CN102503813B - Method for recovering organic acid and cobalt manganese metal in terephthalic acid oxidation residue - Google Patents
Method for recovering organic acid and cobalt manganese metal in terephthalic acid oxidation residue Download PDFInfo
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- CN102503813B CN102503813B CN2011102826807A CN201110282680A CN102503813B CN 102503813 B CN102503813 B CN 102503813B CN 2011102826807 A CN2011102826807 A CN 2011102826807A CN 201110282680 A CN201110282680 A CN 201110282680A CN 102503813 B CN102503813 B CN 102503813B
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- manganese
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- 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 94
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000003647 oxidation Effects 0.000 title claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 41
- 150000007524 organic acids Chemical class 0.000 title claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 34
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 title claims description 40
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000007787 solid Substances 0.000 claims abstract description 91
- 239000000706 filtrate Substances 0.000 claims abstract description 66
- SORNWENKXWLTOD-UHFFFAOYSA-J C(C(=O)[O-])(=O)[O-].[Mn+2].[Co+2].C(C(=O)[O-])(=O)[O-] Chemical compound C(C(=O)[O-])(=O)[O-].[Mn+2].[Co+2].C(C(=O)[O-])(=O)[O-] SORNWENKXWLTOD-UHFFFAOYSA-J 0.000 claims abstract description 57
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000926 separation method Methods 0.000 claims abstract description 41
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 40
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 34
- 239000010941 cobalt Substances 0.000 claims abstract description 34
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007864 aqueous solution Substances 0.000 claims abstract description 33
- 238000001914 filtration Methods 0.000 claims abstract description 31
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 24
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 24
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims abstract description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims abstract description 18
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims abstract description 18
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 16
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 16
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 16
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims abstract 2
- 239000003973 paint Substances 0.000 claims abstract 2
- 238000011084 recovery Methods 0.000 claims description 35
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- 229910020632 Co Mn Inorganic materials 0.000 claims description 23
- 229910020678 Co—Mn Inorganic materials 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 19
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 16
- ZBICJTQZVYWJPB-UHFFFAOYSA-N [Mn].[Co].[Br] Chemical compound [Mn].[Co].[Br] ZBICJTQZVYWJPB-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 9
- 239000011572 manganese Substances 0.000 abstract description 24
- 229910052748 manganese Inorganic materials 0.000 abstract description 19
- -1 permanganate Chemical compound 0.000 abstract description 10
- 238000001816 cooling Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000005711 Benzoic acid Substances 0.000 abstract description 3
- 235000010233 benzoic acid Nutrition 0.000 abstract description 3
- NXTZRSCVEDUAGZ-UHFFFAOYSA-J cobalt(2+);manganese(2+);tetrabromide Chemical compound [Mn+2].[Co+2].[Br-].[Br-].[Br-].[Br-] NXTZRSCVEDUAGZ-UHFFFAOYSA-J 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 abstract 2
- 229940011182 cobalt acetate Drugs 0.000 abstract 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- 239000002244 precipitate Substances 0.000 abstract 2
- 239000012456 homogeneous solution Substances 0.000 abstract 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 14
- 229960000583 acetic acid Drugs 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 235000019253 formic acid Nutrition 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- IMXLQXHCHYKEEE-UHFFFAOYSA-N benzene;formic acid Chemical compound OC=O.C1=CC=CC=C1 IMXLQXHCHYKEEE-UHFFFAOYSA-N 0.000 description 5
- 238000004064 recycling Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 208000005156 Dehydration Diseases 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000012452 mother liquor Substances 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
- 239000010409 thin film Substances 0.000 description 2
- 238000000207 volumetry Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
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- 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
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention belongs to a technology for recovering organic acid and catalyst in terephthalic acid oxidation residue, namely, controlling the solid content of high-temperature oxidation residue discharged from a terephthalic acid (PTA for short) production device to be within the range of 20-45%, and carrying out first-stage filtration separation at the temperature of 55-90 ℃, wherein the separated solid is directly sold for manufacturing resin or paint monomer or returned to an oxidation reactor for use; the first filtrate is treated according to the following process: adding oxalic acid to obtain cobalt manganese oxalate precipitate, filtering to separate cobalt manganese oxalate, further cooling, filtering and separating filtrate, extracting benzoic acid from the separated solid, and sending the filtrate to a wastewater treatment device; or (II) directly cooling the primary filtrate for secondary filtration and separation, wherein the separated solid is used for extracting benzoic acid, oxalic acid is added into the secondary filtrate to obtain cobalt manganese oxalate precipitate, the cobalt manganese oxalate is separated by filtration, and the filtrate is sent to a wastewater treatment device; reacting cobalt manganese oxalate obtained in the process (I) or (II) with oxidant hydrogen peroxide, peracetic acid, bromine, manganate, permanganate, manganese dioxide or/and hydrobromic acid, using aqueous solution of cobalt acetate, aqueous solution of cobalt bromide, aqueous solution of manganese acetate, aqueous solution of manganese bromide, acetic acid or/and pure water as solvent, after cobalt manganese oxalate is completely dissolved, reacting with metal cobalt, metal manganese or/and hydrobromic acid to remove impurities, and filtering to obtain homogeneous solution containing cobalt manganese bromide ions, wherein the mixed solution can be directly mixed with cobalt acetate, manganese acetate, cobalt bromide, manganese bromide, acetic acid or water to be used as an oxidation catalyst of terephthalic acid.
Description
Technical field
The present invention relates to organic acid and Co-Mn metal recovery and reutilization technology method field in a kind of terephthalic acid (being called for short PTA) oxidation residua.Say in more detail the residue filter containing organic acid and Co-Mn metal of PTA device mother liquid evaporation device eliminating is isolated to water-insoluble organic acid solids, filtrate is through further processing recovery organic acid, Co-Mn compound and the Co-Mn compound of recovery being carried out to the homogeneous phase processing and return to the field that the PTA oxidation system recycles again.
Background technology
At present, the production method of PTA is to adopt the compound of cobalt manganese bromine as catalyzer, p-Xylol to be made through the oxidation of air high-temperature liquid-phase, and the compound of these cobalt manganese bromines comprises Cobaltous diacetate, cobaltous bromide, manganese acetate, Manganese dibromide, Hydrogen bromide, tetrabromoethane etc.For guaranteeing the PTA quality, in the PTA production process, 10～20% the mother liquor slurry containing catalyzer must be extracted out, after thin-film evaporator reclaims a large amount of acetic acid, the remaining residue slurries for containing Cobaltous diacetate, manganese acetate, aromatic acid, acetic acid etc.The production equipment of 1,200,000 tons of PTA of a set of annual output, annual to discharge oxidation residua slurries containing organic acid and catalyzer over 1.5 ten thousand tons, wherein contain cobalt 0.5 ~ 1.2%, contain manganese 0.5 ~ 1.2%, contain organic acid 30 ~ 42%, if organic acid, cobalt, Mn catalyst in this part residue slurries can be reclaimed, return mechanism uses or recycling, not only environmental contamination reduction, and direct economic benefit is over 4,000 ten thousand yuan.
The Mitsui chemistry once provided a kind of recovery and treatment method of PTA oxidation residua, the method is through the thin-film evaporator recovery of acetic acid, under 45 ℃, with deionized water, extract, obtain Cobaltous diacetate and manganese acetate extraction liquid and directly return to the use of PTA device after concentrated, the granulation of residue organic acid residue is discharged and is sent incinerator, and the method has application on the PTA device of Jinan chemical fibre, oil of SPC and Plant of Tianjin Petrochemical Company head factory; Also there is patent that the method that reclaims cobalt manganese in the PTA residue by ion-exchange is provided, as Chinese patent 98113765.2,99121153.7,200410030379.7.
The PTA device of E.I.Du Pont Company's technology adopts oxalate to reclaim the cobalt-manganese catalyst in residue, and the residue organic acid waste liquid is directly discharged burning.
The disadvantage that the method for Mitsui Chemicals exists is: only have about 70% cobalt, Mn catalyst to be recycled, and energy consumption is high, equipment is many, and pipeline easily stops up, and the water waste is large; There is the accumulation of the foreign ions such as iron, nickel in the cobalt-manganese catalyst reclaimed, the defects such as the unstable and activity decreased of cobalt and manganese valence state; Organic acid is all sent to burning disposal, contaminate environment in addition; The ion-exchange rule exists treatment unit and complex disposal process, a large amount of other chemical substances of introducing, has increased waste discharge, wastewater treatment capacity increases, the high in cost of production defect, the unstable of PTA residue composition increased difficulty and complexity also to the ion-exchange pre-treatment, and the not mentioned organic acid of the method reclaims.
The defect that the oxalate way of recycling that E.I.Du Pont Company adopts exists is, it is that oxalic acid or the aqueous solution are directly added the mother liquor of extracting out from the PTA device, the precipitation that oxalic acid and cobalt manganese generate and the insoluble organic acid in residue liquid mix and form a kind of dope, and separate by finned whizzer, this dope easily sticks on separating device not easily separated, pipeline and equipment also very easily stop up, need to more isolated liquid more than 90% be returned and be rinsed when separating, therefore the actual efficiency of separating device is very low, and to obtain be cobalt oxalate manganese and organic acid solid mixture, what this mixture was dispersed in aqueous acetic acid while returning to application and live catalyst is mixed to form is heterogeneous solution, can only reach the recycling purpose by improving PTA oxidizing reaction actuator temperature and reducing the internal circulating load that reclaims dispersion liquid during application, this is also the reason that the current PTA of Du Pont technology adopts high temperature oxidation, but the raising of temperature can make the abbreviation of raw materials used PX(p-Xylol while manufacturing PTA) and acetic acid consumption significantly increase, the side reaction aggravation obviously, in addition, this technique is still burning to the residue treatment mode of isolating after cobalt oxalate manganese and acetic acid, has environmental pollution.
Summary of the invention
Purpose of the present invention is exactly to overcome the disadvantage that prior art exists, and adopts new technical characterictic, organic acid and cobalt-manganese catalyst recovery and recycling novel method in a kind of PTA oxidation residua is provided, and is applicable to different PTA devices.
In order to reach purpose of the present invention, at first the present invention carries out while hot single filter by the PTA oxidized residual liquid of extraction and isolates solids wherein, this solids main component is the water-insoluble organic acids such as terephthalic acid, 4-carboxyl benzaldehyde, p-methylbenzoic acid, this solids is returned to oxidation system or sell the raw material for the synthesis of resin, filtrate is processed by following process: (I) adds oxalic acid in one-level filtrate, the filtrate temperature is controlled at 60～100 ℃, the mol ratio of the cobalt manganese total amount in oxalic acid and filtrate is 0.75～1.2: 1, obtain cobalt manganese oxalate precipitation, filter to isolate cobalt oxalate manganese, filtrate further is cooled to 30～5 ℃, then carries out filtering separation, solids after separation is for extracting phenylformic acid, and filtrate is sent wastewater treatment equipment, perhaps (II) directly is cooled to 30～5 ℃ by one-level filtrate, carry out second stage filtering separation, solids after separation is for extracting phenylformic acid, add oxalic acid in secondary filtrate, controlling temperature is 30 ~ 100 ℃, and the mol ratio of the cobalt manganese total amount in oxalic acid and filtrate is 0.75～1.2: 1, obtains cobalt oxalate manganese precipitation, filter to isolate cobalt oxalate manganese, filtrate is sent wastewater treatment equipment, cobalt oxalate manganese and oxidants hydrogen peroxide that above-mentioned (I) or (II) process are obtained, Peracetic Acid, bromine, permanganic acid, mangaic acid, Manganse Dioxide is or/and Hydrogen bromide carries out the homogeneous phase processing reaction, and the use Cobaltous diacetate aqueous solution, the cobaltous bromide aqueous solution, the manganese acetate aqueous solution, the Manganese dibromide aqueous solution, acetic acid or/and pure water as solvent, after solids all dissolves, add cobalt metal in reactor, manganese metal is or/and Hydrogen bromide, continue heating 30 ~ 60min, filter, obtain the homogeneous phase solution containing cobalt manganese bromine, this mixed solution can be directly and Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide, acetic acid or water are mixed the oxide catalyst as PTA, wherein, the mol ratio of cobalt manganese oxalate and hydrogen peroxide or Peracetic Acid is 1: 1.0～1.2, the mol ratio of cobalt manganese oxalate and bromine or Manganse Dioxide or permanganic acid or mangaic acid is stoichiometric ratio, cobalt manganese oxalate and hydrobromic mol ratio are 1: 2.05～10.0.
The recovery method of organic acid and Co-Mn metal in oxidized dregs of terephthalic acid of the present invention, consider and studied due to the different residue component difference impacts that cause in the oxidation technology source of different PTA oxidation units, or rather, the solid content that different PTA oxidation units are discharged residue is different, even widely different, and also can there be very big difference in the residue that same device was discharged in some stage, but usually all in 30 ~ 42% scopes, cobalt manganese content is respectively between 0.5 ~ 1.2%, for this reason, the present invention is directed to this scope studies in detail, also studied simultaneously solid contents after some dehydrations surpass 45% residue and thin up to solid content lower than 20% residue separating effect and influence factor, experiment shows: when solid content surpasses 45%, although still can direct filtration separate, but residue thickness, filtration velocity is slow, in isolated solids, water soluble organic substance and catalyst residue obviously raise, also significantly increase the washing water consumption, now preferably after thin up, refilter separation, water yield increase also contributes to the phenylformic acid in solids and Co-Mn compound are proceeded in water, water soluble organic substance ratio in the solids that flash trapping stage is gone out reduces, experiment shows, while being filtered below adding water adjusting solid content to 20%, the increase of water consumption is no longer obvious for the effect of extracting phenylformic acid and Co-Mn compound, but increase with the water yield, for keeping filtration temperature, have to use hot water or external heat is provided, this increases the process energy consumption, also increase later stage wastewater treatment expense, therefore, the present invention controls and selects solid content to carry out first step filtering separation in 20 ~ 45% scopes, for cobalt manganese, when cobalt and manganese concentration is low to moderate 0.05% respectively in waste liquid, by the present invention, still can make the rate of recovery of cobalt be greater than 98%.
The recovery method of organic acid and Co-Mn metal in oxidized dregs of terephthalic acid of the present invention, that the residue temperature is controlled in 55～90 ℃ of scopes and implements first step filtering separation, filter to isolate solids wherein, temperature range when this temperature range is equal to the residue discharge substantially, both energy-conservation, can avoid again the large filtration velocity that affects of residue fluid viscosity; , separate benzoic acid content in the solids obtained and raise during lower than 55 ℃ when temperature, be unfavorable for returning again oxidation; When temperature, during higher than 90 ℃, while particularly reaching 95 ~ 100 ℃, the filtrate top layer there will be one deck thickness oily matter, and the crisp shape thing of cooling rear overstrike is also still carried dope secretly, disturbs cobalt manganese and solubility organic acid to reclaim.
The recovery method of organic acid and Co-Mn metal in oxidized dregs of terephthalic acid of the present invention, after flash trapping stage is deviate from insoluble organic acid solids, the processing mode of filtrate can be divided into following two kinds of modes: (I) adds oxalic acid in filtrate, the filtrate temperature is controlled at 60～100 ℃, the soluble substances such as phenylformic acid that now contain in solution still are dissolved in the aqueous solution, can not affect precipitation and the filtration of cobalt oxalate manganese, filtered while hot isolates cobalt manganese oxalate compound, filtrate after separation further is cooled to 30～5 ℃, the dissolved organic matters such as phenylformic acid will separate out, carry out again filtering separation, filtrate is sent wastewater treatment equipment, solids is crude benzol formic acid, purify and can obtain meeting the purified petroleum benzin formic acid of pharmaceutical grade standard through the high temperature distillation, perhaps (II) directly is cooled to 30～5 ℃ by one-level filtrate, at first make the dissolved organic matters such as phenylformic acid separate out and carry out filtering separation, add again oxalic acid in filtrate after separation, controlling temperature is 30 ~ 100 ℃, the oxalate particle of the favourable cobalt manganese of high temperature increases and is convenient to and filters, the solution of isolating cobalt manganese oxalate is delivered to wastewater treatment equipment again, and in above-mentioned two kinds of modes, the mol ratio of the cobalt manganese total amount in oxalic acid and filtrate is 0.75～1.2: 1.
The recovery method of organic acid and Co-Mn metal in oxidized dregs of terephthalic acid of the present invention, oxalic acid both can directly add with solid form, also can directly add the aqueous solution containing oxalic acid 10～50%, and the cost of take is minimum is principle.
The recovery method of organic acid and Co-Mn metal in oxidized dregs of terephthalic acid of the present invention, that the cobalt manganese oxalate that separation is obtained carries out the homogeneous phase processing, be about to cobalt manganese oxalate and oxidants hydrogen peroxide, Peracetic Acid, bromine, permanganic acid, mangaic acid, Manganse Dioxide is or/and Hydrogen bromide reacts dissolving, and the use Cobaltous diacetate aqueous solution, the cobaltous bromide aqueous solution, the manganese acetate aqueous solution, the Manganese dibromide aqueous solution, acetic acid is or/and pure water obtains a kind of homogeneous phase solution that contains cobalt manganese bromide anion as solvent and adjusting cobalt and manganese concentration, in reaction process, the mol ratio of cobalt manganese oxalate and hydrogen peroxide or Peracetic Acid is 1: 1.0～1.2, the mol ratio of cobalt manganese oxalate and bromine or Manganse Dioxide or permanganic acid or mangaic acid is stoichiometric ratio, cobalt manganese oxalate and hydrobromic mol ratio are 1: 2.05～10.0.
The recovery method of organic acid and Co-Mn metal in oxidized dregs of terephthalic acid of the present invention, be cobalt manganese oxalate solution that dissolving is obtained further with cobalt, manganese or/and Hydrogen bromide react, to eliminate free bromine residual in solution, to reduce the impurity such as free acid, iron.
The recovery method of organic acid and Co-Mn metal in oxidized dregs of terephthalic acid of the present invention is 40～130 ℃ to the homogeneous phase treatment temp of cobalt manganese oxalate; When temperature during lower than 40 ℃, the decomposition rate of cobalt manganese oxalate is slow and decompose not exclusively, can not get the solution of complete homogeneous phase; When temperature, during higher than 130 ℃, although still can improve the speed of homogeneous phase, the corrodibility increase of bromine, pressure etc. require all will improve to manufacture and the technology controlling and process of equipment, thus the present invention to select the homogeneous phase treatment temp be 40～130 ℃.
The recovery method of organic acid and Co-Mn metal in oxidized dregs of terephthalic acid of the present invention, what obtain contains cobalt (Co
2+), manganese (Mn
2+), bromine (Br
-) homogeneous phase solution can be directly by pumping and live catalyst or aqueous acetic acid etc., be mixed for allotment and prepared the catalyzer of terephthalic acid by p-Xylol through oxidation.
The recovery method of organic acid and Co-Mn metal in oxidized dregs of terephthalic acid of the present invention is directly to send PTA waste water reclamation treatment plant to process the waste water after separation of cobalt manganese oxalate and organic acid.
Embodiment
Further illustrate the present invention below by embodiment:
Embodiment 1:
Get the oxidation residua 1000g of PTA oxidation (first) device, wherein cobalt contents is 0.92%, manganese content is 0.95%, solid content is 40.6%, regulate temperature at 65 ~ 70 ℃, filtered while hot is separated solids wherein, then use approximately with the isopyknic 70 ℃ of hot washes of solids once, be weighed as 181.4g after the solids drying, directly return to oxidation system and reoxidize or sell the raw material for the synthesis of resin, add solid oxalic acid (concentration of oxalic acid >=99.5% in filtrate, lower same) 41.67g, in oxalic acid and filtrate, the mol ratio of cobalt manganese is 1: 1, stirring is warming up to 80 ~ 85 ℃, filtered while hot, isolated pink solid thing is cobalt manganese oxalate compound, and dry rear quality is 56.51g, wherein cobalt manganese content is respectively 16.14%, 15.32%, and the rate of recovery of cobalt manganese is respectively 99.1% and 91.2%, filtrate after separation further is cooled to 10 ~ 5 ℃, now in solution, there are a large amount of white and faint yellow solid thing to separate out, when separating out without solids, filtering separation, filtrate is sent wastewater treatment equipment, solids is crude benzol formic acid etc., through dehydrating, is weighed as 203.1g, by this solids again high temperature distillation purify and can obtain meeting the purified petroleum benzin formic acid of pharmaceutical grade standard, the cobalt manganese oxalate 20g that above-mentioned separation is obtained adds in the 250ml reactor, add containing cobalt 4% Cobaltous diacetate aqueous solution 120g, add bromine 17.68g, the mol ratio of cobalt oxalate manganese and bromine is stoichiometric ratio, stirring heating is warming up to 85 ~ 90 ℃, notice that cooling for reflux is to prevent the bromine volatilization, after solids all dissolves, add again the Hydrogen bromide of 20g cobalt metal and 10g48% in reactor, continue heating 30min, filter, obtain the homogeneous phase solution containing cobalt manganese bromine, this mixed solution can be directly and Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide is mixed the oxide catalyst as PTA.
Embodiment 2:
Embodiment 1 is separated to the cobalt manganese oxalate 20g obtained to add in the 250ml reactor, add containing manganese 6% manganese acetate aqueous solution 100g, add the Hydrogen bromide that 20g concentration is 48% and slowly add the 16.4g27.5% hydrogen peroxide, the mol ratio of cobalt oxalate manganese and hydrogen peroxide is about 1: 1.2, stirring heating is warming up to 95 ~ 100 ℃, notice that cooling for reflux is to prevent the bromine volatilization produced in reaction, after solids all dissolves, add again the 20g cobalt metal in reactor, continue the about 50min of heating, filter, obtain the homogeneous phase solution containing cobalt manganese bromine, this mixed solution can be directly and Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide is mixed the oxide catalyst as PTA.
Embodiment 3:
Get the oxidation residua 500g of PTA oxidation (first) device, one times of thin up, regulate temperature at 85 ~ 90 ℃, filtered while hot is separated solids wherein, use again approximately with the isopyknic 90 ℃ of hot washes of solids once, be weighed as 81.5g after the solids drying, directly return to oxidation system and reoxidize or sell the raw material for the synthesis of resin, add oxalic acid 25.0g in filtrate, in oxalic acid and filtrate, the mol ratio of cobalt manganese is 1.2: 1, stirring is warming up to 80 ~ 85 ℃, filtered while hot, isolated pink solid thing is cobalt manganese oxalate compound, after dry, quality is about 29.57g, and wherein cobalt manganese content is respectively 15.48%, 15.95%, and the rate of recovery of cobalt manganese is respectively 99.5% and 99.3%, filtrate after separation further is cooled to 20 ~ 15 ℃, now in solution, adularescent and faint yellow solid thing are separated out, a small amount of brown oil appears in the solution upper strata, when separating out without solids, filtering separation, filtrate is sent wastewater treatment equipment, solids is crude benzol formic acid etc., its middle and upper part with a small amount of brown dope, is weighed as 110.7g through dehydrating, by this solids again the high temperature distillation purify and can obtain meeting the purified petroleum benzin formic acid of pharmaceutical grade standard, the cobalt manganese oxalate 20g that above-mentioned separation is obtained adds in the 250ml reactor, add the Cobaltous diacetate aqueous solution 100g containing cobalt 3%, manganese acetate aqueous solution 50g containing manganese 6%, Glacial acetic acid 20g, dripping proven concentration under the stirring at normal temperature state is that 98.12% permanganic acid 5.41g is to reactor, the mol ratio of cobalt oxalate manganese and permanganic acid is 1: 0.4, dropwise post-heating and be warming up to 40 ~ 45 ℃, now solids all dissolves, add again the Hydrogen bromide that 20g cobalt metal and 20g concentration are 48% in reactor, continue the about 30min of heating, filter, obtain the homogeneous phase solution containing cobalt manganese bromine, this mixed solution can be directly and Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide is mixed the oxide catalyst as PTA.
Embodiment 4:
Get the oxidation residua 750g after the partial dehydration of PTA oxidation (first) device, add water 250g dilution, regulate temperature at 55 ~ 60 ℃, filtered while hot is separated solids wherein, use again approximately with the isopyknic 60 ℃ of hot washes of solids once, be weighed as 131.7g after the solids drying, directly return to oxidation system and reoxidize or sell the raw material for the synthesis of resin, filtrate is cooled to 30 ~ 25 ℃, filters to isolate the solids of separating out, through dehydrating, be weighed as 155.2g, by this solids again high temperature distillation purify and can obtain meeting the purified petroleum benzin formic acid of pharmaceutical grade standard, filtrate is heated to 40 ~ 45 ℃ and add the aqueous solution 93.7g containing 25% oxalic acid, in oxalic acid and filtrate, the mol ratio of cobalt manganese is 0.75: 1, stir, there are a large amount of pink throw outs to separate out, filtering separation is cobalt manganese oxalate compound, after dry, quality is 31.07g, and wherein cobalt manganese content is respectively 21.96%, 9.77%, and the rate of recovery of cobalt manganese is respectively 98.9% and 42.6%, filtrate after separation is directly sent wastewater treatment equipment, the cobalt manganese oxalate 20g that above-mentioned separation is obtained adds in the 250ml reactor, add the Cobaltous diacetate aqueous solution 100g containing cobalt 3%, manganese acetate aqueous solution 100g containing manganese 6%, Glacial acetic acid 20g, the mangaic acid 6.78g that under the stirring at normal temperature state, the proven concentration of dropping is 98.06% is to reactor, the mol ratio of cobalt oxalate manganese and mangaic acid is 1: 0.5, dropwise post-heating and be warming up to 60-65 ℃, now solids all dissolves, add again the Hydrogen bromide that 20g cobalt metal and 20g concentration are 48% in reactor, continue the about 30min of heating, filter, obtain the homogeneous phase solution containing cobalt manganese bromine, this mixed solution can be directly and Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide is mixed the oxide catalyst as PTA.
Embodiment 5:
Get the oxidation residua 1000g of PTA oxidation (first) device, at air drying, after making its solid content reach 45%, regulate temperature at 85 ~ 90 ℃, filtered while hot is separated solids wherein, find now solution thickness, filtration velocity is slower than embodiment 1 speed, after having filtered, then use approximately with isopyknic 90 ~ 95 ℃ of hot washes of solids once, be weighed as 176.6g after the solids drying, directly return to oxidation system and reoxidize or sell the raw material for the synthesis of resin, add the aqueous solution 91.68g containing 50% oxalic acid in filtrate, in oxalic acid and filtrate, the mol ratio of cobalt manganese is 1.1: 1, stirring is warming up to 95 ~ 100 ℃, filtered while hot, isolated pink solid thing is cobalt manganese oxalate compound, after dry, quality is 57.87g, and wherein cobalt manganese content is respectively 15.82%, 15.63%, and the rate of recovery of cobalt manganese is respectively 99.5% and 95.2%, filtrate after separation further is cooled to 10 ~ 5 ℃, now in solution, there are a large amount of white and faint yellow solid thing to separate out, there is skim brown dope on the solution upper strata, when separating out without solids, filtering separation, filtrate is sent wastewater treatment equipment, and solids is crude benzol formic acid etc., be weighed as 206.9g through dehydrating, by this solids again high temperature distillation purify and can obtain meeting the purified petroleum benzin formic acid of pharmaceutical grade standard, the cobalt manganese oxalate 20g that above-mentioned separation is obtained adds in the 100ml reactor, add the Hydrogen bromide 38.26g that concentration is 48%, cobalt oxalate manganese and hydrobromic mol ratio are 1: 2.05, be heated with stirring to 120 ~ 125 ℃, after solids dissolves, be cooled to normal temperature, filter, the solids oxalic acid obtained recycles, add again the 10g cobalt metal in filtrate, be heated to 100 ~ 105 ℃ and continue the about 60min of reaction, filtrate is the homogeneous phase solution containing cobalt manganese bromine, this mixed solution can be directly and Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide is mixed the oxide catalyst as PTA.
Embodiment 6:
Embodiment 5 is separated to the cobalt manganese oxalate 20g obtained to add in the 250ml reactor, add containing cobalt 10%, brominated 28% cobaltous bromide solution 50g, containing manganese 6% manganese acetate aqueous solution 100g, slowly add the Peracetic Acid that 42.5g concentration is 20%, the mol ratio of cobalt oxalate manganese and Peracetic Acid is about 1: 1, stirring heating is warming up to 95 ~ 100 ℃, notice that cooling for reflux is to prevent the bromine volatilization produced in reaction, after solids all dissolves, add again 2g manganese metal and 12g Hydrogen bromide in reactor, continue reaction 50min, filter, obtain the homogeneous phase solution containing cobalt manganese bromine, this mixed solution can be directly and Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide is mixed the oxide catalyst as PTA.
Embodiment 7:
Get the oxidation residua 1000g of PTA oxidation (second) device, wherein solid content is 33.6%, cobalt contents is 0.65%, manganese content is 0.70%, regulate temperature at 65 ~ 70 ℃, filtered while hot separate solids wherein and with approximately with the isopyknic 70 ℃ of hot washes of solids once, be weighed as 125.9g after the solids drying, directly return to oxidation system and reoxidize or sell the raw material for the synthesis of resin, add the aqueous solution 301.5g containing 10% oxalic acid in filtrate, in oxalic acid and filtrate, the mol ratio of cobalt manganese is about 1: 1, stirring is warming up to 80 ~ 90 ℃, filtered while hot is isolated pink cobalt manganese oxalate, after dry, quality is 40.90g, wherein cobalt manganese content is respectively 15.78%, 15.66%, and the rate of recovery of cobalt manganese is respectively 99.3% and 91.5%, filtrate after separation further is cooled to 10 ~ 5 ℃, now in solution, there are a large amount of white and faint yellow solid thing to separate out, when separating out without solids, filtering separation, filtrate is sent wastewater treatment equipment, solids is crude benzol formic acid etc., through dehydrating, is weighed as 192.2g, by this solids again high temperature distillation purify and can obtain meeting the purified petroleum benzin formic acid of pharmaceutical grade standard, the 40.90g cobalt manganese oxalate that above-mentioned separation is obtained all adds in the 500ml reactor, add the Hydrogen bromide 381.5g that concentration is 48%, cobalt oxalate manganese and hydrobromic mol ratio are 1: 10, be heated with stirring to 120 ~ 125 ℃, after solids dissolves, be cooled to normal temperature, filter, the solids oxalic acid obtained recycles, add again 30g cobalt metal and 5g manganese metal in filtrate, be heated to 120 ~ 125 ℃ and continue the about 60min of reaction, filtrate is the homogeneous phase solution containing cobalt manganese bromine, this mixed solution can be directly and Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide is mixed as the oxide catalyst of PTA or is sent reactor with cobalt metal or/and manganese metal further reacts.
Embodiment 8:
Get the oxidation residua 1000g of PTA oxidation (second) device, regulate temperature at 55 ~ 60 ℃, filtered while hot is separated solids wherein, use again approximately with the isopyknic 60 ℃ of hot washes of solids once, be weighed as 128.2g after the solids drying, directly return to oxidation system and reoxidize or sell the raw material for the synthesis of resin, filtrate is cooled to 10 ~ 5 ℃, filters to isolate the solids of separating out, through dehydrating, be weighed as 191.1g, by this solids again high temperature distillation purify and can obtain meeting the purified petroleum benzin formic acid of pharmaceutical grade standard, filtrate is heated to 50 ~ 55 ℃ and add solid oxalic acid 36g, in oxalic acid and filtrate, the mol ratio of cobalt manganese is about 1.2: 1, stir, pink throw out cobalt manganese oxalate is separated out, filtering separation, after dry, quality is 42.63g, and wherein cobalt manganese content is respectively 15.16%, 16.26%, and the rate of recovery of cobalt manganese is about respectively 99.4% and 99.0%, filtrate after separation is directly sent wastewater treatment equipment, the cobalt manganese oxalate 30g that above-mentioned separation is obtained adds in the 250ml reactor, add the aqueous acetic acid 50g containing cobalt 3% to reach the manganese acetate aqueous solution 30g containing manganese 6%, add the Hydrogen bromide 84g that concentration is 48%, cobalt oxalate manganese and hydrobromic mol ratio are 1: 3, be heated with stirring to boiling, after solids dissolves, be cooled to normal temperature, filter, the solids oxalic acid obtained recycles, filtrate is the homogeneous phase solution containing cobalt manganese bromine, this mixed solution can be directly and Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide is mixed as the oxide catalyst of PTA or is sent to cobalt metal or/and manganese metal further reacts.
Embodiment 9:
Get the oxidation residua 1000g of PTA oxidation (second) device, repeat the front two-stage sepn process of embodiment 6, obtain altogether about 820g containing washing and do not add oxalic acid filtrate, 2 parts of filtrates before getting respectively, wherein 1 part is 41g, be diluted with water to 650g, make wherein cobalt contents be about 0.05%, now manganese content is about 0.054%, another 1 part is 410g, heats and is concentrated into 216g, makes wherein concentration of cobalt ions be about 1.5%, and now manganese content is about 1.62%, the 1st part of solution is heated to 40 ~ 45 ℃ and adds again oxalic acid, the 2nd part of solution has been concentrated to the rear oxalic acid that directly adds therein, the oxalic acid add-on is produced as benchmark to no longer include precipitation in solution, the 1st part and the 2nd part of solution consumption oxalic acid are respectively 1.82g and 16.16g, according to cobalt manganese content meter in PTA residue liquid, the 1st part and the oxalic acid of the 2nd part and the mol ratio of cobalt manganese are about respectively 1.2: 1 and 1.1: 1, the oxalate precipitation obtained is merged to filtering separation, and dry rear quality is 23.49g, and wherein cobalt manganese content is respectively 15.14%, 16.28%, and the rate of recovery of cobalt manganese is about respectively 99.5% and 99.3%, the cobalt manganese oxalate that above-mentioned separation is obtained all adds in the 250ml reactor, add 50g to contain cobalt 10%, brominated 28% the cobaltous bromide aqueous solution, 50g is containing manganese 10%, the Hydrogen bromide that brominated 30% the Manganese dibromide aqueous solution and 20g concentration are 48%, adding content is 99.82% Manganse Dioxide 11.32g again, the mol ratio of cobalt oxalate manganese and Manganse Dioxide is 1: 1, stirring heating is warming up to 125 ~ 130 ℃, notice that cooling for reflux is to prevent the bromine volatilization produced in reaction, after pink solid is dissolved, add again the 20g cobalt metal in reactor, continue heating 50min, filter the homogeneous phase solution obtained containing cobalt manganese bromine, this mixed solution can be directly and Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide is mixed the oxide catalyst as PTA.
Use nomenclature in the present invention:
%: mass percent; G: gram; Min: minute.
In the present invention, the measuring method of solid content is that the PTA oxidation residua is carried out being weighed after the dehydration fully of atmospheric low-temperature slow-drying.
In the present invention, the mensuration of cobalt manganese content is to adopt volumetry.
The permanganic acid used in the present invention, mangaic acid demarcate to determine content by the oxalate volumetry before use; The content of Manganse Dioxide is by iodine and Sulfothiorine volumetric determination.
In the present invention, the rate of recovery calculation formula of cobalt manganese is:
The cobalt of measuring in the original residue of quality ÷ of cobalt or manganese in the oxalate that the rate of recovery %=recovery of cobalt or manganese obtains or the quality of manganese * 100%.
The stoichiometric equation of chemical reaction related in the present invention is:
(1)Co
2++H
2C
2O
4·2H
2O(S)=CoC
2O
4·2H
2O(S)+?2H
+
(2)Mn
2++H
2C
2O
4·2H
2O(S)=MnC
2O
4·2H
2O(S)?+2H
+
(3)CoC
2O
4(S)+Br
2(L)=CoBr
2(L)+2CO
2(g)
(4)MnC
2O
4(S)+Br
2(L)=MnBr
2(L)+2CO
2(g)
(5)CoC
2O
4(S)+CH
3COOOH(L)+2HBr(L)=CoBr
2(L)+2CO
2(g)+CH
3COOH(L)+H
2O(L)?(6)MnC
2O
4(S)+CH
3COOOH(L)+2HBr(L)=MnBr
2(L)+2CO
2(g)+CH
3COOH(L)+H
2O(L)
(7)CoC
2O
4(S)+2HBr(L)+H
2O
2(L)=CoBr
2(L)+2CO
2(g)+2H
2O(L)
(8)MnC
2O
4(S)+2HBr(L)+H
2O
2(L)=MnBr
2(L)+2CO
2(g)+2H
2O(L)
(9)?CoC
2O
4(S)+2HBr(L)=CoBr
2(L)+H
2C
2O
4(S)
(10)MnC
2O
4(S)+2HBr(L)=MnBr
2(L)+H
2C
2O
4(S)
(11)2CoC
2O
4(S)+H
2MnO
4(L)+6H
+=2Co
2+(L)+Mn
2+(L)+4CO
2(g)+4H
2O(L)?(12)2MnC
2O
4(S)+H
2MnO
4(L)+6H
+=3Mn
2+(L)+4CO
2(g)+4H
2O(L)
(13)5CoC
2O
4(S)+2HMnO
4(L)+14H
+=5Co
2+(L)+2Mn
2+(L)+10CO
2(g)+8H
2O(L)
(14)5MnC
2O
4(S)+2HMnO
4(L)+14H
+=7Mn
2+(L)+10CO
2(g)+8H
2O(L)
(15)?CoC
2O
4(S)+MnO
2(s)+4HBr=CoBr
2(L)+MnBr
2(L)+2CO
2(g)+2H
2O(L)
(16)?MnC
2O
4(S)+MnO
2(s)+4HBr=2MnBr
2(L)+2CO
2(g)+2H
2O(L)
(17)?Co(S)+Br
2(L)=CoBr
2(L)
(18)?Mn(S)+Br
2(L)=MnBr
2(L)
(19)?2Fe
2++Br
2(L)=2Fe
3++2Br
-(L)
(20)?2Fe
2++H
2O
2(L)?+2H
+=2Fe
3++2H
2O
(21)Fe
2++CH
3COOOH(L)+H
+=Fe
3++H
2O+CH
3COO
-
In the equation bracket, S represents solid; L represents liquid.
From above-described embodiment 1 to 9, can find out, compared with prior art, the present invention has following characteristics:
(1) the waste heat that the present invention takes full advantage of the PTA residue, directly carrying out filtering separation more than 55 ℃, had both utilized the residue energy, had reduced again the residue viscosity while filtering, and had facilitated filtration.
(2) the present invention takes full advantage of the water-soluble feature of organic acid and is filtered, and the organism reclaimed is conveniently utilized, and has increased added value.
(3) the cobalt manganese that the present invention will reclaim from residue has directly changed into catalyzer, and the rate of recovery is high, has saved PTA catalyzer cost.
(4) the recovery method of the present invention to organic acid in residue and Co-Mn metal, technique is simple, flow process is short, energy consumption is low.
(5) the present invention has reduced environmental pollution to the recovery method of organic acid in residue and Co-Mn metal.
Claims (5)
1. the recovery method of organic acid and Co-Mn metal in an oxidized dregs of terephthalic acid, it is characterized in that the high temperature oxidation residue that will discharge from terephthalic acid (being called for short PTA) production equipment, control solid content and implement first step filtering separation in 20～45% scopes and in 55～90 ℃ of scopes of temperature, isolated solids sells for the manufacture of the monomer of resin or paint or returns to the PTA oxidation reactor and use, one-level filtrate is pressed the row process and processed: (I) adds oxalic acid in one-level filtrate, the filtrate temperature is controlled at 60～100 ℃, obtain cobalt manganese oxalate precipitation, filter to isolate cobalt manganese oxalate, filtrate further is cooled to 30～5 ℃, carry out again filtering separation, solids after separation is for extracting phenylformic acid, filtrate is sent wastewater treatment equipment, perhaps (II) directly is cooled to 30～5 ℃ by one-level filtrate, carry out second stage filtering separation, solids after separation is for extracting phenylformic acid, add oxalic acid in secondary filtrate, controlling temperature is 30 ~ 100 ℃, obtain cobalt manganese oxalate precipitation, filter to isolate cobalt manganese oxalate, filtrate is sent wastewater treatment equipment, cobalt manganese oxalate and oxidants hydrogen peroxide that above-mentioned (I) or (II) process are obtained, Peracetic Acid, bromine, permanganic acid, mangaic acid or/and a kind of and Hydrogen bromide in Manganse Dioxide reacted, and the use Cobaltous diacetate aqueous solution, the cobaltous bromide aqueous solution, the manganese acetate aqueous solution, the Manganese dibromide aqueous solution, acetic acid or/and pure water as solvent, after solids all dissolves, add cobalt metal in reactor, at least one in manganese metal or add cobalt metal, a kind of and Hydrogen bromide in manganese metal, continue heating 30 ~ 60min, filter, obtain the homogeneous phase solution containing cobalt manganese bromine, this mixed solution can be directly and Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide, acetic acid or water are mixed the oxide catalyst as PTA, wherein, the mol ratio of cobalt manganese oxalate and hydrogen peroxide or Peracetic Acid is 1: 1.0～1.2, the mol ratio of cobalt manganese oxalate and bromine or Manganse Dioxide or permanganic acid or mangaic acid is stoichiometric ratio, cobalt manganese oxalate and hydrobromic mol ratio are 1: 2.05～10.0.
2. according to the recovery method of organic acid and Co-Mn metal in the described a kind of oxidized dregs of terephthalic acid of claim l, oxalic acid both can directly add with solid form, and the aqueous solution also can be made into containing oxalic acid 10～50% adds.
3. according to the recovery method of organic acid and Co-Mn metal in the described a kind of oxidized dregs of terephthalic acid of claim l, it is characterized in that the mol ratio of the cobalt manganese total amount in oxalic acid and filtrate is 0.75～1.2: 1.
4. according to the recovery method of organic acid and Co-Mn metal in the described a kind of oxidized dregs of terephthalic acid of claim l, it is characterized in that the homogeneous phase treatment temp to cobalt manganese oxalate is 40 ~ 130 ℃.
5. according to the recovery method of organic acid and Co-Mn metal in the described a kind of oxidized dregs of terephthalic acid of claim l, the homogeneous phase treating processes of cobalt manganese precipitation process and cobalt manganese oxalate is all to carry out under normal pressure.
Priority Applications (1)
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| 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 |
| CN105274345B (en) * | 2015-11-27 | 2017-09-29 | 江苏理工学院 | The method of cobalt and manganese in separating and recovering cobalt manganese waste material |
| CN108367942A (en) * | 2015-12-31 | 2018-08-03 | Bp北美公司 | The method for recycling heavy metal ion |
| CN105688990B (en) * | 2016-01-22 | 2019-02-26 | 福建洋屿环保科技股份有限公司 | A method of regenerating cobalt acetate manganese composite catalyst from PTA oxidation residua |
| CN107176745A (en) * | 2016-03-09 | 2017-09-19 | 王仲甫 | The method for biologically treating wastewater of polybasic carboxylic acid residue |
| CN106432622B (en) * | 2016-09-27 | 2019-01-01 | 辽阳合成催化剂有限公司 | A method of reclaimed materials containing monounsaturated dicarboxylic acid prepares unsaturated polyester resin |
| CN107652177A (en) * | 2017-10-28 | 2018-02-02 | 浙江上虞利星化工有限公司 | A kind of preparation method of cobalt or/and manganese acetate |
| CN107617445B (en) * | 2017-10-28 | 2019-12-27 | 浙江上虞利星化工有限公司 | Method for preparing cobalt-manganese-bromine aqueous solution by utilizing recovered cobalt and manganese |
| CN107597170B (en) * | 2017-10-28 | 2019-06-28 | 浙江上虞利星化工有限公司 | Method for preparing cobalt-manganese-bromine aqueous solution by utilizing recovered cobalt and manganese |
| CN107803211B (en) * | 2017-10-28 | 2019-06-28 | 浙江上虞利星化工有限公司 | Preparation method of cobalt or/and manganese bromide |
| CN109592715B (en) * | 2018-12-21 | 2021-04-20 | 陕西师范大学 | Method for controllably preparing manganese oxide with different structures by taking manganese terephthalate dihydrate as precursor |
| CN113292498B (en) * | 2021-06-16 | 2022-11-25 | 浙江工业大学 | 3-peroxybenzoic acid-1-methylimidazole chloride salt and preparation and application thereof |
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| US4490297A (en) * | 1981-12-24 | 1984-12-25 | Dynamit Nobel Ag | Method for the recovery and reuse of cobalt and/or manganese components of catalysts |
| CN101177394A (en) * | 2006-11-08 | 2008-05-14 | 美琪玛国际股份有限公司 | Crude terephthalic acid (CTA) residue recovery and catalyst purification regeneration system and method |
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| US4490297A (en) * | 1981-12-24 | 1984-12-25 | Dynamit Nobel Ag | Method for the recovery and reuse of cobalt and/or manganese components of catalysts |
| CN101177394A (en) * | 2006-11-08 | 2008-05-14 | 美琪玛国际股份有限公司 | Crude terephthalic acid (CTA) residue recovery and catalyst purification regeneration system and method |
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