CN102503813A - 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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- CN102503813A CN102503813A CN2011102826807A CN201110282680A CN102503813A CN 102503813 A CN102503813 A CN 102503813A CN 2011102826807 A CN2011102826807 A CN 2011102826807A CN 201110282680 A CN201110282680 A CN 201110282680A CN 102503813 A CN102503813 A CN 102503813A
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- acid
- cobalt
- manganese
- cobalt 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 96
- 230000003647 oxidation Effects 0.000 title claims abstract description 56
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 40
- 150000007524 organic acids Chemical class 0.000 title claims abstract description 39
- 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
- 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 58
- 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 42
- 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
- 238000001914 filtration Methods 0.000 claims abstract description 34
- 239000007864 aqueous solution Substances 0.000 claims abstract description 33
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011572 manganese Substances 0.000 claims abstract description 25
- 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
- 229910052748 manganese Inorganic materials 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 17
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 17
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 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
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims abstract 2
- 239000003973 paint Substances 0.000 claims abstract 2
- 239000011347 resin Substances 0.000 claims abstract 2
- 229920005989 resin Polymers 0.000 claims abstract 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 34
- 238000011084 recovery Methods 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 33
- 229910020632 Co Mn Inorganic materials 0.000 claims description 24
- 229910020678 Co—Mn Inorganic materials 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 20
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- ZBICJTQZVYWJPB-UHFFFAOYSA-N [Mn].[Co].[Br] Chemical compound [Mn].[Co].[Br] ZBICJTQZVYWJPB-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 9
- 238000001816 cooling Methods 0.000 abstract description 7
- -1 permanganate Chemical compound 0.000 abstract description 6
- 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
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000000706 filtrate Substances 0.000 abstract 6
- 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 17
- 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
- 238000010792 warming Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 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
- 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
- 229920003002 synthetic resin Polymers 0.000 description 7
- 239000000057 synthetic resin Substances 0.000 description 7
- 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
- 238000010992 reflux Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 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
- 230000009467 reduction Effects 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
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 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
- 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
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 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
- 230000007246 mechanism Effects 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
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 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
- 238000005303 weighing Methods 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
-
- 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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.The residue that contains organic acid and Co-Mn metal that PTA device mother liquid evaporation device is got rid of of saying so in more detail filters to isolate water-insoluble organic acid solids, and filtrating warp further processing reclaims organic acid, Co-Mn compound and the Co-Mn compound that reclaims carried out the homogeneous phase processing return the field that the PTA oxidation system recycles again.
Background technology
At present, the working method of PTA is to adopt the compound of cobalt manganese bromine as catalyzer p-Xylol to be processed 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, must 10～20% the mother liquor slurry that contains catalyzer be extracted out, after thin-film evaporator reclaims a large amount of acetic acid, remaining for containing the residue slurries of Cobaltous diacetate, manganese acetate, aromatic acid, acetic acid etc.One cover is produced the production equipment of 1,200,000 tons of PTA per year; Annual to discharge contain organic acid and catalyzer the oxidation residua slurries above 1.5 ten thousand tons; Wherein contain cobalt 0.5 ~ 1.2%, contain manganese 0.5 ~ 1.2%, contain organic acid 30 ~ 42%, if can organic acid, cobalt, the Mn catalyst in this part residue slurries be reclaimed, return mechanism uses or utilizes; Not only reduce environmental pollution, and direct economic benefit is above 4,000 ten thousand yuan.
The Mitsui chemistry once provided a kind of recovery and treatment method of PTA oxidation residua; This method is to reclaim acetic acid through thin-film evaporator; Under 45 ℃, extract with vaal water; Obtain Cobaltous diacetate and manganese acetate extraction liquid and after concentrating, directly return the use of PTA device, the granulation of residue organic acid residue is discharged and is sent incinerator, and this method has application on the PTA device of Jinan chemical fibre, Oil of Shanghai Petrochemical Company and Plant of Tianjin Petrochemical Company head factory; Also there is patent that the method that reclaims cobalt manganese in the PTA residue through IX is provided, like Chinese patent 98113765.2,99121153.7,200410030379.7.
The PTA device of E.I.Du Pont Company's technology then adopts oxalate to reclaim the cobalt-manganese catalyst in the residue, and residue organic acid waste liquid is directly discharged burning.
The disadvantage that the method for Mitsui Chemicals exists is: have only about 70% cobalt, Mn catalyst to obtain reclaiming, and energy consumption is high, equipment is many, and pipeline is prone to stop up, and the water waste is big; There is the accumulation of foreign ions such as iron, nickel in the cobalt-manganese catalyst that reclaims, defectives such as the unstable and active reduction of cobalt and manganese valence state; Organic acid is all sent to burning disposal, contaminate environment in addition; The IX rule exists treatment unit and complex disposal process, introduces a large amount of other chemical substances, has increased defectives such as waste discharge, wastewater treatment capacity increase, cost height; The instability that the PTA residue is formed has increased difficulty and complexity also for the IX pre-treatment, and the not mentioned organic acid of this method reclaims.
The defective that the oxalate way of recycling that E.I.Du Pont Company adopts exists is; It is that the oxalic acid or the aqueous solution are directly added from the mother liquor that the PTA device is extracted out; Deposition that oxalic acid and cobalt manganese generate and the insoluble organic acid in the residue liquid mix and form a kind of dope; And through finned whizzer separation, this dope sticks on the separating device not easily separated easily, and pipeline and equipment also very easily stop up; Isolating need more isolated liquid more than 90% being returned simultaneously washed; Therefore the actual efficiency of separating device is very low, and to obtain be cobalt oxalate manganese and organic acid solid mixture, and this mixture is dispersed in and returns what mix formation with live catalyst when using in the aqueous acetic acid is heterogeneous solution; Can only reach through the internal circulating load that improves PTA oxidizing reaction actuator temperature and reduction recovery dispersion liquid during application and utilize purpose again; This also is the reason that the present PTA of Du Pont technology adopts high temperature oxidation, but the raising of temperature can make that raw materials used PX (abbreviation of p-Xylol) significantly increases with acetic acid consumption when making PTA, and the side reaction aggravation is obvious; In addition, this technology is still burning to the residue treatment mode of isolating behind cobalt oxalate manganese and the acetic acid, has environmental pollution.
Summary of the invention
The object of the invention is exactly to overcome the disadvantage that prior art exists, and adopts new technical characterictic, provides in a kind of PTA oxidation residua organic acid and cobalt-manganese catalyst to reclaim to reach and utilizes novel method again, and be applicable to different PTA devices.
In order to reach the object of the invention; The present invention at first carries out one-level while hot with the PTA oxidation raffinate of extracting out and filters to isolate solids wherein; This solids staple is water-insoluble organic acids such as terephthalic acid, 4-carboxyl benzaldehyde, p-methylbenzoic acid, and this solids is returned oxidation system or sells the raw material that is used for synthetic resins; Filtrating is handled by following process: (I) adds oxalic acid in one-level filtrating, and the filtrating temperature is controlled at 60～100 ℃, and the mol ratio of the cobalt manganese total amount in oxalic acid and the filtrating is 0.75～1.2: 1; Obtain cobalt manganese oxalate precipitation; Filter to isolate cobalt oxalate manganese, filtrating further is cooled to 30～5 ℃, carries out filtering separation again; Solids after the separation is used to extract phenylformic acid, and filtrating is sent wastewater treatment equipment; Perhaps (II) directly is cooled to 30～5 ℃ with one-level filtrating, carries out second stage filtering separation, and the solids after the separation is used to extract phenylformic acid; In secondary filtrating, add oxalic acid; Controlled temperature is 30 ~ 100 ℃, and the mol ratio of the cobalt manganese total amount in oxalic acid and the filtrating is 0.75～1.2: 1, obtains cobalt oxalate manganese deposition; Filter to isolate cobalt oxalate manganese, filtrating is sent wastewater treatment equipment; With above-mentioned (I) perhaps the cobalt oxalate manganese that obtains of (II) process and oxidants hydrogen peroxide, Peracetic Acid, bromine, permanganic acid, mangaic acid, Manganse Dioxide or/and Hydrogen bromide carries out the homogeneous phase processing reaction; And use the 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; In reactor drum, add cobalt metal, manganese metal or/and Hydrogen bromide continues heating 30 ~ 60min, filter; Promptly obtain containing the homogeneous phase solution of cobalt manganese bromine; This mixed solution can directly mix the oxide catalyst as PTA with Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide, acetic acid or water, and 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 a 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 the terephthalic acid oxidation residua of the present invention is considered and has been studied the residue component differences influence that causes owing to the oxidation technology of different PTA oxidizer units source is different, or rather; The solid content that different PTA oxidizer 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 in stage, but usually all in 30 ~ 42% scopes; Cobalt manganese content is then respectively between 0.5 ~ 1.2%; For this reason, the present invention is directed to this scope and study in great detail, also studied simultaneously some dehydration back solid contents and surpassed 45% residue and thin up and be lower than 20% residue separating effect and influence factor to solid content; Experiment shows: when solid content surpasses 45%; Though still can direct filtration separate, residue thickness, filtration velocity are slow, and water soluble organic substance and catalyst residue obviously raise in the isolated solids; Also significantly increase the washing water consumption; Preferably refilter separation behind the thin up this moment, and water yield increase also helps to change the phenylformic acid in the solids and Co-Mn compound over to aqueous phase, makes the water soluble organic substance ratio minimizing in the solids that flash trapping stage goes out; Experiment shows that when below adding water adjusting solid content to 20%, filtering, 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,, have to use hot water or outer heating is provided for keeping filtration temperature; This increases the process energy consumption; Also increase later stage wastewater treatment expense, therefore, the present invention's control and selection solid content carry out first step filtering separation in 20 ~ 45% scopes; For cobalt manganese, when cobalt and manganese concentration was low to moderate 0.05% respectively in the waste liquid, the recovery that still can make cobalt through the present invention was greater than 98%.
The recovery method of organic acid and Co-Mn metal in the terephthalic acid oxidation residua of the present invention; Be the residue temperature to be controlled at implement first step filtering separation in 55～90 ℃ of scopes; Filter to isolate solids wherein; TR when this TR is equal to the residue discharge basically, both energy-conservation, can avoid the big filtration velocity that influences of residue fluid viscosity again; When temperature is lower than 55 ℃, separate benzoic acid content rising in the solids that obtains, be unfavorable for returning again oxidation; When temperature was higher than 90 ℃, when particularly reaching 95 ~ 100 ℃, one deck thickness oily matter can appear in the filtrating top layer, and the cooling crisp shape thing of back 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 the terephthalic acid oxidation residua of the present invention, be that the processing mode of filtrating can be divided into following dual mode after flash trapping stage is deviate from insoluble organic acid solids: (I) adds oxalic acid in filtrating; The filtrating temperature is controlled at 60～100 ℃; The soluble substances such as phenylformic acid that contain in the solution this moment still are dissolved in the aqueous solution, can not influence the deposition and the filtration of cobalt oxalate manganese, and filtered while hot is promptly isolated cobalt manganese oxalate compound; Filtrating after the separation further is cooled to 30～5 ℃; Dissolved organic matters such as phenylformic acid will separate out, and carry out filtering separation again, and filtrating is sent wastewater treatment equipment; Solids is crude benzol formic acid, and purifying through the high temperature distillation to obtain meeting the purified petroleum benzin formic acid of pharmaceutical grade standard; Perhaps (II) directly is cooled to 30～5 ℃ with one-level filtrating; Dissolved organic matters such as phenylformic acid are separated out and carry out filtering separation, add oxalic acid in the filtrating after the separation again, controlled 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 dual mode, the mol ratio of the cobalt manganese total amount in oxalic acid and the filtrating is 0.75～1.2: 1.
The recovery method of organic acid and Co-Mn metal in the terephthalic acid oxidation residua of the present invention, oxalic acid both can directly add with solid form, also can directly add the aqueous solution that contains oxalic acid 10～50%, and minimum with cost is principle.
The recovery method of organic acid and Co-Mn metal in the terephthalic acid oxidation residua of the present invention; Be that the cobalt manganese oxalate that separation obtains is carried out the homogeneous phase processing; Be about to cobalt manganese oxalate and oxidants hydrogen peroxide, Peracetic Acid, bromine, permanganic acid, mangaic acid, Manganse Dioxide or/and Hydrogen bromide reacts dissolving; And use the 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 obtains a kind of homogeneous phase solution that contains cobalt manganese bromide anion as solvent and adjusting cobalt and manganese concentration, the mol ratio of cobalt manganese oxalate and hydrogen peroxide or Peracetic Acid is 1: 1.0～1.2 in the reaction process; The mol ratio of cobalt manganese oxalate and bromine or Manganse Dioxide or permanganic acid or mangaic acid is a 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 the terephthalic acid oxidation residua of the present invention; Be cobalt manganese oxalate solution that dissolving is obtained further with cobalt, manganese or/and the Hydrogen bromide reaction, to eliminate free bromine residual in the solution, to reduce impurity such as free acid, iron.
The recovery method of organic acid and Co-Mn metal in the terephthalic acid oxidation residua of the present invention is 40～130 ℃ to the homogeneous phase treatment temp of cobalt manganese oxalate; When temperature was lower than 40 ℃, the decomposition rate of cobalt manganese oxalate was slow and decomposition is incomplete, can not get the solution of complete homogeneous phaseization; When temperature was higher than 130 ℃, although still can improve the speed of homogeneous phaseization, the corrodibility increase of bromine, pressure etc. required all will improve to the manufacturing of equipment and technology controlling and process, 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 the terephthalic acid oxidation residua of the present invention, what obtain contains cobalt (Co
2+), manganese (Mn
2+), bromine (Br
-) homogeneous phase solution can directly be mixed for allocating the catalyzer for preparing terephthalic acid by p-Xylol through oxidation through pumping and live catalyst or aqueous acetic acid etc.
The recovery method of organic acid and Co-Mn metal in the terephthalic acid oxidation residua of the present invention is directly to send PTA waste water reclamation treatment plant to handle the waste water behind separation of cobalt manganese oxalate and the organic acid.
Embodiment
Further specify the present invention through embodiment below:
Embodiment 1:
Get the oxidation residua 1000g of PTA oxidation (first) device, wherein cobalt contents is 0.92%, and manganese content is 0.95%; Solid content is 40.6%; Attemperation is at 65 ~ 70 ℃, and filtered while hot is separated solids wherein, and usefulness pact and the isopyknic 70 ℃ of hot washes of solids are once again; Be weighed as 181.4g after the solids drying, directly return oxidation system and reoxidize or sell the raw material that is used for synthetic resins; In filtrating, add solid oxalic acid (concentration of oxalic acid >=99.5%, down together) 41.67g, the mol ratio of cobalt manganese is 1: 1 in oxalic acid and the filtrating; Stirring is warming up to 80 ~ 85 ℃; Filtered while hot, isolated pink solid thing are cobalt manganese oxalate compound, and dry back quality is 56.51g; Wherein cobalt manganese content is respectively 16.14%, 15.32%, and the recovery of cobalt manganese is respectively 99.1% and 91.2%; Filtrating after the separation further is cooled to 10 ~ 5 ℃; Have a large amount of whites and faint yellow solid thing to separate out in the solution this moment, when no solids is separated out, and filtering separation; Filtrating is sent wastewater treatment equipment; Solids is crude benzol formic acid etc., is weighed as 203.1g through dehydrating, with 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 drum, adds and contains cobalt 4% Cobaltous diacetate aqueous solution 120g, adds bromine 17.68g; The mol ratio of cobalt oxalate manganese and bromine is a stoichiometric ratio, and stirring heating is warming up to 85 ~ 90 ℃, notices that cooling for reflux is to prevent the bromine volatilization; After solids all dissolves; The Hydrogen bromide that in reactor drum, adds 20g cobalt metal and 10g48% again continues heating 30min, filters; Promptly obtain containing the homogeneous phase solution of cobalt manganese bromine, this mixed solution can directly mix the oxide catalyst as PTA with Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide.
Embodiment 2:
Embodiment 1 is separated the cobalt manganese oxalate 20g that obtains add in the 250ml reactor drum, add and contain manganese 6% manganese acetate aqueous solution 100g, adding 20g concentration is 48% Hydrogen bromide and slowly adds the 16.4g27.5% hydrogen peroxide; The mol ratio of cobalt oxalate manganese and hydrogen peroxide is about 1: 1.2, and stirring heating is warming up to 95 ~ 100 ℃, notes the bromine volatilization of cooling for reflux to produce in preventing to react; After solids all dissolves; In reactor drum, add the 20g cobalt metal again, continue the about 50min of heating, filter; Promptly obtain containing the homogeneous phase solution of cobalt manganese bromine, this mixed solution can directly mix the oxide catalyst as PTA with Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide.
Embodiment 3:
Get the oxidation residua 500g of PTA oxidation (first) device; One times of thin up; Attemperation is at 85 ~ 90 ℃, and filtered while hot is separated solids wherein, and usefulness pact and the isopyknic 90 ℃ of hot washes of solids are once again; Be weighed as 81.5g after the solids drying, directly return oxidation system and reoxidize or sell the raw material that is used for synthetic resins; In filtrating, add oxalic acid 25.0g; The mol ratio of cobalt manganese is 1.2: 1 in oxalic acid and the filtrating, stirs and is warming up to 80 ~ 85 ℃, filtered while hot; Isolated pink solid thing is cobalt manganese oxalate compound; Dry back quality is about 29.57g, and wherein cobalt manganese content is respectively 15.48%, 15.95%, and the recovery of cobalt manganese is respectively 99.5% and 99.3%; Filtrating after the separation further is cooled to 20 ~ 15 ℃, and adularescent and faint yellow solid thing are separated out in the solution at this moment, and a small amount of brown oil appears in the solution upper strata; When no solids is separated out, filtering separation, filtrating is sent wastewater treatment equipment; Solids is crude benzol formic acid etc.; Its middle and upper part is weighed as 110.7g through dehydrating with a small amount of brown dope, with 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 drum; Add the Cobaltous diacetate aqueous solution 100g that contains cobalt 3%, manganese acetate aqueous solution 50g, the Glacial acetic acid min. 99.5 20g that contains manganese 6%; The stirring at normal temperature state drip down proven concentration be 98.12% permanganic acid 5.41g to reactor drum, the mol ratio of cobalt oxalate manganese and permanganic acid is 1: 0.4, dropwises post-heating and is warming up to 40 ~ 45 ℃; This moment, solids all dissolved; In reactor drum, add 20g cobalt metal and 20g concentration again and be 48% Hydrogen bromide, continue the about 30min of heating, filtration; Promptly obtain containing the homogeneous phase solution of cobalt manganese bromine, this mixed solution can directly mix the oxide catalyst as PTA with Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide.
Embodiment 4:
Get the oxidation residua 750g behind the partly dehydrating of PTA oxidation (first) device; Add water 250g dilution; Attemperation is at 55 ~ 60 ℃, and filtered while hot is separated solids wherein, and usefulness pact and the isopyknic 60 ℃ of hot washes of solids are once again; Be weighed as 131.7g after the solids drying, directly return oxidation system and reoxidize or sell the raw material that is used for synthetic resins; Filtrating is cooled to 30 ~ 25 ℃, filters to isolate the solids of separating out, be weighed as 155.2g through dehydrating, with this solids again high temperature distillation purify and can obtain meeting the purified petroleum benzin formic acid of pharmaceutical grade standard; Filtrating is heated to 40 ~ 45 ℃ also adds the aqueous solution 93.7g that contains 25% oxalic acid; The mol ratio of cobalt manganese is 0.75: 1 in oxalic acid and the filtrating, stirs, and promptly has a large amount of pink throw outs to separate out; Filtering separation is cobalt manganese oxalate compound; Dry back quality is 31.07g, and wherein cobalt manganese content is respectively 21.96%, 9.77%, and the recovery of cobalt manganese is respectively 98.9% and 42.6%; Filtrating after the separation is directly sent wastewater treatment equipment; The cobalt manganese oxalate 20g that above-mentioned separation is obtained adds in the 250ml reactor drum; Add the Cobaltous diacetate aqueous solution 100g that contains cobalt 3%, manganese acetate aqueous solution 100g, the Glacial acetic acid min. 99.5 20g that contains manganese 6%; The stirring at normal temperature state drip down proven concentration be 98.06% mangaic acid 6.78g to reactor drum, the mol ratio of cobalt oxalate manganese and mangaic acid is 1: 0.5, dropwises post-heating and is warming up to 60-65 ℃; This moment, solids all dissolved; In reactor drum, add 20g cobalt metal and 20g concentration again and be 48% Hydrogen bromide, continue the about 30min of heating, filtration; Promptly obtain containing the homogeneous phase solution of cobalt manganese bromine, this mixed solution can directly mix the oxide catalyst as PTA with Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide.
Embodiment 5:
Get the oxidation residua 1000g of PTA oxidation (first) device, at air drying, make its solid content reach 45% after; Attemperation is at 85 ~ 90 ℃, and filtered while hot is separated solids wherein, finds solution thickness this moment; Filtration velocity is slower than embodiment 1 speed, and after having filtered, usefulness pact and isopyknic 90 ~ 95 ℃ of hot washes of solids are once again; Be weighed as 176.6g after the solids drying, directly return oxidation system and reoxidize or sell the raw material that is used for synthetic resins; In filtrating, add the aqueous solution 91.68g that contains 50% oxalic acid; The mol ratio of cobalt manganese is 1.1: 1 in oxalic acid and the filtrating, stirs and is warming up to 95 ~ 100 ℃, filtered while hot; Isolated pink solid thing is cobalt manganese oxalate compound; Dry back quality is 57.87g, and wherein cobalt manganese content is respectively 15.82%, 15.63%, and the recovery of cobalt manganese is respectively 99.5% and 95.2%; Filtrating after the separation further is cooled to 10 ~ 5 ℃, and have a large amount of whites and faint yellow solid thing to separate out in the solution this moment, and there is skim brown dope on the solution upper strata; When no solids is separated out; Filtering separation, filtrating send wastewater treatment equipment, solids to be crude benzol formic acid etc.; Be weighed as 206.9g through dehydrating, with 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 drum, and adding concentration is 48% Hydrogen bromide 38.26g, and cobalt oxalate manganese and hydrobromic mol ratio are 1: 2.05; Be heated with stirring to 120 ~ 125 ℃, after the solids dissolving, be cooled to normal temperature; Filter; The solids oxalic acid that obtains recycles, and in filtrating, adds the 10g cobalt metal again, is heated to 100 ~ 105 ℃ and continues the about 60min of reaction; Filtrating is the homogeneous phase solution that contains cobalt manganese bromine, and this mixed solution can directly mix the oxide catalyst as PTA with Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide.
Embodiment 6:
Embodiment 5 is separated the cobalt manganese oxalate 20g that obtains add in the 250ml reactor drum, add and contain cobalt 10%, brominated 28% cobaltous bromide solution 50g, contain manganese 6% manganese acetate aqueous solution 100g; Slowly adding 42.5g concentration is 20% Peracetic Acid; The mol ratio of cobalt oxalate manganese and Peracetic Acid is about 1: 1, and stirring heating is warming up to 95 ~ 100 ℃, notes the bromine volatilization of cooling for reflux to produce in preventing to react; After solids all dissolves; In reactor drum, add 2g manganese metal and 12g Hydrogen bromide again, continue reaction 50min, filter; Promptly obtain containing the homogeneous phase solution of cobalt manganese bromine, this mixed solution can directly mix the oxide catalyst as PTA with Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide.
Embodiment 7:
Get the oxidation residua 1000g of PTA oxidation (second) device; Wherein solid content is 33.6%, and cobalt contents is 0.65%, and manganese content is 0.70%; Attemperation is at 65 ~ 70 ℃; Filtered while hot separate wherein solids and with approximately with the isopyknic 70 ℃ of hot washes of solids once, be weighed as 125.9g after the solids drying, directly return oxidation system and reoxidize or sell the raw material that is used for synthetic resins; In filtrating, add the aqueous solution 301.5g that contains 10% oxalic acid; The mol ratio of cobalt manganese is about 1: 1 in oxalic acid and the filtrating; Stirring is warming up to 80 ~ 90 ℃, and filtered while hot is isolated pink cobalt manganese oxalate, and dry back quality is 40.90g; Wherein cobalt manganese content is respectively 15.78%, 15.66%, and the recovery of cobalt manganese is respectively 99.3% and 91.5%; Filtrating after the separation further is cooled to 10 ~ 5 ℃; Have a large amount of whites and faint yellow solid thing to separate out in the solution this moment, when no solids is separated out, and filtering separation; Filtrating is sent wastewater treatment equipment; Solids is crude benzol formic acid etc., is weighed as 192.2g through dehydrating, with 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 drum, and adding concentration is 48% Hydrogen bromide 381.5g, and cobalt oxalate manganese and hydrobromic mol ratio are 1: 10; Be heated with stirring to 120 ~ 125 ℃, after the solids dissolving, be cooled to normal temperature; Filter; The solids oxalic acid that obtains recycles, and in filtrating, adds 30g cobalt metal and 5g manganese metal again, is heated to 120 ~ 125 ℃ and continues the about 60min of reaction; Filtrating is the homogeneous phase solution that contains cobalt manganese bromine, and the oxide catalyst that this mixed solution can directly mix with Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide as PTA perhaps send reactor drum and cobalt metal or/and manganese metal further reacts.
Embodiment 8:
Get the oxidation residua 1000g of PTA oxidation (second) device; Attemperation is at 55 ~ 60 ℃; Filtered while hot is separated solids wherein; Usefulness pact and the isopyknic 60 ℃ of hot washes of solids once are weighed as 128.2g after the solids drying again, directly return oxidation system and reoxidize or sell the raw material that is used for synthetic resins; Filtrating is cooled to 10 ~ 5 ℃, filters to isolate the solids of separating out, be weighed as 191.1g through dehydrating, with this solids again high temperature distillation purify and can obtain meeting the purified petroleum benzin formic acid of pharmaceutical grade standard; Filtrating is heated to 50 ~ 55 ℃ and add solid oxalic acid 36g; The mol ratio of cobalt manganese is about 1.2: 1 in oxalic acid and the filtrating, stirs, and pink throw out cobalt manganese oxalate is separated out; Filtering separation; Dry back quality is 42.63g, and wherein cobalt manganese content is respectively 15.16%, 16.26%, and the recovery of cobalt manganese is about 99.4% and 99.0% respectively; Filtrating after the separation is directly sent wastewater treatment equipment; The cobalt manganese oxalate 30g that above-mentioned separation is obtained adds in the 250ml reactor drum, adds the manganese acetate aqueous solution 30g that contains the aqueous acetic acid 50g of cobalt 3% and contain manganese 6%, and adding concentration is 48% Hydrogen bromide 84g; Cobalt oxalate manganese and hydrobromic mol ratio are 1: 3; Be heated with stirring to boiling, after the solids dissolving, be cooled to normal temperature; Filter; The solids oxalic acid that obtains recycles, and filtrating is the homogeneous phase solution that contains cobalt manganese bromine, and this mixed solution can directly mix with Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide as the oxide catalyst of PTA perhaps to be sent to cobalt metal or/and manganese metal further reacts.
Embodiment 9:
Get the oxidation residua 1000g of PTA oxidation (second) device; Repeat the preceding two-stage sepn process of embodiment 6, contain washing and obtain about 820g altogether and do not add oxalic acid filtrating, get 2 parts of preceding filtratings respectively; Wherein 1 part is 41g; Thin up is to 650g, makes wherein that cobalt contents is about 0.05%, and this moment, manganese content was about 0.054%; In addition 1 part be 410g, heats to be concentrated into 216g, makes wherein that concentration of cobalt ions is about 1.5%, and manganese content is about 1.62% at this moment; The 1st part of solution is heated to 40 ~ 45 ℃ adds oxalic acid again; The 2nd part of solution concentration directly added oxalic acid after intact therein; The oxalic acid add-on is produced as benchmark to no longer include deposition in the solution; The 1st part and the 2nd part of solution consumption oxalic acid are respectively 1.82g and 16.16g, and according to cobalt manganese content meter in the PTA residue liquid, the 1st part and the 2nd part oxalic acid and the mol ratio of cobalt manganese are about 1.2: 1 respectively and 1.1: 1; The oxalate precipitation that obtains is merged filtering separation, and dry back quality is 23.49g, and wherein cobalt manganese content is respectively 15.14%, 16.28%, and the recovery of cobalt manganese is about 99.5% and 99.3% respectively; The cobalt manganese oxalate that above-mentioned separation is obtained all adds in the 250ml reactor drum; Adding 50g contains cobalt 10%, brominated 28% the cobaltous bromide aqueous solution, 50g to contain manganese 10%, brominated 30% the Manganese dibromide aqueous solution and 20g concentration is 48% Hydrogen bromide; Adding content again is 99.82% Manganse Dioxide 11.32g, and the mol ratio of cobalt oxalate manganese and Manganse Dioxide is 1: 1, and stirring heating is warming up to 125 ~ 130 ℃; Note the bromine volatilization of cooling for reflux to produce in preventing to react; After the pink solid dissolving, in reactor drum, add the 20g cobalt metal again, continue heating 50min; Filter the homogeneous phase solution that promptly obtains containing cobalt manganese bromine, this mixed solution can directly mix the oxide catalyst as PTA with Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide.
Use nomenclature among the present invention:
%: mass percent; G: gram; Min: minute.
The measuring method of solid content is that the PTA oxidation residua is carried out weighing after the dehydration fully of atmospheric low-temperature slow-drying among the present invention.
Cobalt manganese Determination on content is to adopt volumetry among the present invention.
Employed permanganic acid, mangaic acid are demarcated to confirm content through the oxalate volumetry before use among the present invention; The content of Manganse Dioxide is through iodine and Sulfothiorine volumetric determination.
The recovery calculation formula of cobalt manganese is among the present invention:
The cobalt of measuring in the original residue of quality ÷ of cobalt or manganese in the oxalate that the recovery %=recovery of cobalt or manganese obtains or quality * 100% of manganese.
The stoichiometric equation of chemical reaction that relates among 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
-
S represents solid in the equation bracket; L represents liquid.
Can find out that from the foregoing description 1 to 9 compared with prior art, the present invention has following characteristics:
⑴ the present invention has made full use of the waste heat of PTA residue directly carrying out filtering separation more than 55 ℃, has both utilized the residue energy, has reduced the residue viscosity when filtering again, has made things convenient for filtration.
⑵ the present invention has made full use of the water-soluble characteristic of organic acid and has filtered, and makes the organism of recovery obtain convenient the utilization, has increased added value.
⑶ the cobalt manganese that the present invention will reclaim from residue has directly changed into catalyzer, and the recovery is high, has saved PTA catalyzer cost.
⑷ the present invention is to the recovery method of organic acid in the residue and Co-Mn metal, and technology is simple, flow process is short, energy consumption is low.
⑸ the present invention has reduced environmental pollution to the recovery method of organic acid in the residue and Co-Mn metal.
Claims (6)
1. the recovery method of organic acid and Co-Mn metal in the terephthalic acid oxidation residua; It is characterized in that the high temperature oxidation residue that will from terephthalic acid (be called for short PTA) production equipment, discharge, the control solid content is implemented first step filtering separation in 20～45% scopes and in 55～90 ℃ of scopes of temperature, and isolated solids sells and is used to make the monomer of resin or paint or returns the use of PTA oxidation reactor; One-level filtrating is handled by following process: (I) adds oxalic acid in one-level filtrating; The filtrating temperature is controlled at 60～100 ℃, obtains cobalt manganese oxalate precipitation, filters to isolate cobalt manganese oxalate; Filtrating further is cooled to 30～5 ℃; Carry out filtering separation again, the solids after the separation is used to extract phenylformic acid, and filtrating is sent wastewater treatment equipment; Perhaps (II) directly is cooled to 30～5 ℃ with one-level filtrating; Carry out second stage filtering separation, the solids after the separation is used to extract phenylformic acid, in secondary filtrating, adds oxalic acid; Controlled temperature is 30 ~ 100 ℃; Obtain cobalt manganese oxalate precipitation, filter to isolate cobalt manganese oxalate, filtrating is sent wastewater treatment equipment; With above-mentioned (I) perhaps the cobalt manganese oxalate that obtains of (II) process and oxidants hydrogen peroxide, Peracetic Acid, bromine, permanganic acid, mangaic acid, Manganse Dioxide or/and Hydrogen bromide react; And use the 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; In reactor drum, add cobalt metal, manganese metal or/and Hydrogen bromide continues heating 30 ~ 60min, filter; Promptly obtain containing the homogeneous phase solution of cobalt manganese bromine; This mixed solution can directly mix the oxide catalyst as PTA with Cobaltous diacetate, manganese acetate, cobaltous bromide, Manganese dibromide, acetic acid or water, and 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 terephthalic acid oxidation residua of claim l, oxalic acid both can directly add with solid form, also can be made into the aqueous solution that contains oxalic acid 10～50% and added.
3. according to the recovery method of organic acid and Co-Mn metal in the described a kind of terephthalic acid oxidation residua of claim l, the mol ratio of the cobalt manganese total amount in it is characterized in that oxalic acid and filtrating 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 terephthalic acid oxidation residua 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 terephthalic acid oxidation residua of claim l, the homogeneous phase processing of cobalt manganese deposition and cobalt manganese oxalate all is under normal pressure, to carry out.
6. according to the recovery method of organic acid and Co-Mn metal in the described a kind of terephthalic acid oxidation residua of claim l; Cobalt manganese oxalate solution that it is characterized in that dissolving is obtained and cobalt, manganese are or/and the Hydrogen bromide reaction, to eliminate free bromine residual in the solution, to reduce impurity such as free acid, iron.
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