the first aspect comprises the step of:
  • step (d) passing the effluent of step (c) through a reverse osmosis system to remove the organic salts and organic compounds.
  • the process of the first aspect may further comprise the step of heating the filtrate passing out of step (a) to about at least 50 0 C to about at least 60°C.
  • the filtrate is heated to a temperature of 60 0 C.
  • step (c) it is not necessary to add alkaline solution to the waste water.
  • steps (a) , (b) , (c) and optionally step (d) are undertaken to respectively substantially remove said insoluble aromatic acids, metal impurities, said oxidation catalysts and optionally, said organic salts and organic compounds.
  • a process for the recovery of heavy metal oxidation catalyst from waste water of an aromatic acid production process containing insoluble aromatic acids., heavy metal oxidation catalysts, and metal impurities comprising the steps of:
  • step (f) passing the filtrate of step (e) through an ion exchange resin capable of selectively removing at least one or more of said metal impurities selected from the group comprising of chromium, nickel and iron;
  • step (g) passing the effluent of step (f) through an ion exchange resin to adsorb said oxidation catalysts on the resin;
  • the method may further comprise the step of: (i) passing the effluent from step (g) through a reverse osmosis unit to remove any dissolved organic salts and compounds.
  • the passing step (i) produces industrial grade water.
  • a process for the treatment of waste water containing aromatic acids comprising the step of passing the waste water through a reverse osmosis system at a pH less than about 5.
  • the disclosed process does not require the addition of an alkaline solution to alter the pH of the waste water.
  • a treatment process for removing insoluble aromatic acids, heavy metal oxidation catalysts, metal impurities, from waste water generated in an aromatic acid production process comprising the steps of: passing the waste water through a filtering means to remove entrained solids; passing the filtrate through an ion exchange resin to remove metals and recover oxidation catalysts therefrom; heating the effluent stream from said ion exchange resin to at least 60 C C; and passing the heated effluent stream through a reverse osmosis unit to thereby recover water.
  • the effluent stream may be heated from a temperature of at least 60 0 C to at least 90 0 C.
  • the heating step allows the effluent stream to maintain at saturation state or a less than saturated state, thereby preventing crystallization of any dissolved organic salts or organic compounds, which is otherwise undesirable for a subsequent reverse osmosis step.
  • aromatic acid refers to a compound having an acid group attached to an aromatic ring carbon.
  • An exemplary aromatic acid is terephthalic acid or pure terephthalic acid (PTA) .
  • oxidation catalyst refers to heavy metals such as cobalt metal ions and manganese metal ions, which can be used in the oxidative catalysis of paraxylene to terephthalic acid.
  • heavy metals refers to metals which are typically encountered in industrial waste water having an atomic mass number greater than 24.
  • exemplary heavy metals include arsenic, calcium, chromium, copper, lead, magnesium, mercury, silver, and zinc.
  • organic substances refers to any substances that are comprised of hydrocarbon compounds present or generated during production of aromatic acids, such as terephthalic acid.
  • exemplary organic ' substances include partially oxidized intermediates formed during PTA synthesis such as paratoluic acid and 4-carboxybenzaldehyde, etc.
  • IER ion exchange resin
  • industrial grade water in the context of this specification refers to water that is substantially free of metal ions and organic substances.
  • the term "about”, in the context of concentrations of components of the formulations, typically means +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1% of the stated value, and even more typically +/- 0.5% of the stated value .
  • range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within rhat range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
  • the waste water entering filtration step (a) is mainly comprised of water as its solvent, and may have less than 5 weight percent monocarboxylic acids, more preferably less than 1 weight percent monocarboxylic acids, yet more preferably less than 0.05 weight percent monocarboxylic acids, .
  • the waste water has less than 0.05 percent by weight of monocarboxylic acids.
  • any filtration design commonly known to one skilled in the art may be used.
  • Exemplary filters can include stainless steel membranes, ceramic membranes, polymer membranes, plate and frame filters, bag filters, etc
  • the selective removal of metal impurities in step (b) may comprise the removal of nickel (Ni), Chromium (Cr) and incidental iron (Fe) by adsorption onto the ion exchange resin (IER) .
  • the IER employed here can be a weak acid resin or a chelating resin capable of adsorbing ions of Cr, Ni and Fe.
  • the IER used in step (b) is a weak acid resin.
  • An exemplary resin capable of selective removal of metal impurities such as. Ni ions from waste water is a weakly acidic cation exchange resin like DOWEX MAC-3TM from The Dow Chemical Company, United States of America.
  • a waste water stream having an initial Ni content of about 0.16 parts per million (ppm) may contain less than 0.002 ppm of Ni after passing out from the IER.
  • the oxidation catalysts used in the generation of aromatic acids, such as PTA are typically cobalt (Co) and/or Manganese (Mn) .
  • the removal of oxidation catalysts from the waste water may comprise passing the waste water through a weak acid resin or a chelating resin that is capable of forming a chelate with Co and Mn metal ions.
  • the IER employed here is a chelating resin.
  • the process of the first aspect may comprise, after step (C), a polishing step of:
  • the resin of the IER used in the polishing step (cl) may be a strong acid or a chelating resin. In one embodiment, the resin of step (cl) is a strong acid resin.
  • the prior removal of Cr, Ni and some Fe by the weak acid resin or chelating resin allows the subsequent removal of Co and Mn in the chelating resin to be more selective and efficient.
  • the separation of tramp metal impurities in the polishing step (Cl) from the useful metal catalysts is effected through an innovative arrangement of IERs, thereby negating a need to adjust the pH of the waste water. This advantageously overcomes the problems of low purity and yield associated with catalyst recover via precipitation by alkaline. Also advantageously, this obviates the need for using large volumes of alkaline solution.
  • the disclosed method also negates the need for multiple filtration/sedimentation units to be installed for the purposes of removing the precipitated tramp metals during regeneration step, thus leading to substantial capital savings .
  • the inventors have surprisingly found that the selective removal of Co and Mn is enhanced and made more selective by the prior removal of Ni, Cr and Fe.
  • the highly selective adsorption of Co and Mn onto the chelating resin allows for a high percentage recovery of the oxidation catalyst metals from the waste water.
  • the waste water effluent stream passing out from the chelating resin contains less than 0.02 parts per million (ppm) of cobalt and manganese.
  • the recovered catalysts also possess a relatively higher degree of purity as compared to the catalysts recovered from existing processes, which allows the recovered oxidation catalysts to be recycled for use in further oxidative catalysis for PTA production.
  • the chelating resin may be regenerated using a strong inorganic acid such as hydrochloric (HCl), acetic acid or hydrobromic acid (HBr) .
  • HCl hydrochloric
  • HBr hydrobromic acid
  • the regenerant stream, containing the recovered catalysts and the- acid, may be recycled directly back to PTA production process.
  • the regenerant stream may be passed into a treatment unit to further purify and concentrate the recovered catalysts for recycle.
  • the regenerant stream is passed back to the PTA production process directly, without the need for post-rreatment .
  • the recovered catalyst may comply with the China Industrial Quality Index for the liquid composite catalyst of Co-Mn-Br as provided in Table 1 below. Table 1
  • the process may further comprise the step of: heating the waste water effluent to a temperature at least about 60 0 C, more preferably at least about 7O 0 C. In one embodiment, the heating step is between about 60 0 C to about 90 0 C, more preferably between about 60°C to about 8O 0 C.
  • the high temperature of the effluent stream increases its saturation capacity and prevents the crystallization of the dissolved organic substances.
  • Known prior art processes prevent crystallisation through the addition of NaOH, which as mentioned increases the sodium content of the waste water and is not desirable for water recovery.
  • the disclosed method does not employ NaOH for this purpose.
  • this allows the present method to subsequently use a single stage reverse osmosis unit to recover water.
  • the Na ion content present in the recovered water is also markedly reduced and complies with industrial requirements.
  • the reverse osmosis membrane used in step (d) of the disclosed process can be a cellulosic type membrane, an aromatic polyamide type membrane or a thin film composite (TFC) type having a polyamide surface.
  • TFC thin film composite
  • the ion exchange resins used in the disclosed process can adopt various configurations known in the art.
  • Exemplary resin configurations include fixed bed resins, moving bed resins, pulse bed resins and simulated moving bed resins.
  • the resin beds used are moving bed resins. Moving bed resins allow the adsorption and desorption to occur simultaneously at different sections of the resin bed.
  • the resin can be regenerated continuously without being taken off-line and causing disruption to the disclosed process.
  • Figure 1 shows a rough schematic of the process flow diagram of the treatment of PTA waste water.
  • FIG. 2 shows a detailed schematic of the process flow diagram of the treatment of PTA waste water and the steps for catalyst recovery thereof.
  • Fig. 1 there is shown a process flow diagram for the treatment of PTA waste water.
  • the process comprises passing the waste water 12 through a filter 20, an ion exchange system 40 and a reverse osmosis unit 60.
  • any insoluble PTA 13 is recovered by the filter as retentate and recycled back to the PTA production process 140.
  • the ion exchange column 40 comprises at least two resin beds disposed therein.
  • a weak acid resin bed 40a is provided to adsorb metal ions such as Fe, Cr and Ni from the permeate 14.
  • a regenerant stream 28 is simultaneously passed into weak resin bed 40a to elute the adsorbed metal ions into a regenerant stream 32.
  • the waste water stream now substantially free of the metal ions, exits the weak resin bed 40a as effluent waste water 16.
  • the effluent 16 is subsequently passed into chelating resin bed 40b whereby catalyst metals, cobalt and manganese, are adsorbed thereon.
  • a regenerant stream 34 is simultaneously passed into chelating resin bed 40b to elute the catalyst metals into a regenerant stream 36.
  • the recovered catalyst 58 can be recycled directly back into the PTA production process 140 for further oxidative catalysis reactions.
  • a reverse osmosis unit 60 is provided to remove the dissolved organic salts and organic compounds as retentate stream 25 and recover industrial grade water 44.
  • Fig. 2 there is shown a detailed process flow diagram 10 for PTA waste water treatment and catalyst recovery.
  • the PTA waste water generated from the PTA purification process is at a temperature of about 100 0 C - 130 0 C and a pH of between 1.8 to about 3.5.
  • the PTA waste water stream 12 is first -passed through a stainless steel membrane filter 20 to recover any insoluble PTA 13 entrained in the waste water. Whilst only a stainless steel membrane is disclosed here, it should be clear that- any alternative means of filtration practicable by one skilled in the art could be substituted here.
  • the recovered PTA 13 is recycled directly back to the aromatic acid production process.
  • the filtrate stream 14 contains trace amounts of metal impurities such as Mg, Ca, Ni, Fe, and Cr in their respective ionic forms and also oxidation catalysts Co and Mn, also in ionic form.
  • filtrate 14 undergoes heating via a heat exchanger 11 to increase its temperature by about 10 to 20 °C, before it is passed through an ion exchange resin (IER) system 40.
  • the IER system 40 comprises a weak acid ⁇ resin bed 40a, a chelating resin bed 40b and a strong acid resin bed 40c.
  • Each of these resin beds can adopt either fixed bed, simulated moving bed or moving bed configuration.
  • the resin beds are of a moving bed design.
  • Corrosive metal impurities such as Ni, Cr and Fe are selectively adsorbed onto the weak acid resin bed 40a.
  • the effluent stream 16 that passes our thereafter is substantially free of Ni, Cr and Fe.
  • regenerant 28 is introduced into the weak acid resin bed 40a to elute the adsorbed cations, Ni, Cr and Fe, from the weak acid resin bed 40a, regenerating the resin bed 40a in the process.
  • the regenerant 28 used here is a 4-8% hydrochloric acid (HCl) .
  • the regenerant stream 32, containing the HCl regenerant and the eluted metals Ni, Cr and Fe, is discharged to a waste water treatment unit 70 for further treatment and disposal.
  • the separation of metal impurities like Ni from the useful oxidation catalysts does not require the addition of large amounts of expensive base like NaOH.
  • this selective removal of metal impurities in a first resin bed is a highly selective process, it is able to remove substantially almost all of the corrosive metal impurities from the waste water.
  • the weak acid resin employed in this step does not adsorb the useful Co and Mn ions, thereby concentrating the catalyst metals in the effluent stream that exits the resin bed 40a. This is helpful in the subsequent recovery of the catalysts .
  • a portion of the weak acid resin bed 40a is constantly being regenerated as a separate portion continues to adsorb the corrosive metal ions.
  • adsorption and desorption processes occur simultaneously and negates the need to take the resin bed system 40 offline for resin regeneration. This is turns reduces disruptions to the overall process and improves the ion exchange efficiency.
  • the effluent stream 16 is then passed through a chelating resin bed 40b.
  • This step allows for the selective removal of the oxidation catalyst metals, Co and Mn, from the waste water.
  • the expended resin is regenerated with a 4% HCl stream 34, thereby forming a reqenerant stream 36, containing the regenerant 34 and oxidation catalysts Co and Mn.
  • the regenerant stream 36 is then recycled directly back to the PTA production process 80.
  • the remaining metals that are present within the mother liquor include metals like Ca, Mg and Na.
  • the effluent stream 18 then passes through a strong acid resin bed 40c to capture all the remaining metals subsisting in the waste water.
  • the expended strong acid resin 40c is regenerated with a 4-8% HCl stream 38 and the purge stream 42 is similarly discharged to a waste water treatment unit 90 for further treatment and disposal.
  • the effluent stream 22 exiting from strong acid resin bed 40c is substantially free of metal impurities and oxidation catalysts.
  • further treatment steps are undertaken to remove any dissolved organic impurities that may still be present within the effluent stream 22.
  • a reverse osmosis (RO) membrane unit 60 is employed here to remove any dissolved organic salts and compounds.
  • a heat exchanger 50 is installed therebetween the resin column 40 and the RO unit 60.
  • the effluent stream 22 is heated up to a temperature of 60 0 C to 90 0 C to increase the saturation point of the mother liquor.
  • the saturation extent of the waste water is increased, thereby preventing organic salts and compounds from crystallizing.
  • NaOH is added into the waste water to suppress such crystallization.
  • This method entails significant economic drawbacks as the costs of NaOH remain a huge proportion of the total operating costs.
  • the present method boasts of considerable economic advantages.
  • the heated stream 24 is filtered through the RO membrane 60 which separates the bulk of the organic salts and compounds from the waste water, forming industrial grade water that is substantially free of organic salts.
  • the retentate stream 25 containing the removed organic substances is routed to a waste water treatment unit (not shown) . Trace amounts of organic impurities may still be present after filtration through the RO membrane 60.
  • a resin bed 100 is provided after the RO unit to further "polish" the RO filtrate by removing any trace organic substances. Water stream 44 thus formed is of sufficiently high purity and is suitable for industrial applications. This recovered water 44 can also be recycled directly back for use in the PTA production process .
  • the disclosed method may be used to recover useful oxidation catalysts from the waste water generated by PTA production, without necessitating the use of large amounts of expensive NaOH.
  • the disclosed method selectively separates Ni, Cr and Fe from the bulk of the metals in a first selective IER.
  • this allows the oxidation catalysts to be concentrated in the mother liquor and also reduces the possibility of metal impurities binding to a second IER designated for removal of Co and Mn.
  • the disclosed method also employs selective IER to separate the useful metal catalysts from the metal impurities.
  • this method yields a higher purity catalyst recovery as opposed to separation via differential pH precipitation.
  • the disclosed method may recover substantially all of the catalyst metals entrained in the PTA waste water.
  • the recovered catalyst also complies with the industrial standards as set out in Table 1.
  • the recovered catalyst is suitable to be directly recycled back into the PTA production process.
  • the temperature of the effluent stream exiting the IER column is preheated to about 60 0 C to about 90 °C prior to entry into the reverse osmosis unit.
  • the high temperature advantageously increases the saturation capacity of the effluent waste water and prevents any dissolved organic substances from crystallizing, thereby hindering the osmosis process.
  • NaOH is not used in suppressing the crystallization of the organic substances, the sodium content of the waste water is kept low. Accordingly, the disclosed method is able to recover water from PTA waste water with the use of a single stage reverse osmosis unit rather than a double stage RO unit. Furthermore, this also serves to lower the overall NaOH demanded by the process, again leading to substantial cost savings.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Treatment Of Water By Ion Exchange (AREA)

Abstract

L’invention concerne un procédé de traitement destiné à éliminer des acides aromatiques insolubles, des catalyseurs d’oxydation de métaux lourds, et des impuretés métalliques provenant d’eaux usées produites dans un procédé de production d’un acide aromatique. Le procédé de traitement comprend les étapes consistant à : (a) filtrer les eaux usées pour récupérer les acides aromatiques insolubles ; (b) faire passer le filtrat obtenu à l’étape (a) à travers une résine échangeuse d’ions pour éliminer sélectivement au moins une impureté de métal lourd ; et (c) faire passer l’effluent obtenu à l’étape (b) à travers une résine échangeuse d’ions pour éliminer sélectivement les catalyseurs d’oxydation.
PCT/SG2008/000486 2008-12-17 2008-12-17 Procédé de traitement d’eaux usées produites dans un procédé de production d’acide aromatique WO2010071599A1 (fr)

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PCT/SG2008/000486 WO2010071599A1 (fr) 2008-12-17 2008-12-17 Procédé de traitement d’eaux usées produites dans un procédé de production d’acide aromatique
TW098143103A TW201026613A (en) 2008-12-17 2009-12-16 Process for the treatment of waste water generated in an aromatic acid production process

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PCT/SG2008/000486 WO2010071599A1 (fr) 2008-12-17 2008-12-17 Procédé de traitement d’eaux usées produites dans un procédé de production d’acide aromatique

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CN103241860A (zh) * 2013-04-27 2013-08-14 浙江晶泉水处理设备有限公司 不锈钢酸洗废水组合处理装置及工艺
CN104045183A (zh) * 2014-06-16 2014-09-17 济南嘉能可环境工程有限公司 两段镍回收系统及其工艺
WO2014189786A1 (fr) * 2013-05-20 2014-11-27 Invista Technologies S.A R.L. Épuration et recyclage d'eaux usées d'usine pure
CN104843819A (zh) * 2015-05-26 2015-08-19 陕西厚亿节能环保新材料科技有限公司 一种连续处理重金属液体的方法
CN106432622A (zh) * 2016-09-27 2017-02-22 辽阳合成催化剂有限公司 一种含饱和二元酸回收料制备不饱和聚酯树脂的方法
CN108751557A (zh) * 2018-07-04 2018-11-06 广东益诺欧环保股份有限公司 一种废酸资源化回收方法和系统
CN109081460A (zh) * 2018-09-03 2018-12-25 福州大学 一种吸附处理PTA废水中溶解性AOCs和Co(II)/Mn(II)的方法
CN110372116A (zh) * 2019-08-09 2019-10-25 大连凯信石化科技有限公司 一种回收pta氧化装置废水中醋酸的方法
CN110395786A (zh) * 2019-07-18 2019-11-01 大连凯信石化科技有限公司 一种回收pta母固废水中重金属离子的方法
CN111747591A (zh) * 2020-06-28 2020-10-09 江苏扬农化工集团有限公司 含tta高盐废水的处理方法
WO2021169483A1 (fr) * 2020-02-26 2021-09-02 苏州晶洲装备科技有限公司 Dispositif et procédé d'élimination d'ions métalliques lourds dans un liquide résiduaire photovoltaïque
CN115282939A (zh) * 2022-08-04 2022-11-04 南京大学 一种高选择性除铁树脂及pta废水中钴锰催化剂回收回用方法与系统
CN116639769A (zh) * 2023-07-27 2023-08-25 杭州永洁达净化科技有限公司 一种抛光废酸的回收方法及系统

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Cited By (16)

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Publication number Priority date Publication date Assignee Title
CN103241860A (zh) * 2013-04-27 2013-08-14 浙江晶泉水处理设备有限公司 不锈钢酸洗废水组合处理装置及工艺
WO2014189786A1 (fr) * 2013-05-20 2014-11-27 Invista Technologies S.A R.L. Épuration et recyclage d'eaux usées d'usine pure
CN104045183A (zh) * 2014-06-16 2014-09-17 济南嘉能可环境工程有限公司 两段镍回收系统及其工艺
CN104045183B (zh) * 2014-06-16 2016-08-17 济南嘉能可环境工程有限公司 两段镍回收系统及其工艺
CN104843819A (zh) * 2015-05-26 2015-08-19 陕西厚亿节能环保新材料科技有限公司 一种连续处理重金属液体的方法
CN106432622B (zh) * 2016-09-27 2019-01-01 辽阳合成催化剂有限公司 一种含饱和二元酸回收料制备不饱和聚酯树脂的方法
CN106432622A (zh) * 2016-09-27 2017-02-22 辽阳合成催化剂有限公司 一种含饱和二元酸回收料制备不饱和聚酯树脂的方法
CN108751557A (zh) * 2018-07-04 2018-11-06 广东益诺欧环保股份有限公司 一种废酸资源化回收方法和系统
CN109081460A (zh) * 2018-09-03 2018-12-25 福州大学 一种吸附处理PTA废水中溶解性AOCs和Co(II)/Mn(II)的方法
CN110395786A (zh) * 2019-07-18 2019-11-01 大连凯信石化科技有限公司 一种回收pta母固废水中重金属离子的方法
CN110372116A (zh) * 2019-08-09 2019-10-25 大连凯信石化科技有限公司 一种回收pta氧化装置废水中醋酸的方法
WO2021169483A1 (fr) * 2020-02-26 2021-09-02 苏州晶洲装备科技有限公司 Dispositif et procédé d'élimination d'ions métalliques lourds dans un liquide résiduaire photovoltaïque
CN111747591A (zh) * 2020-06-28 2020-10-09 江苏扬农化工集团有限公司 含tta高盐废水的处理方法
CN115282939A (zh) * 2022-08-04 2022-11-04 南京大学 一种高选择性除铁树脂及pta废水中钴锰催化剂回收回用方法与系统
CN116639769A (zh) * 2023-07-27 2023-08-25 杭州永洁达净化科技有限公司 一种抛光废酸的回收方法及系统
CN116639769B (zh) * 2023-07-27 2023-10-20 杭州永洁达净化科技有限公司 一种抛光废酸的回收方法及系统

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