CN1594118A - Method for recovering mother solid water in aromatic carboxylic acid production - Google Patents
Method for recovering mother solid water in aromatic carboxylic acid production Download PDFInfo
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- CN1594118A CN1594118A CN 200410041380 CN200410041380A CN1594118A CN 1594118 A CN1594118 A CN 1594118A CN 200410041380 CN200410041380 CN 200410041380 CN 200410041380 A CN200410041380 A CN 200410041380A CN 1594118 A CN1594118 A CN 1594118A
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- acid
- water
- mother liquor
- ion exchange
- membrane
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- 238000000034 method Methods 0.000 title claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000007787 solid Substances 0.000 title abstract description 21
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000012528 membrane Substances 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 26
- 238000011282 treatment Methods 0.000 claims abstract description 24
- 239000000919 ceramic Substances 0.000 claims abstract description 19
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 11
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- 230000000149 penetrating effect Effects 0.000 claims abstract description 9
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- 239000012452 mother liquor Substances 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- 238000005342 ion exchange Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003456 ion exchange resin Substances 0.000 claims description 10
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000005374 membrane filtration Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 13
- 150000007524 organic acids Chemical class 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000003729 cation exchange resin Substances 0.000 abstract 1
- 238000004886 process control Methods 0.000 abstract 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 44
- 239000002351 wastewater Substances 0.000 description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000012545 processing Methods 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 230000004907 flux Effects 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- 229910052737 gold Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005273 aeration Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
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- 238000011069 regeneration method Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
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- 239000002910 solid waste Substances 0.000 description 2
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 108090000862 Ion Channels Proteins 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
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- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
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- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical group O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention discloses a method for recovering mother solid water in aromatic carboxylic acid production, wherein the mother solid water treated by the method contains phthalic acid, metal ions and organic acid byproducts. The treatment process comprises the following steps: passing the mother solid water stream through an inorganic ceramic membrane to remove insoluble solid phthalic acid and insoluble organic acid by-products therefrom; the penetrating fluid passes through strong acid type cation exchange resin to remove metal ions in the penetrating fluid; the treated water meets the requirements of process control indexes and can be recycled in the production of aromatic carboxylic acid.
Description
Technical field
The present invention relates to a kind of treatment process of aromatic carboxylic acid factory effluent.
Background technology
Pure terephthalic acid (hereinafter to be referred as PTA) is a main raw material of producing polyester, is indispensable starting material during terylene is produced.Refined unit in PTA produces, thick PT because wherein contain a large amount of suspended solids compositions (being mainly PTA), therefore are called mother liquor through in hydrogenating reduction, crystallization, centrifugation, washing, the dry mother liquor that obtains afterwards.Mainly form by p-Xylol, acetic acid, terephthalic acid (PTA), p-methylbenzoic acid (4-CBA) etc.The COD of this waste water (chemical oxygen demand) is higher, is a kind of more unmanageable organic chemical waste water.
The processing to this waste water abroad is mainly the flocculation-biochemical aeration of Japan and the extended aeration process of U.S. AMOCO, and the former need dilute with river, and flow process is longer, and the COD in the waste water after handling is about 800mg/L, does not reach emission standard far away.Since AMOCO60 age later development since three grades of aerobe oxide treatment PTA waste water technologies, biological treatment is main treatment technology always.Anaerobism and the aerobic bio-oxidation treatment process that combines have been trended towards using in recent years.Anaerobic technique is used to handle high concentrated organic wastewater, also recyclable biogas, but the water quality inferiority of treat effluent, Se Hei and foreign odor is arranged; The water quality of aerobic process treat effluent is better.But, in treating processes, need bio-aeration processing through reaching 5～6 days.Thereby caused that the treatment facility floor space is big, construction investment and energy consumption be all than higher, and the most important thing is that the waste water handled can not reuse, at today that water resources lacks day by day more and more incompatible society, industrial expansion.
In recent years, domestic PTA manufacturer explores treatment technology again on the basis of three grades of aerobic treatment, anaerobism and aerobic (anaerobic-aerobic two stage biological treatment process), the anaerobism novel procesies such as (A/O bio membrane processes) that combines with bio-contact oxidation successively occurred.What is more important when the bio-aeration pool method reclaims component, can cause damaging bacterium, perhaps produces unavailable sludgd deposition in the bottom, aeration tank.
Chinese patent application CN1033176A has proposed a kind ofly to handle method of terephthalic acid in the trade effluent with molysite, and mainly adopting ferric sulfate or iron trichloride is terephthaldehyde's Acid precipitation in the waste water, is removed by filtering then.Regulate Ph to 4～5.5, add an amount of polyacrylamide simultaneously to improve the sedimentation effect of terephthalic acid, the clearance of terephthalic acid can reach more than 90%.Chinese patent CN1039784A has proposed a kind of PTA Wastewater Treatment by pre-treatment, anaerobic biological treatment, aerobe treatment combination.Chinese patent application 1123770A has proposed a kind of two sections aerobe methods of band selector and has handled the method that the terephthalic acid high density is produced waste water, the one-level aerobic reactor adds biological selector, one-level and secondary aerobic reactor are provided with sludge settling jar and mud return-flow system separately respectively, the COD of waste water can be reduced to below the 80mg/L by 4000～7000mg/L, P-phthalic acid at concentration is reduced to below the 10mg/L by 800～1200mg/L; Chinese patent application 1315295A adopts membrane sepn and resin absorption isolation technique to combine, and pure terephthalic acid's factory effluent is handled, and its COD is reduced to below the 150mg/L, and terephthalic acid and phenylformic acid are reduced to below the 5ppm.Though realized the reuse of water, mainly adopt membrane sepn and resin absorption isolation technique to come terephthalic acid and organic acid impurity in the treating water, the metal ion in the treating water pointedly not is as Na
+, Cr
3+, Co
2+, Ni
+Deng, the existence of metal ion can make catalyzer lose activity, thereby has increased the usage quantity of catalyzer in actual production, has increased cost.
These methods mostly are the angles from discharge of wastewater, make the COD of waste water up to standard.Biochemical process is with the PTA biodegrade, and processing cost is higher, and causes the significant wastage of resource; The treatment effect of flocculence is relatively poor relatively, and needs to add new chemical substance in waste water, can cause secondary pollution.These methods have reduced the COD of waste water to a certain extent, have alleviated the load of sewage disposal, but complex disposal process, cycle are long, sewage after treatment still difficulty reach direct emission standards.The more important thing is that these methods are passive must the processing waste water, the purpose of processing only is discharging, has added acid, alkali and other chemical in the treating processes again, easily forms secondary pollution, and waste water is not carried out recycling.PTA factory gives off a large amount of contaminated wastewater environment on the one hand; Need on the other hand to replenish respective amount through the fresh process water of special processing dissolving water as refining crude terephthalic acid, increased the pressure of deficient water resources day by day.As the production equipment of 450,000 tons of PTA of a cover annual output, quantity of wastewater effluent is about 100t/h.Therefore the method for wastewater treatment of seeking to reduce effectively the quantity discharged of pollutent and process water consumption has become the task of top priority of PTA industry.
Summary of the invention
The objective of the invention is to provide the recovery method of mother liquor in a kind of aromatic carboxylic acid production at above deficiency.Present method may further comprise the steps:
A, membrane filtration: mother liquor inorganic ceramic membrane filtration.Concentrated solution returns the press filtration operation, and penetrating fluid enrichment between mineral membrane and film overcoat enters ion exchange unit then.
B, ion-exchange: the penetrating fluid process cationic exchange device with the A step, the Hydrogen resin cation (R.C.) is arranged in the device, the water through after the ion exchange treatment returns refining step and recycles.
The used film of A step can be a kind of in aluminum oxide, zirconium white, the titanium oxide, membrane pore size 0.05～0.8 μ m, filtration area 0.1-1m
2, service temperature 20-100 ℃, working pressure 0.10-0.40MPa.
B step ion exchange resin adopts hydrogen type strong acid type resin cation (R.C.), better adopts Rohm﹠amp; The Amberjet1500H of Haas company or 1600H strong acid type resin, ion exchange column are single-column or twin columns, and stacking volume 100～500ml, flow are 100-200ml/h, service temperature 50-90 ℃.
A step and B step can be carried out continuously, also can distinguish periodical operation.
The present invention can handle phthalic acid mother water, as terephthalic acid, also can handle the naphthalic acid mother liquor.
This treatment process is simple, floor space is little, energy consumption is low, can reach the reuse water standard.The feature of this treatment process is " the ceramic membrane micro-filtration separates and ion-exchange absorption " combination.This combination process has overcome the deficiency of existing technology, valuable aromatic carboxylic acid solid in the not only recyclable mother liquor, also removed the metal ion in the water, made the solid waste water of mother of processing can reach the controlling index of reuse technology water, thereby reduce the total emissions amount of waste water.
Description of drawings
Accompanying drawing 1 is that aromatic carboxylic acid provided by the invention is produced mother liquor recycling and processing device schema;
The 1-mother liquor; The 2-membrane separation unit; The 3-concentrated solution; The 4-penetrating fluid; The 5-storage tank; The 6-ion exchange unit
Below in conjunction with accompanying drawing the present invention is described in further detail.
It is 0.05-0.8 μ m that membrane separation unit adopts membrane pore size, and acidproof base number is at 0～14 suite of equipment.
The mother liquor screen apparatus of flowing through earlier usually carries out pre-treatment, the solid of larger particles is held back, with the anti-clogging plug membrane channel.Selecting sieve mesh for use is 10 orders.Filter with inorganic ceramic film device 2 then, produce concentrated solution 3 and penetrating fluid 4.Inorganic ceramic film can make particle diameter be retained down greater than the insoluble solids particle of 50nm, the pollution when reducing the operation of follow-up ion exchange unit.Concentrated solution returns concentration tank, and small part is got back to press filtration unit recovery part aromatic carboxylic acid and organic acid by product.Penetrating fluid enters storage tank 4 and advances next operating unit, carries out ion-exchange.
With being pumped into ion exchange unit 6, after ion-exchange, obtain qualified reuse mother liquor from the penetrating fluid of storage tank 4.In the bed Hydrogen resin cation (R.C.) is arranged, resin cation (R.C.) can be removed each metal ion species, otherwise these handle mother liquor later when reuse, and metal ion wherein can pollute catalyzer, causes poisoning of catalyst.Were it not for top membrane filter unit, insoluble organic acid solid may exchange bed by contaminated ion in the mother liquor, makes cationic exchange capacity sharply descend.This patent adopts Rohm ﹠amp; The Amberjet1500H of Haas company or 1600H strong acid type resin, effect is better.
The service temperature of inorganic ceramic film device is approximately 20-100 ℃, approaches waste water liquid effluent temperature, has saved energy to greatest extent, can obtain higher membrane flux simultaneously; Working pressure is 0.15～0.4MPa, crossflow velocity 1.0～5.0m/s.
Ion exchange unit operating procedure condition is: ion exchange column is single-column or twin columns, and column internal diameter 2～5cm, resin loading height are 15～30cm, and the buildup of resin volume is 100～500ml, and flow is 100～200ml/h, and the exchange operations temperature is 50～90 ℃.
Through the water after the ion exchange treatment, concentration of metal ions can reach the technical indicator (mg/l) of reuse water: Fe
2+≤ 0.1; Na
+≤ 5.0; Cr
3+≤ 0.1; Cr
2+≤ 0.5; Co
2+≤ 0.5; Mn
2+≤ 0.3; Ni
+≤ 0.1, return refined unit and recycle.
In the process of membrane operations, As time goes on membrane flux can descend, and can recover membrane flux by the mode of carrying out sub-high pressure recoil at regular intervals.During recoil, the high-pressure air in the air compressor machine (will wash open attached to the solid particulate in film and the duct, thereby recover membrane flux by 0.3～0.4MPa) surface along pipeline 3 reverse quick impact ceramic membranes.Preferable recoil pressure is 0.15～0.40Mpa, and the recoil time is 1～5 second, and the recoil cycle is 5～60 minutes.
But if through after the more recoil cycle, film pollutes still inevitable, can not recover membrane flux by the recoil operation merely, and it is comparatively serious to show that film pollutes, and at this moment just need clean film.
The present invention adopts after the first alkali cleaning method of pickling that the film of getting dirty is cleaned.Can select simple static rinse method: the film of will getting dirty is statically placed in the aqueous solution that fills 3～10%NaOH, cleans with clear water after 30～60 minutes; And then be placed on 3～5%HNO
3The aqueous solution in, clean with clear water after 30～60 minutes.The membrane flux recovery rate can reach more than 90%, and decay is slower in time.Also can select dynamic continuous wash method: close waste water import and outlet valve, use earlier the flushing with clean water film device, the discharging clear water; In purge tank, add the aqueous solution of 1～5%NaOH, close pipeline, only of short duration opening near end the time; The buck circulation was cleaned about 30 minutes; The discharging buck reduces to 10 in order to cleaning next time to continue to use to the pH value to the buck jar; The aqueous solution that in purge tank, adds 1～5% hydrochloric acid or nitric acid, operation is as alkali cleaning; At last with clear water clean to the pH value be 6.
After handling a certain amount of mother liquor, need carry out manipulation of regeneration to ion exchange bed.In reprocessing cycle, can be by the realization that contacts of arbitrary acid and resin, this acid will neither damage resin again can be from metal ion under the resin displacement.The range of choice of regenerating acid is hydrochloric acid, bromic acid or acetic acid, and acetic acid, bromic acid can be diluted to 1～20%, are preferably 2～10%; It is effective especially that acetic acid can be diluted to 5～30% pairs of regenerating resins, and can recycle in the production operation of some terephthalic acid.After a regeneration period, acetic acid, Hydrogen bromide can be recycled directly in the production technique of terephthalic acid or before the circulation and at first use.The regenerated process makes the regenerating acid Zeo-karb device of once flowing through exactly.In regenerative process, Zeo-karb discharges metal ion.
Embodiment
Embodiment 1:
Raw material waste water: get the female solid waste water of certain chemical plant pta, filter filtration area 0.1m earlier through aluminum oxide
2, fenestra aperture 0.05 μ m, working pressure 0.10MPa; Through ion exchange unit, ion exchange resin is selected Amberjet1500H for use again, and the buildup of resin volume is 100ml, and flow is 100ml/h, and the pta solids content is 0.2% (wt) before the wastewater treatment, and concentration of metal ions is: Ni
+0.211mg/L, Fe
2+1.117mg/L, Cr
3+0.046mg/L, Co
2+4.602mg/L, Na
+100.5mg/L, Mn
2+14.41mg/L, handle back pta solid and be concentrated to 5.0% (wt), returning the PTA quality that reclaims after the press filtration workshop section is 80% of total amount, underwater gold belongs to concentration and is: Ni
+＜0.01mg/L, Fe
2+＜0.01mg/L, Cr
3+＜0.01mg/L, Co
2+＜0.01mg/L, Na
+0.95mg/L, Mn
2+＜0.01mg/L reaches the technic index of reuse water.
Embodiment 2: the mother liquor index is with embodiment 1 before handling, and treatment process is with embodiment 1, ceramic membrane material selection zirconium white, and the fenestra aperture is 0.2 μ m, filtration area 1m
2, working pressure 0.40MPa; Ion exchange resin is selected Amberjet1600H for use, and the buildup of resin volume is 150ml, and flow is 140ml/h, and after the processing, the pta solid is concentrated to 5.2% (wt), and returning the PTA quality that reclaims after the press filtration workshop section is 82% of total amount, and underwater gold belongs to concentration and is: Ni
+＜0.01mg/L, Fe
2+＜0.01mg/L, Cr
3+＜0.01mg/L, Co
2+＜0.01mg/L, Na
+0.84mg/L, Mn
2+＜0.01mg/L reaches the technic index of reuse water.
Embodiment 3: the mother liquor index is with embodiment 1 before handling, and treatment process is with embodiment 1, ceramic membrane material selection titanium oxide, and the fenestra aperture is 0.8 μ m, filtration area 1m
2, working pressure 0.30MPa; Ion exchange resin is selected Amberjet1500H for use, and the buildup of resin volume is 350ml, and flow is 200ml/h, and after the processing, the pta solid is concentrated to 5.3% (wt), and returning the PTA quality that reclaims after the press filtration workshop section is 81% of total amount, and underwater gold belongs to concentration and is: Ni
+＜0.01mg/L, Fe
2+＜0.01mg/L, Cr
3+＜0.01mg/L, Co
2+＜0.01mg/L, Na
+0.70mg/L, Mn
2+＜0.01mg/L reaches the technic index of reuse water.
Embodiment 4: mother liquor index before handling: the pta solids content is 0.27% (wt), and concentration of metal ions is: Ni
+0.254mg/L, Fe
2+1.025mg/L, Cr
3+0.050mg/L, Co
2+5.024mg/L, Na
+99.56mg/L, Mn
2+13.67mg/L treatment process is with embodiment 1, ceramic membrane material selection aluminum oxide, and the fenestra aperture is 0.8 μ m, filtration area 1m
2, working pressure 0.10MPa; Ion exchange resin is selected Amberjet1600H for use, and the buildup of resin volume is 250ml, and flow is 175ml/h, and after the processing, the pta solid is concentrated to 5.2% (wt), and returning the PTA quality that reclaims after the press filtration workshop section is 81% of total amount, and underwater gold belongs to concentration and is: Ni
+＜0.01mg/L, Fe
2+＜0.01mg/L, Cr
3+＜0.01mg/L, Co
2+＜0.01mg/L, Na
+0.84mg/L, Mn
2+＜0.01mg/L reaches the technic index of reuse water.
Embodiment 5: the mother liquor index is with embodiment 2 before handling, and treatment process is with embodiment 1, ceramic membrane material selection zirconium white, and the fenestra aperture is 0.2 μ m, filtration area 1m
2, working pressure 0.20MPa; Ion exchange resin is selected Amberjet1500H for use, and the buildup of resin volume is 400ml, and flow is 185ml/h, and after the processing, the pta solid is concentrated to 4.9% (wt), and returning the PTA quality that reclaims after the press filtration workshop section is 80% of total amount, and underwater gold belongs to concentration and is: Ni
+＜0.01mg/L, Fe
2+＜0.01mg/L, Cr
3+＜0.01mg/L, Co
2+＜0.01mg/L, Na
+0.68mg/L, Mn
2+＜0.01mg/L reaches the technic index of reuse water.
Embodiment 6: the mother liquor index is with embodiment 2 before handling, and treatment process is with embodiment 1, ceramic membrane material selection zirconium white, and the fenestra aperture is 0.2 μ m, filtration area 1m
2, working pressure 0.40MPa; Ion exchange resin is selected Amberjet1600H for use, and the buildup of resin volume is 500ml, and flow is 200ml/h, and after the processing, the pta solid is concentrated to 5.1% (wt), and returning the PTA quality that reclaims after the press filtration workshop section is 84% of total amount, and underwater gold belongs to concentration and is: Ni
+＜0.01mg/L, Fe
2+＜0.01mg/L, Cr
3+＜0.01mg/L, Co
2+＜0.01mg/L, Na
+0.57mg/L, Mn
2+＜0.01mg/L reaches the technic index of reuse water.
Embodiment 7: adopt after the first alkali cleaning method of pickling that film is cleaned, add 5%NAOH solution in concentration tank, close pipeline 3, the buck wash cycles was discharged buck after 30 minutes.
In concentration tank, add 5% hydrochloric acid or aqueous nitric acid, close pipeline 3, pickling discharging in 30 minutes sour water.In concentration tank, add clear water clean to the ceramic membrane pH value be 6.Polluting the pre-ceramic membrane flux is 300-1000L/ (h*m
2), cleaning the back membrane flux is 290-1000L/ (h*m
2).
Embodiment 8: the hydrochloric acid with 5% is regenerated to contaminated ion exchange column, and the loading capacity of Zeo-karb is 40-80g/l before polluting, and regeneration back loading capacity is 38-80g/l.
Embodiment 9: raw material waste water: get certain factory 2, and 6-naphthalic acid waste water, solid content is 0.26% (wt) before the wastewater treatment, concentration of metal ions is: Ni
+0.321mg/L, Fe
2+1.251mg/L, Cr
3+0.049mg/L, Co
2+5.023mg/L, Na
+98.504mg/L, Mn
2+12.532mg/L.Filter filtration area 0.1m earlier through pellumina
2, fenestra aperture 0.05 μ m, working pressure 0.10MPa; Through ion exchange unit, ion exchange resin is selected Amberjet1600H for use again, and the buildup of resin volume is 100ml, flow is 100ml/h, handles the back solid and is concentrated to 5.2% (wt), 2 of recovery, 6-naphthalic acid quality is 84% of a total amount, and underwater gold belongs to concentration and is: Ni
+＜0.01mg/L, Fe
2+＜0.01mg/L, Cr
3+＜0.01mg/L, Co
2+＜0.01mg/L, Na
+0.84mg/L, Mn
2+＜0.01mg/L reaches the technic index of reuse water.
Claims (5)
1, the recovery method of mother liquor during a kind of aromatic carboxylic acid is produced may further comprise the steps:
A, membrane filtration: mother liquor inorganic ceramic membrane filtration, concentrated solution returns the press filtration operation, and penetrating fluid enrichment between mineral membrane and film overcoat enters ion exchange unit then,
B, ion-exchange: the penetrating fluid process cationic exchange device with the A step, the Hydrogen resin cation (R.C.) is arranged in the device, the water through after the ion exchange treatment returns refining step and recycles;
The used ceramic membrane of A step can be a kind of in aluminum oxide, zirconium white, the titanium oxide,
B step ion exchange resin adopts hydrogen type strong acid type resin cation (R.C.),
A step and B step can be carried out continuously, also can distinguish periodical operation.
2, method according to claim 1 is characterized in that membrane pore size 0.05～0.8 μ m, filtration area 0.1-1m
2, service temperature 20-100 ℃, working pressure 0.10-0.40MPa, ion exchange unit are single-column or twin columns, and stacking volume 100～500ml, flow are 100-200ml/h, and service temperature 50-90 ℃, ion exchange resin adopts Rohm ﹠amp; The Amberjet1500H of Haas company or 1600H strong acid type resin.
3, method according to claim 1 and 2 is characterized in that described mother liquor is a phthalic acid mother water.
4, method according to claim 1 and 2 is characterized in that described mother liquor is the naphthalic acid mother liquor.
5, according to the treatment process of the described ceramic membrane of claim 1, may further comprise the steps: recoiled time 1-5 second with the reverse quick impact ceramic membrane surface of 0.3-0.4MPa high-pressure air, and perhaps cleaned in every 5-60 minute with following step:
A, in concentration tank, add 1-5%N
aOH solution is closed pipeline 3, and the buck wash cycles was discharged buck after 30 minutes,
B, in concentration tank, add 1-5% hydrochloric acid or aqueous nitric acid, close pipeline 3, pickling discharging in 30 minutes sour water,
C, in concentration tank, add clear water clean to the ceramic membrane pH value be 6.
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|---|---|---|---|
| CN 200410041380 CN1276879C (en) | 2004-07-15 | 2004-07-15 | Method for recovering mother solid water in aromatic carboxylic acid production |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249454A (en) * | 2011-05-17 | 2011-11-23 | 李大伟 | Method for comprehensively utilizing PTA (pure terephthalic acid) wastewater containing solid particles |
| CN101745410B (en) * | 2008-12-17 | 2012-07-18 | 凯能高科技工程（上海）有限公司 | Method for recycling catalyst from waste water produced in purifying process of aromatic acids |
| CN110128266A (en) * | 2019-03-27 | 2019-08-16 | 佰仕邦水处理环保科技(大连)有限公司 | A kind for the treatment of process of the liquor abstraction liquid for p-phthalic acid's oxidation unit |
| CN110255769A (en) * | 2019-07-02 | 2019-09-20 | 佰仕邦水处理环保科技(大连)有限公司 | A kind for the treatment of process of the aqueous solution for terephthalic acid production plant |
| CN114804546A (en) * | 2022-06-02 | 2022-07-29 | 无锡市兴盛环保设备有限公司 | PTA mother liquor recovery processing method based on membrane technology |
-
2004
- 2004-07-15 CN CN 200410041380 patent/CN1276879C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745410B (en) * | 2008-12-17 | 2012-07-18 | 凯能高科技工程（上海）有限公司 | Method for recycling catalyst from waste water produced in purifying process of aromatic acids |
| CN102249454A (en) * | 2011-05-17 | 2011-11-23 | 李大伟 | Method for comprehensively utilizing PTA (pure terephthalic acid) wastewater containing solid particles |
| CN110128266A (en) * | 2019-03-27 | 2019-08-16 | 佰仕邦水处理环保科技(大连)有限公司 | A kind for the treatment of process of the liquor abstraction liquid for p-phthalic acid's oxidation unit |
| CN110128266B (en) * | 2019-03-27 | 2022-12-27 | 佰仕邦水处理环保科技(大连)有限公司 | Treatment process of mother liquor extract for purified terephthalic acid oxidation unit |
| CN110255769A (en) * | 2019-07-02 | 2019-09-20 | 佰仕邦水处理环保科技(大连)有限公司 | A kind for the treatment of process of the aqueous solution for terephthalic acid production plant |
| CN114804546A (en) * | 2022-06-02 | 2022-07-29 | 无锡市兴盛环保设备有限公司 | PTA mother liquor recovery processing method based on membrane technology |
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| Publication number | Publication date |
|---|---|
| CN1276879C (en) | 2006-09-27 |
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