CN1293260A - Method for recovering cobalt and manganese catalyst in terephthalic acid oxidation residue - Google Patents
Method for recovering cobalt and manganese catalyst in terephthalic acid oxidation residue Download PDFInfo
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- CN1293260A CN1293260A CN99121153A CN99121153A CN1293260A CN 1293260 A CN1293260 A CN 1293260A CN 99121153 A CN99121153 A CN 99121153A CN 99121153 A CN99121153 A CN 99121153A CN 1293260 A CN1293260 A CN 1293260A
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- manganese
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- terephthalic acid
- ions
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 28
- 239000011572 manganese Substances 0.000 title claims abstract description 28
- 239000010941 cobalt Substances 0.000 title claims description 32
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 32
- 229910017052 cobalt Inorganic materials 0.000 title claims description 31
- 230000003647 oxidation Effects 0.000 title claims description 31
- 238000007254 oxidation reaction Methods 0.000 title claims description 31
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 238000011084 recovery Methods 0.000 claims abstract description 12
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 7
- -1 iron ions Chemical class 0.000 claims abstract description 6
- 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 4
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 4
- 229910021655 trace metal ion Inorganic materials 0.000 claims abstract description 3
- 239000005416 organic matter Substances 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 230000009286 beneficial effect Effects 0.000 claims description 4
- 229910001437 manganese ion Inorganic materials 0.000 claims description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 4
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000004304 potassium nitrite Substances 0.000 claims description 2
- 235000010289 potassium nitrite Nutrition 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 235000010288 sodium nitrite Nutrition 0.000 claims description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims 1
- 150000002696 manganese Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 25
- 239000002253 acid Substances 0.000 abstract description 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 4
- 150000001768 cations Chemical group 0.000 abstract description 3
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 229960000583 acetic acid Drugs 0.000 description 9
- 238000005341 cation exchange Methods 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000011656 manganese carbonate Substances 0.000 description 5
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 229960004365 benzoic acid Drugs 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- HJZMCWKYJQFMPG-UHFFFAOYSA-J cobalt(2+);manganese(2+);dicarbonate Chemical compound [Mn+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HJZMCWKYJQFMPG-UHFFFAOYSA-J 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JXNCBISRWFPKJU-UHFFFAOYSA-N acetic acid;manganese Chemical compound [Mn].CC(O)=O JXNCBISRWFPKJU-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- BYMAUHXAUBWFOR-UHFFFAOYSA-J cobalt(2+) manganese(2+) tetraacetate Chemical compound [Mn+2].[Co+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O BYMAUHXAUBWFOR-UHFFFAOYSA-J 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Catalysts (AREA)
Abstract
The present invention belongs to the field of catalyst recovering technology. The present invention features that on the basis of washing terephthalic acid oxidizing residue and adding dilute sulfuric acid to saturate most of organic matter, the water solution containing Co, Mn and other trace metal ions is cation exchanged with strong acid cation exchange resin, and before adding strong alkali solution to neutralize and eliminate Fe ions, oxidant is added to the solution to eliminate Fe in the solution2+Complete conversion to Fe3+So that iron ions are completely removed during the neutralization process. The method can ensure that the recovery rate of the cobalt-manganese catalyst is not less than 95 percent, and the purity of the recovered crystal dried cobalt acetate and manganese acetate catalyst is not less than 99.7 percent.
Description
The invention belongs to a catalyst recovery technology, and mainly provides a method for recovering a cobalt and manganese catalyst in terephthalic acid oxidation residues.
Terephthalic acid, abbreviated in english as TA, is produced by oxidation of p-diphenyl. The technological process is carried out under the conditions of high temperature, excessive oxygen and cobalt and manganese acetate as catalysts, and the main chemical reaction equation is as follows: . The reaction product is filtered, crystallized, separated and dried, TA crystal is sent to PTA unit, most of mother liquor is recycled to feedThe mixing tank continues to react, the rest is sent to the solvent recovery tank, most of the solvent is removed from the solid residue through evaporation, and the solid residue (comprising organic matters, byproducts, TA and catalyst) is mixed with process water, pulped and then sent to the post-treatment (sewage treatment plant).
The part of residues contain a large amount of metal ions such as cobalt, manganese and the like and organic matters, the COD of the part of residues is more than 3000mg/l, and after the part of residues enter a sewage treatment field, a lot of problems are brought to sewage treatment. Firstly, the heavy metal causes activated sludge poisoning, and secondly, high construction cost and operation cost are brought by high-concentration organic wastewater, so that direct discharge not only increases the environmental protection cost, but also causes economic loss.
Around this problem, methods for treating and recovering TA oxidation residues have been proposed at home and abroad, and japanese patent No. FP 0515788: and (3) adding carbonate into the acidic aqueous solution containing cobalt and manganese obtained by washing the oxidized residues to ensure that the pH of the solution is more than or equal to 8.5, precipitating the cobalt and manganese in the form of carbonate, and reacting acetic acid with the cobalt-manganese carbonate to obtain the cobalt acetate and manganese acetate mixed catalyst. The process is simple, but cannot be returned to an oxidation working section for continuous use, and the economic benefit is poor.
German patent GER offfen 2260498: leaching the oxidation residue from which acetic acid and terephthalic acid are separated with dilute sulfuric acid to obtain an acidic aqueous solution containing cobalt and manganese, adjusting the pH value of the solution to 5.5 to remove iron ions with a valence of 3, and then adjusting the pH value to 9.1 with a sodium carbonate solution to convert the cobalt and manganese into carbonic acid precipitates. Finally, the recovery rate of cobalt is 95.6 percent, the recovery rate of manganese is 91.7 percent, and the purified cobalt manganese carbonate can be returned to the oxidation section for continuous use after being dissolved in acetic acid. The disadvantage is that the purity of the recovered catalyst is general, which has an influence on the recycling.
Chinese patent CN 1088132: provides a method for recovering cobalt and manganese from 20-100% acetic acid solution, which aims to: the solution is firstly passed through strong acid positive ion resin column, then the resin column is washed by inorganic or organic acid and its salt solution, so that cobalt and manganese can be separated. The process is simple, and the recovered cobalt acetate and manganese acetate can not be recycled.
A publication by Yangzi petrochemical institute of Yangzi petrochemical institute describes a method for recovering oxidation residue (Yangzi petrochemical 1995 (1)). Washing the residue with water at certain temperature, recovering Co, Mn catalyst and PT acid from the filtered solution, heating and evaporating the filter cake to obtain benzoic acid and mixed phthalic acid. The process has large investment, and the recovered cobalt and manganese acetic acid catalyst can not be recycled.
The invention aims to provide a method for recovering cobalt and manganese catalysts in TA oxidation residues, which has the characteristics of high recovery rate and high purity of the recovered catalysts.
The invention adopts the technical scheme that the invention completes the invention task: on the basis of washing TA oxidation residue with water and adding dilute sulfuric acid to saturate and separate out most of organic matters, the water solution containing cobalt, manganese ions and other trace metal ions is subjected to cation exchange by strong acid cation exchange resin to completely separate the organic matters from the metal ions,the catalyst is beneficial to be recovered, and the product purity is improved; before adding strong alkali solution to neutralize and remove iron ions, an oxidation method is adopted, namely oxidant is added into the solution to lead Fe in the solution2+Complete conversion to Fe3+So that the iron ions are completely removed in the subsequent neutralization iron removal process.
The aqueous solution containing Co and Mn obtained by washing the oxidation residue contains dissolved organic matters which are not beneficial to or even interfere with the recovery of the catalyst in the subsequent process, and the solution is subjected to cation exchange on the basis of the washing process, so that cations such as cobalt and manganese are exchanged, and are completely separated from benzene carboxylic acid and other organic substances which are dissolved in the solution and have the hindrance on removing Fe, and the Fe content in the recovered catalyst is greatly reduced compared with the prior art, and the method is also beneficial to the concentration and crystallization process of cobalt acetate and manganese acetate. Adding oxidant into the metal ion acidic aqueous solution obtained by the cation exchange process, namely adding an oxidation process before the solution neutralization (iron removal) process, so that ferrous ions in the acidic aqueous solution can be completely converted into ferric ions, and Fe is further converted3+Is completely removed in the process of neutralizing and removing iron.
The cation exchange process adopts strong acid cation resin column.
The oxidant adopted in the oxidation process is hydrogen peroxide. Other oxidizing agents such as sodium nitrite, potassium chlorate, sodium chlorate, etc. may also be used, which increase the production costs and cause new pollution, which is detrimental to the process effluent treatment, but has little effect on the recovered end product.
The recovery method provided by the invention can ensure that the recovery rate of the cobalt-manganese catalyst is not less than 95 percent, and the purity of the recovered crystal dried cobalt acetate and manganese acetate catalyst is not less than 99.7 percent.
The method has better economic benefit by recovering the cobalt and manganese catalysts and organic matters in the TA oxidation residue. The annual output value can reach more than 600 ten thousand yuan when 60 tons of cobalt and manganese catalysts are recovered annually.
Meanwhile, the COD and heavy metal content of the chemical fiber sewage can be greatly reduced, the investment cost and the operation cost of water treatment can be reduced, the qualified discharge of the sewage treatment can be ensured, and the social benefit is very considerable.
Example (b):
the invention relates to a method for recovering cobalt and manganese catalysts in TA oxidation residues, which comprises the following steps:
the process can be divided into seven steps, which are sequentially as follows: 1. adding acid to remove organic matters; 2. cation exchange; 3. oxidizing ferrous ions; 4. neutralizing with strong alkali to remove ferric ions; 5. preparing cobalt carbonate and manganese carbonate; 6. washing the cobalt manganese carbonate salt with water; 7. the catalyst is prepared by dissolving glacial acetic acid.
The specific description is as follows:
washing of oxidation residue: after the thin film evaporation and the acetic acid removal, dry oxidation residues containing organic matters, catalysts and impurities can be obtained, and the dry residues are 50% of the wet residues (containing dilute acetic acid) in terms of the experimental results of Liaoyang chemical fiber oxidation residues. In the embodiment, a certain weight of dry slag is put into a water washing stirrer, deionized water with the weight about 10 times that of the dry slag and a small amount of dilute sulfuric acid capable of leading the PG value of the solution to reach 2-3 are added, the mixture is stirred and washed for 1 hour at the temperature of 90-100 ℃, and Co is used for washing2+、Mn2+Catalyst andthe water-soluble organic substances are dissolved into water solubility, and some organic substances such as benzoic acid and the like are saturated in the aqueous solution. And after the dissolution is finished, cooling the materials to separate out the organic matters in the water as clean as possible, wherein the water solution only contains the cobalt and manganese catalysts and a small amount of organic matters, filtering and separating to obtain organic residues as filter cakes and orange-red catalyst solution as filtrate.
Cation exchange: the water solution containing cobalt and manganese ions passes through a cation exchange column formed by 732 type strong acid cation exchange resin, the cobalt, manganese ions and impurity ions thereof are exchanged, the discharged water solution is an acidic water solution containing a small amount of organic matters, the complete separation of the catalyst and the organic matters can be realized through the process, the recovery of the catalyst is prevented from being interfered by the organic matters in the subsequent process, and the discharged acidic water solution (discharged from the bottom of the resin column) can be returned to a water washing section to be used as water for washing, so that the water and dilute sulfuric acid can be saved, and the recovery rate of the organic matters in the oxidation residues can be improved.
The resin column which has exchanged cobalt, manganese and other ions is added with 5 percent hydrochloric acid from the top of the column, so that the cobalt, manganese and other ions exchanged in the resin are completely absorbed and the acid aqueous solution only containing cobalt, manganese and other metal ions is obtained. The resin column is washed to be neutral by deionized water and can be used for next exchange.
Hydrogen peroxide oxidation: adding a proper amount of 27.5% hydrogen peroxide into the obtained metal ion acidic aqueous solution, stirring the solution in a reaction kettle at about 100 ℃ until the hydrogen peroxide is completely decomposed, and completely converting a small amount of ferrous ions in the aqueous solution into ferric ions. The adding amount of the hydrogen peroxide is determined by the content of ferrous ions in the solution so as to lead the Fe in the solution to be dissolved2+Conversion to Fe3+The standard is.
The oxidant can also be potassium nitrite, sodium salt, potassium chlorate, etc.
And (3) a neutralization iron removal process: adding 5% NaOH solution into the aqueous solution treated by hydrogen peroxide for neutralization, and optionally addingstrong alkali solution such as potassium hydroxide for neutralization to make the pH value reach about 5, wherein Fe3+With Fe (OH)3The form is completely precipitated, and Na+、Co2+、Mn2+、Ca2+、Mg2+And Zn2+Very little remains in solution (the process is totally treated with deionized water, Ca)2+、Mg2+Very little, no consideration is given to the removal of Ca by addition of NaF2+、Mg2+)。
CoCO3、MnCO3The preparation of (1): adding carbonate solution to the above solution, e.g.5％Na2CO3Adjusting pH =9.05, Co2+、Mn2+Ionized by CoCO3And MnCO3Form precipitate, Zn2+Due to traces remaining in solution. It is emphasized that Co-peroxide is used in alkaline environment2+、Mn2+Respectively converted into Co2O3、MnO2Thus adding Na throughout2CO3In the process, the equipment is under nitrogen or CO2Under the protection of gas, Na is optionally used2CO3The solution is heated and boiled before use to expel the dissolved oxygen therefrom. Filtering and washing the precipitate with deionized water (generally washing with water for 4-5 times, and deionized water: precipitate = 6: 1) under the protection of protective gas to completely remove the substances existing in the form of ions in water, and finally obtaining pure Co2CO3、MnCO3And (3) salt.
Dissolving acetic acid: dissolving pure CoCO with glacial acetic acid3，MnCO3The salt (60 ℃ at normal pressure) can directly enter an oxidation section of PTA production to be used as a catalyst. Or dissolving the precipitate with aqueous acetic acid solution, evaporating, concentrating, crystallizing, and drying to obtain cobalt acetate-manganese mixed catalyst containing 4 crystal waters.
The used reagents require: the strong acid and alkali used must not introduce any other impurities which can affect the purification, such as calcium, magnesium and the like.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99121153A CN1120893C (en) | 1999-10-19 | 1999-10-19 | Method for recovering cobalt and manganese catalyst in terephthalic acid oxidation residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99121153A CN1120893C (en) | 1999-10-19 | 1999-10-19 | Method for recovering cobalt and manganese catalyst in terephthalic acid oxidation residue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1293260A true CN1293260A (en) | 2001-05-02 |
| CN1120893C CN1120893C (en) | 2003-09-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| CN99121153A Expired - Fee Related CN1120893C (en) | 1999-10-19 | 1999-10-19 | Method for recovering cobalt and manganese catalyst in terephthalic acid oxidation residue |
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| WO2009127117A1 (en) * | 2008-04-03 | 2009-10-22 | Shen Fuchang | A process for resource processing purified terephthalic acid waste residue |
| CN102174705A (en) * | 2011-03-10 | 2011-09-07 | 中信锦州金属股份有限公司 | Method for producing electrolytic manganese metal by using hydrogen peroxide to remove iron |
| CN102241581A (en) * | 2011-04-29 | 2011-11-16 | 金瑞新材料科技股份有限公司 | Method for preparing manganese acetate from electrolytic manganese metal leaching residue |
| CN102824919A (en) * | 2011-06-14 | 2012-12-19 | 逸盛大化石化有限公司 | Method for reducing oxidation catalyst in PTA production apparatus |
| CN103627904A (en) * | 2013-11-29 | 2014-03-12 | 湖南邦普循环科技有限公司 | Method for recovering cobalt manganese from cobalt manganese catalyst wastes |
| CN103861650A (en) * | 2012-12-17 | 2014-06-18 | 兴忠行股份有限公司 | Method for reclaiming cobalt-manganese catalyst from terephthalic acid reaction mother liquor |
| CN104844445A (en) * | 2015-03-27 | 2015-08-19 | 中国昆仑工程公司 | Method for recycling acetic acid from blanking residues of PTA (purified terephthalic acid) film evaporator |
| CN105645634A (en) * | 2016-01-11 | 2016-06-08 | 浙江奇彩环境科技股份有限公司 | Treatment method of epoxy resin synthesis wastewater |
| CN105688990A (en) * | 2016-01-22 | 2016-06-22 | 福建洋屿环保科技股份有限公司 | Method for regenerating cobalt and manganese acetate compound catalyst from PTA (Pure Terephthalic Acid) oxidization residues |
| CN107586973A (en) * | 2017-07-18 | 2018-01-16 | 百川化工(如皋)有限公司 | Method for recovering cobalt and manganese from cobalt and manganese catalyst waste |
| CN114147052A (en) * | 2020-09-05 | 2022-03-08 | 中国石油化工股份有限公司 | High-boiling-point substance metal ion adsorption renewable system and process |
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| CN101172947B (en) * | 2006-11-03 | 2011-04-27 | 美琪玛国际股份有限公司 | Purified terephthalic acid mother liquor recovery and catalyst purification and regeneration system and method |
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- 1999-10-19 CN CN99121153A patent/CN1120893C/en not_active Expired - Fee Related
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| WO2009127117A1 (en) * | 2008-04-03 | 2009-10-22 | Shen Fuchang | A process for resource processing purified terephthalic acid waste residue |
| CN102174705A (en) * | 2011-03-10 | 2011-09-07 | 中信锦州金属股份有限公司 | Method for producing electrolytic manganese metal by using hydrogen peroxide to remove iron |
| CN102174705B (en) * | 2011-03-10 | 2012-12-12 | 中信锦州金属股份有限公司 | Method for producing electrolytic manganese metal by using hydrogen peroxide to remove iron |
| CN102241581A (en) * | 2011-04-29 | 2011-11-16 | 金瑞新材料科技股份有限公司 | Method for preparing manganese acetate from electrolytic manganese metal leaching residue |
| CN102241581B (en) * | 2011-04-29 | 2013-06-05 | 金瑞新材料科技股份有限公司 | Method for preparing manganese acetate from electrolytic manganese metal leaching residue |
| CN102824919A (en) * | 2011-06-14 | 2012-12-19 | 逸盛大化石化有限公司 | Method for reducing oxidation catalyst in PTA production apparatus |
| CN103861650A (en) * | 2012-12-17 | 2014-06-18 | 兴忠行股份有限公司 | Method for reclaiming cobalt-manganese catalyst from terephthalic acid reaction mother liquor |
| CN103627904A (en) * | 2013-11-29 | 2014-03-12 | 湖南邦普循环科技有限公司 | Method for recovering cobalt manganese from cobalt manganese catalyst wastes |
| CN104844445A (en) * | 2015-03-27 | 2015-08-19 | 中国昆仑工程公司 | Method for recycling acetic acid from blanking residues of PTA (purified terephthalic acid) film evaporator |
| CN104844445B (en) * | 2015-03-27 | 2017-06-20 | 中国昆仑工程有限公司 | The method of recovery of acetic acid from PTA thin film evaporator blanking residues |
| CN105645634B (en) * | 2016-01-11 | 2019-01-15 | 浙江奇彩环境科技股份有限公司 | A kind of processing method of epoxy resin synthetic wastewater |
| CN105645634A (en) * | 2016-01-11 | 2016-06-08 | 浙江奇彩环境科技股份有限公司 | Treatment method of epoxy resin synthesis wastewater |
| CN105688990A (en) * | 2016-01-22 | 2016-06-22 | 福建洋屿环保科技股份有限公司 | Method for regenerating cobalt and manganese acetate compound catalyst from PTA (Pure Terephthalic Acid) oxidization residues |
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| CN107586973A (en) * | 2017-07-18 | 2018-01-16 | 百川化工(如皋)有限公司 | Method for recovering cobalt and manganese from cobalt and manganese catalyst waste |
| CN114147052A (en) * | 2020-09-05 | 2022-03-08 | 中国石油化工股份有限公司 | High-boiling-point substance metal ion adsorption renewable system and process |
| CN114147052B (en) * | 2020-09-05 | 2023-01-24 | 中国石油化工股份有限公司 | High-boiling-point substance metal ion adsorption renewable system and process |
| CN115282939A (en) * | 2022-08-04 | 2022-11-04 | 南京大学 | Method and system for recycling cobalt and manganese catalysts in high-selectivity iron-removing resin and PTA wastewater |
| CN116967254A (en) * | 2023-06-20 | 2023-10-31 | 浙江利星科技股份有限公司 | A method for treating xylene oxidation residue |
| CN116986612A (en) * | 2023-06-20 | 2023-11-03 | 海南逸盛石化有限公司 | High-efficiency treatment method for terephthalic acid oxidation residues and incineration device thereof |
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