CN1215761A - Method for recovery of Co-Mn metal from p-phthalic acid residual liquid - Google Patents
Method for recovery of Co-Mn metal from p-phthalic acid residual liquid Download PDFInfo
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- CN1215761A CN1215761A CN97119183A CN97119183A CN1215761A CN 1215761 A CN1215761 A CN 1215761A CN 97119183 A CN97119183 A CN 97119183A CN 97119183 A CN97119183 A CN 97119183A CN 1215761 A CN1215761 A CN 1215761A
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Abstract
A process for recovering Co and Mn metals from residual tere-phthalic acid liquid features that the Co-Mn containing extract obtained by extracting twice reacts with the S-containing waste alkali solution which is discharged from production of ethylene or the waste alkali solution after carbonating to recover Co-Mn metals. Its advantages are use of waste, less investment, simple method and high recovery.
Description
The invention belongs to the method for chemical industry waste recovery metal, more specifically say so and from the residue liquid of producing pure terephthalic acid (PTA), reclaim the method for cobalt, manganese metal.
Pure terephthalic acid (PTA) is a main raw material of producing polyester.The method of producing PTA at present generally is to adopt oxidizing process promptly to make catalyzer with Cobaltous diacetate and manganese acetate, in acetum, obtains through high-temperature liquid-phase atmospheric oxidation p-Xylol.For guaranteeing the PTA quality, in producing, also 10～20% mother liquor must be extracted out PTA, reclaim a large amount of acetic acid through thin-film evaporator, remaining for containing terephthalic acid (TA) raffinate of cobalt, manganese, monobasic and binary aralkyl carboxylic acid, acetic acid.This part raffinate adopts the water making beating that adds equivalent to discharge.One cover is produced 600,000 tons of/year para-phthalic acid (pta)s, will discharge raffinate every year and exceed ten thousand tons, wherein contains the cobalt amount and is about 35.5 tons, if the cobalt in this part raffinate, manganese metal can be reclaimed, will produce very big benefit.
Cobalt is a kind of non-ferrous metal of costliness, and each state all takes much count of the recovery of cobalt, and the method that reclaims cobalt at present roughly has methods such as extraction, ion-exchange, chemical precipitation.USP4312778 proposes the residue raffinate 25～100 ℃ of following water benzene extraction carboxylic acid production processes, separates to obtain catalyst metal components; USP4162991 adopts ion exchange method promptly to use strongly basic anion exchange resin adsorption of cobalt and bromide ion, makes cobalt and bromide ion desorb with water content greater than 10% low lipid monoprotic acid; Fudan University proposes water extraction terephthaldehyde acid residue liquid with i.e. (4-pyridine sulfo-) sodium acetate extraction of P507 soda soap Co, Mn → the add HCl Na that strips → add
2CO
3Be converted into Co, Mn carbonate.This method consumes acetic acid, Na
2CO
3More, P507 price height, Co, Mn loss is big; Shanghai general petrochemicals factory adopts the Mitsui oiling technology, its to the effect that: 10% mother liquor is entered catalyst recovery devices, reclaims acetic acid through thin-film evaporator, under 45 ℃ with the deionized water extraction, the reuse after concentrated of the acetic acid of gained, cobalt, manganese extraction liquid.Adopt catalyst recovery devices, about 70% catalyst acetic acid cobalt, manganese acetate be directly return mechanism use after concentrating, but the energy consumption height, equipment is many, and pipeline easily stops up, and other has 30% water to discharge, and increases the load of water treatment device.
The objective of the invention is to propose the method that a kind of waste lye of discharging with ethylene unit reclaims the cobalt manganese in terephthalic acid (TA) the residue liquid.
Technical scheme of the present invention: steam cobalt, manganese in acetic acid → twice extraction → sulfur-containing waste lye recovery extraction liquid.
Technical scheme of the present invention: steam cobalt, manganese in the waste lye recovery extraction liquid after acetic acid → twice extraction → carbonating is handled.
Concrete operations step of the present invention comprises:
1. steam acetic acid in the terephthalic acid raffinate with common rectifying tower, remaining is the residue liquid that contains 2～3% acetic acid;
2. the residue liquid that is contained 2～3% acetic acid (1) step is cooled to room temperature, add twice extraction of water then, extraction water/slag is 2.5～5.0 for the first time, extraction water/slag 2.5 for the second time, stirring velocity 100～the 120r/min of twice extraction, churning time 0.25～0.5h, each back of stirring stops 1-1.2h, promptly obtain cobalt, manganese extraction liquid then after filtration, extraction liquid gives over to raffinate usefulness next time for the second time;
3. in sulfur-containing waste lye, add the extraction liquid first time in (2) step,, add Na again to mixture PH＜7.5
2OH solution, making PH is 8.5～9.0;
4. add cationic-type polyacrylamide (1%M-PAM) in the mixture that obtains of (3) step, add-on is 10 of a reaction mass amount
-4, make cobalt manganese slag flocculation sediment, obtain cobalt manganese slag after filtration.
Obtain containing cobalt at last, the manganese slag can adopt method commonly used to reclaim Co-Mn metal or its product.
Above-mentioned steps (1) is if acetic acid content＜5% o'clock need not redistillation acetic acid.Concrete operations: the residue liquid that does not distill acetic acid adopts and to staticly settle, layering, siphon upper strata cobalt manganese liquid, water gaging single extraction, the same step of other extraction conditions (2) such as adds again in wet slag.Cobalt manganese content accounts for about 60% of cobalt manganese total amount in the described cobalt manganese liquid.
The described filtration of step (2) can be adopted suction filtration or centrifuging.
The described sulfur-containing waste lye of step (3) be discharge in the ethylene production sulfur-containing waste lye, this waste lye contains 10～12% Na
2S, 4～5% Na
2CO
3, 1～3% NaOH.
Above-mentioned steps (3) can also be used CO
2Sulfur-containing waste lye after the processing, this waste lye contains Na
2CO
3And NaHCO
3Concrete operations with this waste lye: add the waste lye after carbonating is handled in the manganese cobalt extraction liquid with (2) step gained, the reaction beginning is not heated, do not stir, be raised to 8.0 backs to pH value and stir, stirring velocity 120～220r/min keeps 50～60 ℃ of temperature of reaction, reacting final pH value is 8.4～9.4, restir 0.5h is incubated 50～60 ℃, 1.5～2h, directly obtains cobalt manganese slag.Can save for the 4th step with this waste lye and promptly need not add M-PAM, because of what obtain mainly is cobalt manganese carbonate after the reaction, particle is bigger, easily precipitation.The concentration of the waste lye after described carbonating is handled does not have influence to reaction result, and can institute consumes the salkali waste liquid measure only need be enough to precipitate cobalt manganese from total amount calculating and get final product.
The cobalt manganese slag that the present invention obtains can adopt known industrial process to reclaim Co-Mn metal or its product.For example use H
2SO
4Dissolving makes expensive pure cobalt by electrolysis, and manganous sulfate can make the chemical reagent MnSO of different grades by filtration, evaporative crystallization, dehydration, drying in the mother liquor
4H
2O; Also can be after the oxidation calcination, carbonate is changed into be insoluble to the MnO of olefin(e) acid
2, add diluted acid dissolved oxygen cobalt again, produce cobalt naphthenate (paint siccative) and manganese reagent respectively.
Major advantage of the present invention: the TA raffinate that (1) can make the PTA device produce obtains administering, and reclaims cobalt, manganese metals resources, the recyclable about 35.5 tons cobalt of the device of 600,000 tons of PTA/, and eliminated partial area because the environmental pollution that the TA raffinate brings; (2) the present invention is because the sulfur-containing waste lye that adopts ethylene unit to discharge reclaims cobalt, the manganese metal in the TA raffinate, the treatment of wastes with processes of wastes against one another, comprehensive utilization, and no longer produce new pollution again, therefore the effective ways of a disposal of waste gas, water and industrial residue are provided, by experiment as can be known, behind sulfur-containing waste lye recovery cobalt manganese, the water quality of discharge water: Co
2+＜5mg/l, Mn
2+＜20mg/l, S＜400mg/l, PH＜9.0, CODcr about 1.0 * 10
5Mg/l can carry out biochemical treatment; Waste lye after handling with carbonating reclaims cobalt manganese since the sulfide of this waste lye own just very low (sulfide＜20mg/l, oil＜30mg/l), S and CODcr in the discharge water are lower, therefore more can carry out biochemical treatment;
(3) adopt method less investment of the present invention, energy consumption is low, and used equipment is simple, Co-Mn metal rate of recovery height, and in sum, method of the present invention is that economic benefit or social benefit are all very obvious.
Further set forth characteristics of the present invention with example below.
Example 1
This example is that different water/slag ratioes is carried out the test of twice extraction cobalt manganese, and test is carried out under room temperature 100r/min condition, and the TA raffinate component of test usefulness sees Table 1, twice extraction results and sees Table 2.Test-results is selected suitable water/slag ratio as can be known, and through twice extraction, cobalt, manganese percentage extraction reach more than 95%.The single extraction liquid of water/slag ratio less (＜2.5), because of acidity is bigger, aralkyl carboxylic acid dissolving is more, increases in the mutual reactance alkali number consumption and discharge water CODcr value is increased; The total percentage extraction of single extraction liquid of water/slag ratio big (＞6) increases few, but water displacement increases, so single extraction water/slag is 2.5～5.0, and reextraction water/slag is 2.5 the most suitable.
Example 2
This example is to reclaim the test of cobalt manganese with the sulfur-bearing waste residue liquid.The sulfur-containing wasting alkali fluid component sees Table 3.The used raffinate of the present invention is the C sample of table 1, and used waste lye is the 3rd a batch of waste lye in the table 3.Process of the test:
Extraction: the C4.20Kg that materialses (containing Co15.43g, Mn41.43g) steams acetic acid earlier, steams acetic acid 1.49Kg, water 0.17Kg.Get 2.54Kg still slag liquid, be cooled to room temperature, add the extraction fluid that ortho-water 4.70Kg and 4.60Kg last time extracted and (contain Co3.23g, Mn8.84g) carry out single extraction, extraction conditions is a room temperature, stirring velocity 100～120r/min, churning time is 0.25～0.5h, stir the back and stop 1～1.5h, obtain a cobalt manganese extraction liquid 8.24Kg then after filtration and (contain cobalt 15.58g, manganese 41.45g), get 3.06Kg slag (water ratio about 64%) in addition, add the 4.20Kg ortho-water again in this slag, carry out reextraction, extraction conditions is the same, get the 4.87Kg extraction fluid and (contain cobalt 2.96g, manganese 8.52g), 2.39Kg raffinate residue (moisture about 64%, Co0.12g, Mn0.30g), extraction fluid is waited until usefulness when doing following batch of residue extraction, and purpose is to reduce the discharging water yield.
Mutual reactance generates cobalt manganese slag: add table 3 the 3rd lot sample sulfur-containing waste lye 2.15Kg (containing S98.9g) in encloses container, add above-mentioned single extraction liquid 3.73Kg (containing cobalt 7.05g, manganese 18.76g) from the bottom with conduit, add-on reaches about 7.0 with pH value and exceeds, stirring at low speed is 90～150r/min from slow to fast, and the gas that generates in the reaction is drawn from encloses container and fed the NaOH solution absorption.Add 4.5%NaOH solution 0.52Kg again, making final pH value is 8.8, the 0.1%M-PAN flocculation agent that adds 0.065Kg then, slowly stir 2min, stop half an hour, filter 0.254Kg (containing 31.4%Co, Mn) black slag, other has 6.211Kg discharge water (containing Co0.026g, Mn0.0447g, S2.48g).
By above-mentioned test-results as can be known, cobalt manganese single extraction rate 80.0%, the 78.7% reextraction rate that is respectively is respectively 19.2%, 20.6%, total percentage extraction is respectively 99.2%, 99.3%, mutual reactance cobalt manganese deposition rate is respectively 99.7%, 99.8%, the removal of sulphur rate is 97.5%, cobalt manganese sulphur content difference 4.19ppm, 7.20ppm, 400ppm in the discharge water.
Example 3
This example is an acetic acid content lower (＜5%) in the TA residue liquid, and residue liquid is discharged through the making beating of fetching water again, and content of the test directly extracts for not steaming acetic acid, and used residue liquid is E sample in the table 1, process of the test:
Get the E sample, room temperature, stir, stirring velocity is 100～120r/min, churning time is that 0.5h (do not have precipitation as sample, churning time can shorten) leaves standstill then, and time of repose is more than 3 days, obviously layering, the siphon supernatant liquor does not filter, and gets wet slag (water ratio about 60%), adds the equivalent ortho-water and extracts, extraction conditions is with extraction conditions in the example 2, filter extraction liquid and TA raffinate slag, again siphon supernatant liquor and extraction liquid are mixed and alkali (sulfur-containing waste lye, carbonating are handled waste lye afterwards, chemistry is joined alkali) mutual reactance generation cobalt manganese slag, the mutual reactance condition is seen example 2 and following example 4 respectively.
Example 4
Waste lye after this example is handled with olefin plant carbonic acid reclaims the test of cobalt manganese.
The olefin plant carbonating is handled the waste lye component and is seen Table 5, the sample that 97-3.21 and 97-4-18 got, and Co, Mn extraction liquid adopt example 2,3 methods to make.
Process of the test: progressively add the waste lye after carbonating is handled in cobalt manganese extraction liquid, reaction is initially the acetic acid in waste lye and the extraction liquid, and the acid-base neutralisation reaction between the residual aralkyl carboxylic acid has a large amount of CO
2Bubble produces, and does not heat (exothermic heat of reaction) this moment and does not stir, along with the bubble minimizing is carried out in reaction, pH value rises to about 8.0, continues to add waste lye, stirring at low speed, speed is 120～220r/min, and the insulation water-bath keeps temperature of reaction between 50～60 ℃, constantly has this moment precipitation to generate, when pH value is 8.4～9.4, stop to add waste lye, reaction terminating, stir half an hour, be incubated 50～60 ℃, 2.0h, placement is spent the night, filter, obtain red cobalt manganese slag.
Test-results sees Table 6, and the waste lye after being handled with carbonating as can be known by test reclaims cobalt manganese, and the reaction conditions gentleness is easy to operate, no toxic gas H
2S produces, and need not add flocculation agent, and Co, the Mn rate of recovery are higher, and products therefrom is a cobalt manganese carbonate, easily subsequent disposal.
Table 1 test TA raffinate component table (m%)
| TA raffinate sample | ????HAC | Water | Colloidal solid | ?Co 2+ | Mn 2+ |
| ????A | ????62.8 | ?5.80 | ????30.8 | ?0.16 | ?0.43 |
| ????B | ????43.4 | ?3.70 | ????51.9 | ?0.26 | ?0.68 |
| ????C | ????41.2 | ?4.10 | ????53.3 | ?0.37 | ?0.99 |
| ????D | ????11.1 | ?56.0 | ????32.2 | ?0.31 | ?0.28 |
| ????E | ????4.23 | ?69.3 | ????26.2 | ?0.17 | ?0.14 |
Different water/the slag ratioes of table 2, and twice extraction cobalt manganese test [notes] (room temperature, 100r/min)
| TA raffinate sample | Water/slag | Co percentage extraction (m%) | Mn percentage extraction (m%) | |||||
| Once | Secondary | Once | Secondary | Always | Once | Secondary | Always | |
| ????B | ?2.5 | ?2.5 | ?78.5 | ?16.8 | ?95.3 | ?78.8 | ?16.3 | ?95.1 |
| ????B | ?3.0 | ?2.5 | ?80.9 | ?15.1 | ?96.0 | ?79.3 | ?16.3 | ?95.6 |
| ????B | ?3.7 | ?2.5 | ?81.9 | ?13.9 | ?95.8 | ?81.4 | ?14.4 | ?95.8 |
| ????B | ?4.4 | ?2.5 | ?83.0 | ?12.5 | ?95.5 | ?82.4 | ?12.8 | ?94.9 |
| ????B | ?5.0 | ?2.5 | ?85.0 | ?12.0 | ?97.0 | ?84.4 | ?12.2 | ?96.6 |
Annotate: 1. the B sample is steamed acetic acid earlier, again twice extraction.
Grain slag than in slag be that the slag that steams behind acetic acid and the water is heavy.
3. cobalt manganese content is by atomic absorption spectroscopy determination.
4. percentage extraction calculation formula:
Table 3 sulfur-containing wasting alkali fluid component table
| Component | Form |
| First second batch the 3rd batch | |
| Proportion Na 2S,m％ ????Na 2CO 3,m％ ????NaOH,m％ ????S 2-mg/l | ????1.16??????1.19????????1.18 ????9.31??????10.34???????8.24 ????3.31??????5.13????????3.64 ????4.98??????3.71????????4.86 ????5.14×10 45.80×10 4??5.43×10 4 |
Cobalt in table 4 siphon liquid, the extraction liquid, manganese content (m%)
Table 5 olefin plant carbonating is handled the back waste lye
Table 6 carbonating is handled the back waste lye and is reclaimed Co, Mn test
| Acetic acid | Cobalt | Cobalt distributes | Manganese | Manganese distributes | |
| 1995.6.30 sample | 4.23 | ?0.18 | ?100 | ?0.15 | ?100 |
| Siphon liquid | 5.32 | ?0.22 | ?59.7 | ?0.18 | ?57.5 |
| Extraction liquid (once) | 2.15 | ?0.084 | ?34.0 | ?0.076 | ?36.5 |
| Recrement | 0.042 | ?6.0 | ?0.036 | ?5.8 |
| Sample time | ????PH | ?Na 2CO 3,m％ | NaHCO 3,m％ | Oil, mg/l | Sulfide, mg/l |
| ?97-3-21 ?97-4-18 ?97-5-8 | ?9.12 ?8.97 ?9.16 | ????5.41 ????2.33 ????1.60 | ?4.4 ?3.02 ?5.96 | ????3.1 | ?28.4 ?8.66 ?12.18 |
| Co, Mn extraction liquid | Waste lye | Final pH value | The rate of recovery (m%) | Remarks | |||||
| V(ml) | Co (m％ | Mn (m％) | V(ml) | Na 2CO 3(m％) | NaHCO 3(m％) | Co | Mn | ||
| 600 | ?1.67×10 3 | 2.68×10 3 | 900 870 | ?5.41 | ?4.4 | ?9.26 ?9.06 | ?99.7 ?99.7 | ?100 ?100 | Co, Mn extraction liquid are taken from Co, Mn and are reclaimed factory, and waste lye is taken from the 97.3.21 olefin plant and discharged alkali lye |
| 100 | ?1.67×10 3 | 2.66×10 3 | 460 480 | ?2.33 | ?3.02 | ?9.41 ?9.36 | ?99.5 ?98.5 | ?100 ?100 | Co, Mn extraction liquid are taken from Co, Mn and are reclaimed factory, and waste lye is taken from the 97.4.18 olefin plant and discharged alkali lye |
| 300 | ?1.94×10 3 | 1.84×10 3 | 750 780 | ?5.41 | ?4.4 | ?9.18 ?9.23 | ?99.3 ?99.3 | ?100 ?100 | Co, Mn extraction liquid are taken from the laboratory, and waste lye is taken from the 97.3.21 olefin plant and discharged alkali lye |
| 100 | ?1.94×10 3 | 1.84×10 3 | 1000 800 | ?2.33 | ?3.02 | ?9.01 ?8.92 | ?96.3 ?98.3 | ?100 ?100 | Co, Mn extraction liquid are taken from the laboratory, and waste lye is taken from the 97.4.18 olefin plant and discharged alkali lye |
Claims (4)
1. a method that reclaims the Co-Mn metal in the terephthalic acid raffinate comprises distillation, extraction process, it is characterized in that concrete operating process comprises:
(1) steam acetic acid in the terephthalic acid raffinate with common rectifying tower, remaining is the residue liquid that contains 2～3% acetic acid;
(2) (1) is gone on foot the residue liquid that contains 2～3% acetic acid and be cooled to room temperature, add twice extraction of water then, extraction water/slag is 2.5～5.0 for the first time, extraction water/slag is 2.5 for the second time, stirring velocity 100～the 120r/min of twice extraction, churning time 0.25～0.5h, each back of stirring stops 1～1.2h, obtain cobalt, manganese extraction liquid then after filtration, extraction liquid gives over to next raffinate usefulness for the second time;
(3) add the extraction liquid first time in (2) step in sulfur-containing waste lye, to mixture PH＜7.5, add NaOH again, making PH is 8.5～9.0;
(4) add cationic-type polyacrylamide in the mixture that obtains of (3) step, add-on is 10 of a reaction mass amount
-4, make cobalt manganese slag flocculation sediment, obtain cobalt manganese slag after filtration.
2. in accordance with the method for claim 1, it is characterized in that acetic acid content in the terephthalic acid raffinate is less than saving distilation steps at 5% o'clock, the residue liquid that does not steam acetic acid can be adopted staticly settle, layering, siphon upper strata cobalt manganese liquid such as adds again at the water gaging single extraction in wet slag.
3. in accordance with the method for claim 1, it is characterized in that the described sulfur-containing waste lye of step (3) is 10～12% the Na of containing that discharges in the ethylene production
2S, 4～5% Na
2CO
3Waste lye with 1～3% NaOH.
4. according to claim 1 or 2 described methods, it is characterized in that step (3) can also use CO
2Sulfur-containing waste lye after the processing, its operating process: add CO in the cobalt manganese extraction liquid with gained
2Contain Na after the processing
2CO
3And NaHCO
3Waste lye, be raised to 8.0 backs to PH and stir, stirring velocity 120～220r/min keeps 50～60 ℃ of temperature of reaction, reacting final PH is 8.4～9.4 o'clock restir 0.5h, is incubated 50～60 ℃, 1.5～2h, directly obtains cobalt manganese slag.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97119183A CN1117163C (en) | 1997-10-27 | 1997-10-27 | Method for recovery of Co-Mn metal from P-phthalic acid residual liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97119183A CN1117163C (en) | 1997-10-27 | 1997-10-27 | Method for recovery of Co-Mn metal from P-phthalic acid residual liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1215761A true CN1215761A (en) | 1999-05-05 |
| CN1117163C CN1117163C (en) | 2003-08-06 |
Family
ID=5175260
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97119183A Expired - Fee Related CN1117163C (en) | 1997-10-27 | 1997-10-27 | Method for recovery of Co-Mn metal from P-phthalic acid residual liquid |
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|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843630B (en) * | 2005-04-08 | 2010-05-12 | 三井化学株式会社 | Method for reclaiming oxidation catalyst |
| CN103937999A (en) * | 2014-04-23 | 2014-07-23 | 北京科技大学 | Method and device for extracting metal manganese from ferromanganese through vacuum distillation |
| CN104743615A (en) * | 2013-12-31 | 2015-07-01 | 新煤化工设计院（上海）有限公司 | Method for recovering cobalt manganese catalyst in terephthalic acid waste solid mother solution |
-
1997
- 1997-10-27 CN CN97119183A patent/CN1117163C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843630B (en) * | 2005-04-08 | 2010-05-12 | 三井化学株式会社 | Method for reclaiming oxidation catalyst |
| CN104743615A (en) * | 2013-12-31 | 2015-07-01 | 新煤化工设计院（上海）有限公司 | Method for recovering cobalt manganese catalyst in terephthalic acid waste solid mother solution |
| CN104743615B (en) * | 2013-12-31 | 2017-01-25 | 新煤化工设计院（上海）有限公司 | Method for recovering cobalt manganese catalyst in terephthalic acid waste solid mother solution |
| CN103937999A (en) * | 2014-04-23 | 2014-07-23 | 北京科技大学 | Method and device for extracting metal manganese from ferromanganese through vacuum distillation |
| CN103937999B (en) * | 2014-04-23 | 2015-09-23 | 北京科技大学 | A kind of vacuum distilling ferromanganese extracts method and the device of manganese metal |
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| Publication number | Publication date |
|---|---|
| CN1117163C (en) | 2003-08-06 |
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