CN100344379C - Catalyst solution for preparing terephthalic acid and preparation method thereof - Google Patents
Catalyst solution for preparing terephthalic acid and preparation method thereof Download PDFInfo
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- CN100344379C CN100344379C CNB2004100053363A CN200410005336A CN100344379C CN 100344379 C CN100344379 C CN 100344379C CN B2004100053363 A CNB2004100053363 A CN B2004100053363A CN 200410005336 A CN200410005336 A CN 200410005336A CN 100344379 C CN100344379 C CN 100344379C
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- terephthalic acid
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Abstract
The present invention proposes a catalyst solution system for preparing terephthalic acid, which comprises a Co, Mn and Br catalyst solution (CMB) and a Co and Br catalyst solution. The catalyst solution system is characterized in that when the catalyst solution system is used in oxidation reaction, and the weight percentage of Br/Mn in the CMB is greater than 2.909, or only Co and Br are used as catalyst main components, the present high-corrosiveness CoAc2 and HBr are replaced by adding CoBr2 as a source of the Co and the Br. The present invention proposes a catalyst preparation method by matching a preparation method of terephthalic acid, which has the step that the catalyst solution system is used in oxidation reaction under the stir of the terephthalic acid and oxygen containing gas. The catalyst for preparing the terephthalic acid can improve the corrosiveness of the traditional catalyst to PTA production equipment.
Description
Technical field
The present invention is relevant a kind of catalyst solution system and use preparation method each other who is used for the preparation of terephthalic acid (TPA).
Background technology
Terephthalic acid (TPA) (Purifled Terephthalic Acid, PTA) by extensively as various industrial production raw materials, is example to produce clothing with polyester fiber (Polyester), its primary raw material PETG (Polyethyleneterephthalate, PET), the main mode of producing at general industry is promptly carried out esterification and polycondensation reaction generation PET with terephthalic acid (TPA) (PTA) and ethylene glycol (EG).
Terephthalic acid (TPA) be with paraxylene (Para-xylene, PX) and O
2Chemical reaction is made, because the state of atom in the oxygen molecule is to be in triple spin states, can't produce reciprocation with the hydrocarbon atom on hydrocarbon compound (CPX) molecule of the single spin states of tool, carry out the oxidation reaction of chemistry, so in its production process, must be by comprising at least a acetate (Co that do not contain, Mn, Cr, Ni, Cu etc. are main) heavy metal compound, cross plating and solvent acetic acid forms wrong salt, and the wrong salt of these metals just makes metal ion be absorbed oxygen molecule because of the adhesion of coordination misfit field, become the oxidation reaction that open beginning reacted paraxylene of the single spin states of easily reaction and change its ground state through catalysis, it is a kind of spontaneous oxidation reaction, that is as long as opening beginning reaction and just can producing enough number of free radical of transition metal impels the amplitude of PX oxidation reaction constantly to enlarge.But the transition cobalt metal itself through opening the beginning reaction also is oxidized to 3 valency cobalts, under higher PX oxidizing reaction temperature, very easily carry out the decarboxylation reaction with acetic acid and PTA, and form products such as carbon dioxide, methyl acetate, trihemellitic acid and benzoic acid, phenols, biphenyl respectively, cause the problem of cost of material and quality.Owing to open the required trivalent cobalt ions of beginning reaction and do not require too high concentration, but, make Co if it is to utilize a kind of stable dentate and the misfit of trivalent cobalt that its accumulation too much just impels above-mentioned problem, the mode of improvement
+ 3Life cycle in acetic acid reduces to the shortest, combines with cobalt salt and the bromide that works out is the easiest, and reaches follow-up requirement.And via utilizing the acetate concentration that is adopted to control the selection rate (Partenheimer et al.US No.5,081,290) of oxidizing reaction rate and oxidation reaction.Development is typically and utilizes cobalt (Co), manganese (Mn), the isoionic catalytic action of bromine (Br) so far, makes its reaction rate and product quality all reach optimal conditions.
Early stage PTA oxidation catalyst is to take from solid-state cobalt compound, solid-state manganese compound and liquid bromine compound to add mixing preparation respectively and become the required concentration of PTA processing procedure.
Because the easy deliquescence caking of solid-state cobalt acetate and manganese acetate, be not easy very much in the storage, and the PTA manufacturer must consume manpower and prepare the compound and the dissolving of liquid bromic acid of solid-state cobalt and manganese man-hour, very inconvenient, therefore change gradually with cobalt acetate solution, manganese acetate solution and directly mix acetate solution (Cobalt, the Manganese Acetate in Solution that is made into cobalt manganese, CMA), hand over the PTA manufacturer to use, make the PTA manufacturer can save operation and costs such as crystallization, separation, the universe are dry, packing.When using this type of cobalt manganese acetate solution (CMA), the PTA manufacturer only need look the HBr that the production demand adds appropriate amount, and required bromine (Br) gets final product in the catalytic action to replenish.
But HBr is except that being the strong acid and containing free molecular bromine (Free Bromine) to have high risk, and no matter the PTA manufacturer stores or use the puzzlement that all causes easily on environmental protection, the industry security.And the interpolation of HBr also need consume manpower.Therefore further HBr is added cobalt manganese bromate solution (CMA) again, this is the cobalt manganese bromine catalyst solution that is widely used most in recent years, and (BrominatedCobalt Manganese Acetate in Solution is called Co.Mr.Br catalyst solution, CMB).
But the Br major part that is used in the PTA processing procedure oxidation catalyst is taken from HBr, and this HBr contains the free acid (Free Acid) and the free bromine (Free Bromine) of a great deal of.No matter it stores or during operation, all causes great negative effect for PTA factory hardware, comprises the corrosion phenomenon that causes hardware, situation more serious in addition can cause the environmental protection worker to pacify incident.
For solving this kind puzzlement, the inventor attempts to originate with different Br in R﹠D process and finds out the minimum prescription of corrosion.Using MnBr
2After substituting HBr, after testing, really can reduce corrosivity.MnBr
2The source of Mn also is provided simultaneously.But in the catalyst prescription,, all must add HBr again to mend the deficiency of Br if the ratio of Mn/Br is lower than at 1/2.9 o'clock.But so cause CMB corrosivity significantly to promote.
Summary of the invention
Purpose of the present invention is promptly providing a kind of cobalt, manganese, bromine catalyst solution (CMB) preparation method of terephthalic acid utilized, and it can effectively reduce the corrosivity of CMB, stores and processing safety and production quality to promote PTA factory.
For reaching above-mentioned purpose, the present invention proposes a kind of catalyst solution system that is used for the preparation of terephthalic acid (TPA), and it comprises Co, Mn, Br acetum (CMB), it is characterized in that being used in the reaction, in ratio＞2.909 of Br/Mn percentage by weight o'clock, inserts CoBr
2The source of making Co, Br is to replace the HBr of highly corrosive.
The present invention cooperates a kind of terephthalic acid (TPA) preparation method, and it is in paraxylene and the stirring reaction of gas that comprises oxygen, uses above-mentioned catalyst solution system.
For reaching above-mentioned purpose, in a part, the present invention proposes a kind of catalyst solution system that is used for the preparation of terephthalic acid (TPA), and it comprises Co, Mn, Br acetum (CMB) and CoBr
2, it is characterized in that being used in the reaction, in ratio＞2.909 of Br/Mn percentage by weight o'clock, insert CoBr
2And do not need the HBr of highly corrosive.
As mentioned above, the present invention proposes a kind of catalyst solution system that is used for the terephthalic acid (TPA) preparation, and it comprises Co, Mn, Br acetum (CMB) and CoBr
2, wherein be directly to mix with manganous bromide and cobaltous bromide solution to be made into Co, Mn, Br catalyst solution (CMB), it is characterized in that being used in the terephthalic acid (TPA) preparation feedback, when need add the HBr source, be no more than under the cooperation concentration of Co, Mn, so with CoBr
2, MnBr
2Preparation, and then stop using height to lose the HBr of property.
A kind of terephthalic acid (TPA) preparation method is proposed in another part of the present invention, it is to use the above catalyst solution system in right-dimethylbenzene and the stirring reaction of gas that comprises oxygen, wherein be as catalyst with Co, Mn, Br acetum (CMB), and it is characterized in that in this reaction, in ratio＞2.909 of Br/Mn percentage by weight o'clock, insert CoBr
2And do not need the HBr of highly corrosive.
Characteristics of the present invention, technology contents and the effect that can reach will cooperate following chart to be described in detail, as shown in the figure:
Description of drawings
Fig. 1 is the corrosivity comparison sheet (static state) of CMB solution of the present invention and other CMB solution.
The specific embodiment
It is to implement with the technology of knowing in the skill that the present invention utilizes cobalt, manganese, bromine catalyst solution system (CMB) preparation method of terephthalic acid, for example above-cited US No.5,081,290.Its available for example continous way, semi continuous or batch formula are carried out.In with initiation material, that is PX, after importing in the reactor with solvent and catalyst system capable, the content of reactor is heated to about 150 to the 205 ℃ temperature of preferably, import oxygenous gas, for example air or purity oxygen, along with the carrying out of exothermicity oxidation reaction, temperature can rise to about 170 to 270 ℃ steady temperature.Be via measuring the progress that oxygen absorbs monitoring reaction in reaction is carried out.Stop in oxygen picked-up, that is when contained oxygen concentration increased fast from the steam admixture of gas that reactor extracts, the manufacturing reaction of PTA was fully.Can isolate with centrifugal process or filtration method then this moment with reactant as for being cooled to about 35 ℃ to 120 ℃ temperature in the partial crystallization device.
In above-mentioned preparation process, the metal that organic impurities that produces because of side reaction and equipment corrosion get off is accumulated in mother liquor gradually, must quantitatively discharge one to control its concentration, adds top Br with Br
2, CH
3The gas of Br discharges with reactor off-gas, Part of Co, Mn also flow out with the product of giving birth to powder in addition, thus must constantly mend into fresh CMB solution, to keep the required concentration of reaction, the prescription of the required CMB of each PTA processing procedure, then the degree that runs off according to Co, Mn, Br is allocated.
The present invention will give specifically at length illustrating with the following examples, but the present invention is not limited by it.
Embodiment
The preparation of catalyst
Directly mix the acetate solution that is made into cobalt manganese with cobalt acetate solution, manganese acetate solution, MnBr is gone in allotment
2To substitute HBr, in this prescription, if the MB/Br ratio is lower than 1/2.9, then at cobalt: manganese: bromine (Co:Mn:Br) is A:B:C, during (1) BX2.9＜C, promptly adds CoBr
2So that the Br of AX2.7 to be provided.The amount of then required Co, Mn can be by MnBr
2And CoBr
2Add the etching problem that significantly reduces HBr and followed.(2) AX2.7+BX2.9＞C, then the source of Br can be fully by MnBr
2With CoBr
2Provide, and not enough Co is then provided by cobalt acetate.
The preparation of PTA
Utilize reaction technology mentioned above to prepare PTA, and the corrosivity of more different catalyst system capables, it is as shown in the table for the result.
In the variant solution testing chart as shown in Figure 1, on behalf of CMB solution, the A1 curve use 100%Br, and the A2 curve represents its Br part from MnBr
2, part is from HBr in addition, and the A3 curve is represented the present invention, and its Br is only by bromide.
By finding out in this chart, when required Br complete 100% took from HBr, this solution almost reached the top of corrosion between 14 days-21 days.When the Mn/Br ratio is lower than 1/2.9 and insert HBr to replenish Br when not enough, shown in the A2 curve, then its corrosion peak value also arrived between 14 days-28 days.
But originating as Br with bromide, shown in the A3 curve, the corrosivity of CMB solution is significantly reduced, even and reach 90 days during, its corrosivity also remains on extreme lower position.The present invention thereby can effectively improve the corrosivity of CMB promotes factory's operation and storage safe and production quality.
As implied above, cobalt, manganese, bromine as the special ratios of ratio＞2.909 of above-mentioned Br/Mn percentage by weight under, be CoBr
2The optimal situation of adding, the then visual PTA of bromide manufacturer different product processing procedure aequum is inserted, and becomes a kind of more convenient use and safe cobalt, manganese, bromine acetum.
Above illustrated embodiment only with for conveniently illustrating the present invention, not from the present invention's spirit category, is had the knack of various simple and easy the increasing and modification that the dealer of this delegation institute can do, and all must include in claim.
Claims (1)
1. the preparation method of a terephthalic acid (TPA), be right-dimethylbenzene with comprise in the gas stirring reaction of oxygen, the compound method of employed catalyst solution is: directly mix the acetate solution that is made into cobalt manganese with cobalt acetate solution, manganese acetate solution, MnBr is gone in allotment
2,, add CoBr when the amount of required Br during greater than 2.9 times of Mn
2, so that the amount of Br increases 2.7 times of amount of Co again.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100053363A CN100344379C (en) | 2004-02-11 | 2004-02-11 | Catalyst solution for preparing terephthalic acid and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100053363A CN100344379C (en) | 2004-02-11 | 2004-02-11 | Catalyst solution for preparing terephthalic acid and preparation method thereof |
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| CN1654122A CN1654122A (en) | 2005-08-17 |
| CN100344379C true CN100344379C (en) | 2007-10-24 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4051178A (en) * | 1975-06-25 | 1977-09-27 | Mitsubishi Chemical Industries Limited | Process for producing terephthalic acid |
| US4873361A (en) * | 1987-02-19 | 1989-10-10 | Amoco Corporation | Process for production of p-acetoxybenzoic acid from p-acetoxyacetophenone |
| 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 |
| US5081290A (en) * | 1990-06-21 | 1992-01-14 | Amoco Corporation | Process for making aromatic polycarboxylic acids and oxidation catalyst system |
| CN1084845A (en) * | 1992-05-21 | 1994-04-06 | 帝国化学工业公司 | Bromine catalysed oxidation processes |
| CN1334792A (en) * | 1999-04-28 | 2002-02-06 | 三星综合化学株式会社 | Method for production of aromatic carboxylic acids |
-
2004
- 2004-02-11 CN CNB2004100053363A patent/CN100344379C/en not_active Ceased
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4051178A (en) * | 1975-06-25 | 1977-09-27 | Mitsubishi Chemical Industries Limited | Process for producing terephthalic acid |
| US4873361A (en) * | 1987-02-19 | 1989-10-10 | Amoco Corporation | Process for production of p-acetoxybenzoic acid from p-acetoxyacetophenone |
| 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 |
| US5081290A (en) * | 1990-06-21 | 1992-01-14 | Amoco Corporation | Process for making aromatic polycarboxylic acids and oxidation catalyst system |
| CN1084845A (en) * | 1992-05-21 | 1994-04-06 | 帝国化学工业公司 | Bromine catalysed oxidation processes |
| CN1334792A (en) * | 1999-04-28 | 2002-02-06 | 三星综合化学株式会社 | Method for production of aromatic carboxylic acids |
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| Publication number | Publication date |
|---|---|
| CN1654122A (en) | 2005-08-17 |
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