CN100462144C - Preparation method of composition - Google Patents
Preparation method of composition Download PDFInfo
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- CN100462144C CN100462144C CNB2006100690197A CN200610069019A CN100462144C CN 100462144 C CN100462144 C CN 100462144C CN B2006100690197 A CNB2006100690197 A CN B2006100690197A CN 200610069019 A CN200610069019 A CN 200610069019A CN 100462144 C CN100462144 C CN 100462144C
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- cobalt
- manganese
- compound
- reactor
- bromine
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- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 64
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 64
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 64
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 56
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 45
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 44
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 43
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011572 manganese Substances 0.000 claims abstract description 35
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 31
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 20
- 150000002697 manganese compounds Chemical class 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims abstract description 7
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 37
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 4
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 4
- 229940093474 manganese carbonate Drugs 0.000 claims description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 3
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 16
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 abstract 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 description 21
- 239000012535 impurity Substances 0.000 description 16
- 229960000583 acetic acid Drugs 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 11
- 230000001105 regulatory effect Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000001143 conditioned effect Effects 0.000 description 7
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 6
- 125000001246 bromo group Chemical group Br* 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 4
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- -1 manganese, manganese compound Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910020632 Co Mn Inorganic materials 0.000 description 1
- 229910020678 Co—Mn Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 230000003197 catalytic effect 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
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing a composition, namely a cobalt containing compound is prepared by adding at least one of cobalt or a cobalt compound, manganese or a manganese compound and an aqueous hydrobromic acid solution into a reactor to react directly or in the presence of at least one of acetic acid, hydrogen peroxide or peracetic acid and bromine2+) Manganese (Mn)2+) Bromine (Br)-) A homogeneous aqueous solution of at least two of (1). The homogeneous composition water solution can be directly mixed with cobalt acetate, manganese acetate, bromide or acetic acid water solution to prepare the catalyst for preparing terephthalic acid by oxidizing p-xylene or preparing trimellitic anhydride by oxidizing trimellitic acid.
Description
Technical field
The present invention relates to-kind of preparation of compositions method field.Say so in more detail directly or in acetic acid, hydrogen peroxide, bromine, carry out prepared in reaction under at least a existence condition and contain cobalt (Co by at least a and hydrobromic acid aqueous solution in cobalt, cobalt compound, manganese, the manganese compound
2+), manganese (Mn
2+), bromine (Br
-) at least two kinds the method for homogeneous composition.
Background technology
As everyone knows, contain cobalt (Co
2+), manganese (Mn
2+), bromine (Br
-) at least two kinds homogeneous phase aqueous solution composition be mainly used in PTA (abbreviation of terephthalic acid (TPA)) and TMA (trimellitic anhydride) manufacturing industry, and use as catalyst, general PTA carbon monoxide-olefin polymeric preparation method adopts two kinds of waters in crystal cobalt acetate, manganese acetate, hydrobromic acid or the tetrabromoethane bought or aqueous acetic acid dissolving preparation at least both at home and abroad at present; Also having a kind of is " chemical encyclopedia " that " chemical encyclopedia " editorial board writes, the 1st edition, the 6th volume (Chemical Industry Press, Beijing, in August, 1994) the method by cobalt carbonate and hydrobromic acid prepared in reaction cobaltous bromide, 614 pages of records of the 11st volume of the 107th page of record by manganese monoxide or manganese carbonate or manganous hydroxide and hydrobromic acid prepared in reaction manganous bromide.
One of disadvantage that prior art exists is a carbon monoxide-olefin polymeric application cost height, because crystal cobalt acetate, manganese acetate production process complexity, price height; The preparation process of cobaltous bromide and manganous bromide does not have the removal of impurities process, and the trace 4 valency manganese ions that contain in trace 3 valency cobalt ions that contain in the general cobalt compound and the manganese compound can not be removed, can not use as catalyst without purifying, therefore to used raw material require high, production cost is high.
Be crystal because of the Co-Mn compound that uses when two of the disadvantage that prior art exists is the allotment carbon monoxide-olefin polymeric, therefore need special course of dissolution, complicated operation.
Three of the disadvantage that prior art exists is sedimentation and oxidation, the incomplete phenomenon of dissolving to take place easily when dissolving modulation catalyst composition and with the side reaction of cobalt and manganese with produce free bromine, catalytic activity instability and selectivity reduce when causing using.
Summary of the invention
Purpose of the present invention is exactly to overcome the disadvantage that prior art exists, adopt new technical characterictic, the novel preparation method of a kind of low cost, the high activity homogeneous catalyst composition aqueous solution is provided, and said composition can be directly used in by p xylene oxidation and make PTA and made the high activated catalyst of TMA by trimethyl benzene oxidation.
In order to reach purpose of the present invention, at least a and hydrobromic acid aqueous solution in the cobalt that use cost of the present invention and price are lower, cobalt compound, manganese, the manganese compound directly or carry out prepared in reaction under at least a existence condition in acetic acid, hydrogen peroxide, bromine, by conditioned reaction thing proportioning, temperature with utilize metal to participate in the pH value and the reduction high volence metal ion of reaction regulator solution, thereby obtain a kind of cobalt (Co that contains
2+), manganese (Mn
2+), bromine (Br
-) at least two kinds high activity homogeneous phase aqueous solution composition.
Introduce the present invention below in detail:
The present invention adds at least a and hydrobromic acid aqueous solution of cobalt, cobalt compound, manganese, manganese compound directly or carry out prepared in reaction under at least a existence condition contain cobalt (Co in acetic acid, hydrogen peroxide or Peracetic acid, bromine in reactor
2+), manganese (Mn
2+), bromine (Br
-) at least two kinds homogeneous phase aqueous solution method for compositions.Wherein cobalt or cobalt compound or manganese or manganese compound and hydrobromic mol ratio are 1:0.1～5.0; The mol ratio of cobalt or cobalt compound or manganese or manganese compound and acetic acid is 1:0.1～1.0; The mol ratio of cobalt or cobalt compound or manganese or manganese compound and hydrogen peroxide or Peracetic acid or bromine is 1:0.005～0.1, and reaction temperature is controlled at 20～130 ℃.
Preparation of compositions method of the present invention, hydrobromic acid concentration is 2～48%, when using metallic cobalt or manganese metal as raw material, minimum amount is higher than metallic cobalt with liquid level or manganese metal is a benchmark, when hydrobromic acid concentration less than 2% the time, cobaltous bromide or manganous bromide concentration are low excessively in the product, need to increase energy consumption and carry out concentration; When hydrobromic acid concentration was higher than 48%, hydrobromic acid needed special preparation, thus the present invention to select hydrobromic acid concentration be 2～48%.
Preparation of compositions method of the present invention, cobalt or manganese and hydrobromic mol ratio generally are controlled at 1:0.1～5.0; When the mol ratio of metallic cobalt or manganese during less than 1:0.1, productive rate is low excessively in the unit interval; When cobalt or manganese and hydrobromic mol ratio during greater than 1:5.0, the increase of hydrobromic acid consumption does not have obvious influence to the reaction time, and free hydrobromic acid content is also too high in the product, meet the easy oxidation of air and separate out free bromine, so the present invention to select cobalt or manganese and hydrobromic mol ratio be 1:0.1～5.0.
Preparation of compositions method of the present invention, cobalt compound or manganese compound and hydrobromic mol ratio generally are controlled at 1:2.0～2.2; During less than 1:2.0, cobalt compound or manganese compound reaction are incomplete, filtration difficulty; When cobalt or cobalt compound or manganese or manganese compound and hydrobromic mol ratio during greater than 1:2.2, free hydrobromic acid too high levels in the product, increase and remove the difficulty of bringing impurity in the raw material, product can not be directly as the catalyst on PTA or the TMA device, so the present invention to select cobalt compound or manganese compound and hydrobromic mol ratio be to prepare compositions in 1:2.0～2.2 scopes.
Preparation of compositions method of the present invention, by using the speed of acetic acid control cobalt or cobalt compound or manganese or manganese compound and hydrobromic acid reaction, prevent the too fast and heat accumulation of reaction speed, regulate the ratio of cobalt in the composition, manganese, bromide ion simultaneously, the mol ratio of cobalt or cobalt compound or manganese or manganese compound and acetic acid is generally in 1:0.1～1.0, when mol ratio is lower than 1:0.1, acetic acid does not have the effect of three kinds of ion ratios in reaction speed and the composition, but when mol ratio during greater than 1:1.0, the acetic acid consumption increases not remarkable to the influence of reaction speed.
Preparation of compositions method of the present invention, by adding hydrogen peroxide or Peracetic acid or bromine, the iron that raw material can be brought into changes the iron ion of 3 valence states into, thereby the pH value by regulator solution removes de-iron, and wherein the mol ratio of cobalt or cobalt compound or manganese or manganese compound and hydrogen peroxide or Peracetic acid or bromine is respectively 1:0.005～0.1.
Preparation of compositions method of the present invention can be used cylindricality or tower reactor or tank reactor, by heating and condensing unit on the conditioned reaction device, makes reaction temperature remain on 20～130 ℃.When temperature of reactor was lower than 20 ℃, reaction speed was slow, reaction is incomplete, and cobalt or cobalt compound or manganese or manganese compound conversion ratio are low; When temperature is higher than 130 ℃, need the reaction system pressurization, and reaction is very violent, control gas is discharged difficulty to be increased, and the bromide spill-out also significantly increases, and equipment corrosion is serious, the technical process instability, so the present invention controls reaction temperature in 20～130 ℃ of scopes.
Preparation of compositions method of the present invention, what obtain contains cobalt (Co
2+), manganese (Mn
2+), bromine (Br
-) at least two kinds homogeneous composition promptly present liquid condition at normal temperatures, when preparing the catalyst of terephthalic acid (TPA) or prepare the catalyst of trimellitic anhydride by inclined to one side triphen oxidation, oxidation do not need heating for dissolving being used to allocate by paraxylene, can directly mix with acetic acid or aqueous acetic acid by pumping, simple to operate.
The specific embodiment
Further specify the present invention below by embodiment:
Embodiment 1:
At volume is in the reactor of 500ml, add 30g technical grade manganese metal, with 180g concentration is that 48% hydrobromic acid adds in the reactor, by regulating hydrobromic flow velocity, heating and condensing unit on the reactor, make reaction temperature remain on 95 ± 5 ℃, treat that the solution pH value reaches at 4～6 o'clock, reaction time needs 30min approximately, add 20g technical grade metallic cobalt again, 115g hydrobromic acid and 2.0g bromine, the control reaction temperature is at 130 ± 5 ℃, treat that the solution pH value reaches at 4～6 o'clock, filter that filtrate is regulated pH value less than 4 with hydrobromic acid aqueous solution, promptly obtain containing cobalt, manganese, the homogeneous composition of bromine, wherein cobalt content is 5.71%, manganese content is 8.57%, bromine content is 41.1%, and impurity content meets PTA catalyst required standard, and the remaining solid thing recycles in the reactor.
Embodiment 2:
At volume is in the reactor of 500ml, adding 200g technical grade metallic cobalt and 115g concentration are 48% hydrobromic acid, iron content is 1200 μ g/g in the cobalt, heating and condensing unit on the conditioned reaction device, make reactant liquor boiling circulating reflux, treat that the solution pH value reaches at 4～6 o'clock, the hydrogen peroxide that adds 2.0g27.5%, continued to add thermal response 15 minutes, and filtered, filtrate is regulated pH value less than 4 with hydrobromic acid aqueous solution, promptly obtain containing the homogeneous composition of cobalt and bromine, wherein cobalt content is 14.2%, bromine content is 41.5%, and impurity content meets PTA catalyst required standard, and remaining metallic cobalt recycles in the reactor.
Embodiment 3:
At volume is in the reactor of 500ml, adding 20g technical grade metallic cobalt and 285g concentration are 48% hydrobromic acid, by heating and condensing unit on the conditioned reaction device, make reactant liquor keep the boiling circulating reflux, after treating that the technical grade metallic cobalt dissolves fully, add 40g manganese carbonate (manganese content is 46%) and 12g manganese metal in batches, treat that the solution pH value reaches at 4～6 o'clock, filter, and regulate the filtrate pH value less than 4 with hydrobromic acid aqueous solution, promptly obtain containing cobalt, manganese, the homogeneous composition of bromine, wherein cobalt content is 5.7%, manganese content 8.0%, bromine content is 39.7%, and impurity content meets PTA catalyst required standard.Remaining manganese metal recycles in the reactor.
Embodiment 4:
At volume is in the reactor of 500ml, add 27.5g technical grade manganese metal, with 150g concentration is that 48% hydrobromic acid and 30g acetic acid add in the reactor, by regulating the flow velocity of hydrobromic acid and acetic acid, the control reaction temperature remains on 50 ± 5 ℃, after adding hydrobromic acid and acetic acid, in reaction system, add the 8g bromine, continue 30min, add 30g technical grade metallic cobalt again, the 150g hydrobromic acid, intensification and control reaction temperature treat that at 125 ± 5 ℃ the solution pH value reaches at 4～6 o'clock, standing sedimentation, filter and regulate the filtrate pH value less than 4, promptly obtain containing cobalt with hydrobromic acid, manganese, the homogeneous composition of bromine, wherein cobalt content is 7.5%, manganese content is 6.9%, bromine content is 38.4%, impurity content meets PTA catalyst required standard, and remaining solids recycles in the reactor.
Embodiment 5:
At volume is in the reactor of 500ml, add 60g technical grade manganese carbonate (manganese content is 46%), 66g technical grade cobalt carbonate (cobalt content is 45%) and 350g concentration are that 48% hydrobromic acid adds in the reactor, by regulating hydrobromic flow velocity, heating and condensing unit on the reactor, make reaction temperature remain on 25 ± 5 ℃, when bubble not had occurs, add the 3g manganese metal, and rising temperature to 105 ± 5 ℃ and keeping more than the 15min, filter, add hydrobromic acid in the filtrate and regulate the filtrate pH value less than 4, promptly obtain containing cobalt, manganese, the homogeneous composition of bromine, wherein cobalt content is 6.8%, manganese content is 6.9%, bromine content is 39.6%, and impurity content meets PTA catalyst required standard.
Embodiment 6:
At volume is in the reactor of 500ml, add 50g manganese dioxide (manganese content is 49%) and 31g manganese metal, with 350g concentration is that 48% hydrobromic acid adds in the reactor, by heating and condensing unit on the conditioned reaction device, make reaction temperature remain on 80 ± 5 ℃, interval sampling and measuring manganese ion content, when content is basicly stable, isolated by filtration, add 3g manganese metal and the temperature to 105 that raises ± 5 ℃ in the filtrate and keep more than the 15min, treat that the solution pH value reaches at 4～6 o'clock, slowly adds the 1g Peracetic acid, leave standstill 15min, filter, add hydrobromic acid in the filtrate and regulate the filtrate pH value, promptly obtain containing manganese less than 4, the homogeneous composition of bromine, wherein manganese content 13.9%, bromine content is 41.1%, and impurity content meets PTA catalyst required standard.
Embodiment 7:
At volume is in the reactor of 500ml, add 56g technical grade manganese metal, with 335g concentration is that 48% hydrobromic acid adds in the reactor, by regulating heating and condensing unit on hydrobromic flow velocity, the reactor, make reaction temperature remain on 60 ± 5 ℃, treat that the solution pH value reaches at 4～6 o'clock, filter, add hydrobromic acid aqueous solution in the filtrate and regulate the filtrate pH value less than 4, promptly obtain containing the homogeneous composition of manganese, bromine, wherein manganese content is 12.8%, bromine content is 37.3%, and impurity content meets PTA catalyst required standard.
Embodiment 8:
The hydrobromic acid 200g that in the cylindricality of total measurement (volume) 0.4L or tower reactor, adds 500g metallic cobalt and 2%, by heater on the conditioned reaction device, make reactant liquor keep 100 ± 5 ℃, treat that the solution pH value reaches at 4～6 o'clock, filter, add hydrobromic acid in the filtrate and regulate the filtrate pH value, promptly obtain containing the homogeneous composition of cobalt, bromine less than 4, wherein cobalt content is 0.69%, bromine content is 4.2%, and impurity content meets PTA catalyst required standard.
Embodiment 9:
At volume is in the reactor of 500ml, add 40g cobalt hydroxide (cobalt content is 63.4%), 30g manganous hydroxide (manganese content is 61.8%) and 15g manganese metal, with 340g concentration is that 48% hydrobromic acid adds in the reactor, by regulating hydrobromic flow velocity, heating and condensing unit on the reactor, make reaction temperature remain on 95 ± 5 ℃, treat that the solution pH value reaches at 4～6 o'clock, filter, add hydrobromic acid aqueous solution in the filtrate and regulate the filtrate pH value less than 4, promptly obtain containing the homogeneous composition of cobalt and bromine, wherein cobalt content is 5.9%, manganese content 7.2%, bromine content is 36.8%, and impurity content meets PTA catalyst required standard.
Embodiment 10:
At volume is in the reactor of 500ml, add the 25g cobalt oxide and (contain cobalt black and cobalt sesquioxide, cobalt content is 72%), 50g cobalt carbonate (cobalt content is 45%) and 22g metallic cobalt, with 340g concentration is that 48% hydrobromic acid adds in the reactor, by regulating hydrobromic flow velocity, heating and condensing unit on the reactor, make reaction temperature rise to 110 ± 5 ℃, too fast and the gas of preventing from the temperature-rise period to heat up is taken hydrobromic acid out of, treat that the solution pH value reaches at 4～6 o'clock, standing sedimentation, clear liquid filters, add hydrobromic acid aqueous solution in the filtrate and regulate the filtrate pH value less than 4, promptly obtain containing the homogeneous composition of cobalt and bromine, wherein cobalt content is 13.6%, bromine content is 36.9%, impurity content meets PTA catalyst required standard, and remaining solids recycles in the reactor.
Embodiment 11:
At volume is the hydrobromic acid 40kg that adds 100kg metallic cobalt and 48% in the reactor of 100L, by heater on the conditioned reaction device, make reactant liquor keep 125 ± 5 ℃, treat that the solution pH value reaches at 4～6 o'clock, filter, add hydrobromic acid aqueous solution in the filtrate and regulate the filtrate pH value less than 4, promptly obtain containing the homogeneous composition of cobalt, bromine, wherein cobalt content is 13.5%, and bromine content is 36.7%, impurity content meets PTA catalyst required standard, and remaining metallic cobalt recycles in the reactor.
Embodiment 12:
At volume is in the reactor of 100L, add 10.4kg technical grade electrolytic manganese, with 40kg concentration is that 48% hydrobromic acid and 8kg glacial acetic acid mixed liquor add in the reactor, by regulating the flow velocity of mixed liquor, heating and condensing unit on the reactor, make reaction temperature remain on 90 ± 5 ℃, treat that the solution pH value reaches at 4～6 o'clock, filter, add hydrobromic acid aqueous solution in the filtrate and regulate the filtrate pH value less than 4, promptly obtain containing manganese, the binary homogeneous composition of bromine, wherein manganese content is 12.8%, bromine content is 23.9%, impurity content meets PTA catalyst required standard, and remaining manganese is reused in the reactor.Get that present embodiment composition 39kg mixes with embodiment 11 composition 29.6kg and water transfers to that 100kg promptly obtains containing cobalt 4.0%, contains manganese 5.0%, brominated 20.2% ternary composition.
Use symbol description among the present invention:
%: mass percent; G: gram; Kg: kilogram; Min: minute; Ml: milliliter; L: rise.
The stoichiometric equation of chemical reaction that relates among the present invention is:
(1)Co(S)+2HBr(L)＝CoBr
2(L)
(2)Mn(S)+2HBr(L)＝MnBr
2(L)
(3)CoCO
3(S)+2HBr(L)＝CoBr
2(L)+H
2O(L)+CO
2(g)
(4)MnCO
3(S)+2HBr(L)＝MnBr
2(L)+H
2O(L)+CO
2(g)
(5)MnO
2(S)+Mn(S)+4HBr(L)＝2MnBr
2(L)+2H
2O(L)
(6)Co
2O
3(S)+Co(S)+6HBr(L)＝3CoBr
2(L)+3H
2O(L)
(7)2Fe
2++Br
2(L)＝2Fe
3++2Br
-(L)
(8)2Fe
2++H
2O
2(L)＝2Fe
3++2OH
-
(9)Fe
2++CH
3COOOH(L)＝Fe
3++OH
-+CH
3COO
-
(S) represents solid in the equation bracket; (L) represent liquid; (g) represent gas.
The measured value of impurity content is lower than the reduced value that calculates according to crystal cobalt acetate, crystal manganese acetate, cobaltous bromide, manganous bromide product standard regulation in the present composition.The mensuration of cobalt, manganese, bromine adopts titration among the present invention, and metal impurities adopt atomic absorption method, chloride and sulfate to adopt colorimetric method.
Claims (4)
1. one kind contains Br and Co
2+, Mn
2+In the preparation method of at least a homogeneous composition, it is characterized in that in reactor, adding cobalt, cobalt compound, manganese, at least a and hydrobromic acid aqueous solution in the manganese compound is directly or at acetic acid, hydrogen peroxide or Peracetic acid, carry out prepared in reaction in the bromine under at least a existence condition, wherein cobalt compound is a cobalt carbonate, cobalt hydroxide, cobalt oxide, cobalt sesquioxide, manganese compound is a manganese carbonate, manganous hydroxide, manganese dioxide, cobalt or cobalt compound or manganese or manganese compound and hydrobromic mol ratio are 1:1.5～5.0, with the mol ratio of acetic acid be 1:0.1～1.0, with the mol ratio of hydrogen peroxide or Peracetic acid or bromine be 1:0.005～0.1, reaction temperature is 20～130 ℃, said composition directly or and cobalt acetate, manganese acetate, hydrobromic acid, tetrabromoethane, acetic acid, at least a in the water is mixed for allocating by paraxylene and prepares the catalyst of terephthalic acid (TPA) or prepared the catalyst of trimellitic anhydride by inclined to one side triphen through oxidation.
2. the preparation method of homogeneous composition according to claim 1 is characterized in that reactor is tank reactor or tower or cylindricality reactor.
3. the preparation method of homogeneous composition according to claim 1 is characterized in that composition is to concentrate on to prepare in the same reactor or prepare respectively, mixes then in different reactors.
4. the preparation method of homogeneous composition according to claim 1 when it is characterized in that using the reaction of cobalt compound or manganese compound and hydrobromic acid, adds metallic cobalt or manganese metal.
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| 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 |
| 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 |
| CN107744820B (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 composite aqueous solution by utilizing recovered cobalt and manganese |
| CN114906879A (en) * | 2022-04-29 | 2022-08-16 | 海南昂扬科技有限公司 | Production process of cobalt bromide solution |
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| GB1603393A (en) * | 1978-05-25 | 1981-11-25 | Asahi Chemical Ind | Process for the production of a high purity terephthalic acid |
| CN1036948A (en) * | 1988-03-29 | 1989-11-08 | 阿莫科公司 | The used group VIII noble metals reactivation of catalyst of purified terephthalic crude product method |
| CN1128254A (en) * | 1995-06-20 | 1996-08-07 | 济南化纤研究院 | Preparation method of cobalt acetate |
| CN1417193A (en) * | 2001-11-06 | 2003-05-14 | 黑龙江省石油化学研究院 | Liquid phase catalytic mesitylene air oxidizing process of preparing benzenetricarboxylic acid |
| US20060004223A1 (en) * | 2004-06-30 | 2006-01-05 | General Electric Company | Method of making halophthalic acids and halophthalic anhydrides |
-
2006
- 2006-09-22 CN CNB2006100690197A patent/CN100462144C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1603393A (en) * | 1978-05-25 | 1981-11-25 | Asahi Chemical Ind | Process for the production of a high purity terephthalic acid |
| CN1036948A (en) * | 1988-03-29 | 1989-11-08 | 阿莫科公司 | The used group VIII noble metals reactivation of catalyst of purified terephthalic crude product method |
| CN1128254A (en) * | 1995-06-20 | 1996-08-07 | 济南化纤研究院 | Preparation method of cobalt acetate |
| CN1417193A (en) * | 2001-11-06 | 2003-05-14 | 黑龙江省石油化学研究院 | Liquid phase catalytic mesitylene air oxidizing process of preparing benzenetricarboxylic acid |
| US20060004223A1 (en) * | 2004-06-30 | 2006-01-05 | General Electric Company | Method of making halophthalic acids and halophthalic anhydrides |
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