CN1510023A - Process for primary refining coarse p-phthalic acid by solvent washing process - Google Patents
Process for primary refining coarse p-phthalic acid by solvent washing process Download PDFInfo
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- CN1510023A CN1510023A CNA021585571A CN02158557A CN1510023A CN 1510023 A CN1510023 A CN 1510023A CN A021585571 A CNA021585571 A CN A021585571A CN 02158557 A CN02158557 A CN 02158557A CN 1510023 A CN1510023 A CN 1510023A
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- terephthalic acid
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Abstract
A process for primarily refining coarse terephthalic acid (CTA) by solvent washing method includes such steps as using the mixture of p-xylene (PX), water and acetic acid to wash the acetic acid contained terephthalic acid slurry generated by the oxidizing reactor for preparing terephthalic acid by oxidizing PX, solid-liquid separating to obtain CTA crystal containing acetic acid and catalyst, washing with water, mixing with water, and hydrorefining.
Description
Technical field
The process for purification that the invention belongs to terephthalic acid relates to a kind of method of solvent wash method primary purification crude terephthalic acid.
Background technology
The production method of terephthalic acid normally p-Xylol (PX) in the presence of the catalyzer that contains cobalt, manganese and bromine etc., is reacted with molecular oxygen in acetate.From the acetate slurry of reaction product terephthalic acid isolated crude terephthalic acid through hydrofining with remove wherein carboxyl benzaldehyde (4-CBA) is obtained the pure terephthalic acid.Crude terephthalic acid (PTA) before the hydrofining must be through thorough drying to remove wherein remaining acetate.Drying plant cost height in the drying process in this method, and auxiliary facility is many, complicated operation.
Around how omitting drying program, several solutions had been proposed once.Mainly be with the acetate in the water displacement terephthalic acid slurry.With water countercurrent washing terephthalic acid slurry, terephthalic acid slurry enters in the tower from tower top in a multistage tower in U.S. Patent No. 5008450 propositions, and water imports from the bottom.U.S. Patent No. 5200557, European patent are openly reported No. 502628 etc. and also to be proposed to be imported into terephthalic acid slurry in transition band or the filter vat with the water countercurrent washing.Though these methods have been omitted drying step, can produce the mixture of big water gaging and acetate simultaneously, increase separation costs.Chinese patent CN1129693A proposes earlier with p-Xylol washing terephthalic acid slurry, after solid-liquid separation, again with the water washing filter cake.Though this method has reduced the washing water consumption, also successfully saved drying process simultaneously, catalyzer index residual in the CTA slurry as the charging of PTA operation is too high, has influenced hydrofining.
Summary of the invention
The method that the purpose of this invention is to provide a kind of solvent wash method primary purification crude terephthalic acid, it is the mixed solvent of using by p-Xylol (PX), water and acetate configuration, and washing is by the acetate slurry of the terephthalic acid of the PX oxidation system para-phthalic acid (pta) oxidation reactor institute output CTA crystalline method that contains acetate and catalyzer through the solid-liquid separation gained.Can successfully save drying process, can reduce the generation of water and acetate mixture again as far as possible, can also guarantee residual qualified the improving one's methods of catalyzer index in the thick TA slurry as the charging of crude terephthalic acid (PTA) operation simultaneously.
Technical scheme content of the present invention is: following sets forth in detail the present invention.
A kind of method of solvent wash method primary purification crude terephthalic acid, it is characterized in that: use the mixed solvent by p-Xylol, water and acetate configuration, washing is by the crude terephthalic acid crystallization that contains acetate and catalyzer through the solid-liquid separation gained of the acetate slurry of the terephthalic acid of p xylene oxidation system para-phthalic acid (pta) oxidation reactor institute output.
Crystallization after the washing directly mixes with water, as the hydrorefined charging of pure terephthalic acid, no longer needs to remove through the crude terephthalic acid drying process of acetate.
Use the crude terephthalic acid crystallization that contains acetate and catalyzer by the mixed solvent making beating washing of p-Xylol, water and acetate preparation, used mixed solvent is by p-Xylol: 10-95%, water: 10-90%, acetate: 0-80% is formulated, and changes with crude terephthalic acid crystalline moisture percentage and to adjust.
Use the crude terephthalic acid crystallization that contains acetate and catalyzer by the mixed solvent displacement washing of p-Xylol, water and acetate preparation, used mixed solvent is by p-Xylol: 10-95%, water: 10-90%, acetate: 0-80% is formulated, and changes with crude terephthalic acid crystalline moisture percentage and to adjust.
To be mixed to proper concn with water then and deliver to pure terephthalic acid's device by the washed terephthalic acid crystals water of the mixed solvent displacement washing of p-Xylol, water and acetate preparation.
To be mixed to proper concn with water then and deliver to pure terephthalic acid's device by the washed terephthalic acid crystals water making beating of the mixed solvent washing of p-Xylol, water and acetate preparation.
The washed mother liquor of mixed solvent is after phase-splitting is handled, and the upper strata p-Xylol has the part Returning reacting system mutually at least, and lower floor's water has the solvent of a part as the preparation catalyzer at least.
Mixed solvent that is used to wash and water can also be divided into two portions to be used, and a part is used for displacement washing, and another part is used for the making beating washing.The acetate slurry of the terephthalic acid of crude terephthalic acid device p xylene oxidation reactor output can be earlier with acetate or acetic acid water solution making beating washing through the crude terephthalic acid crystallization that contains acetate and catalyzer of solid-liquid separation gained, wash through mixed solvent again, thereby further reduce as Co, Mn catalyst residue amount in the thick TA slurry of PCA operation charging, reduce Co, Mn catalyst consumption.
The method of solvent wash method primary purification crude terephthalic acid provided by the invention has the following advantages:
1. drying process of improving one's methods when having saved primary purification CTA provided by the invention has reduced equipment manufacturing cost, has simplified operation.
2. can significantly reduce the consumption of acetic acid with provided by the invention improving one's methods.
3. reduce the generation of aqueous acetic acid, promptly reduced the separation costs of water and acetic acid.
4. guarantee that catalyzer index residual in the thick TA slurry as the charging of PTA operation is qualified.
5. there is not the waste water and dregs discharging
Specific embodiment:
Below illustrate the present invention so that embodiment is more detailed.
P-Xylol in the presence of catalyzer, carries out oxidizing reaction with molecular oxygen in acetic acid solvent, oxidation reactor product is the acetate slurry of terephthalic acid.After this slurry carried out solid-liquid separation, obtain the crude terephthalic acid crystallization, still contain a considerable amount of solvent acetic acid and catalyzer in this crystallization, these two must be removed, otherwise will have a strong impact on later hydrogenation operation.
In the present invention, with the above crude terephthalic acid crystallization that from the acetate slurry of terephthalic acid, obtains through solid-liquid separation, at first use mixed solvent washing by p-Xylol (PX), water and acetate configuration, in this mixed solvent, the ratio of PX, water and acetate changes and corresponding adjustment with crude terephthalic acid crystalline moisture percentage.Its amplitude of fluctuating is PX10～95%, water 10～90%, acetate 0～80%.This washing process is usually between room temperature to 100 ℃, carry out under the normal pressure.In the crude terephthalic acid crystallization that contains acetate, add above-mentioned mixed solvent, carry out solid-liquid separation after the washing.Washing methods has two kinds, and first kind is making beating washing, promptly with mixed solvent to crude terephthalic acid crystallization pull an oar, carry out solid-liquid separation after the washing.Second kind is to go up mixed solvent in the crude terephthalic acid crystallization, and the mixed solvent liquid level should be higher than the crude terephthalic acid crystal surface.Remove through pressurization or filtration under diminished pressure then and desolvate.Undesirable as the once washing effect, can repeatedly wash, be preferably 2～3 times.The amount of the mixed solvent of washing usefulness, with respect to the crude terephthalic acid crystallization, as washing with first method, then each consumption is 0.1～3 times of crude terephthalic acid crystallization weight, is preferably 0.3～1 times.Repeatedly wash as need, then each consumption is 0.1～2 times, is preferably 0.2～0.6 times., as washing with second method, then each consumption is 0.5～5 times of crude terephthalic acid crystallization weight, is preferably 1～3 times.Repeatedly wash as need, then each consumption is 0.2～3 times, is preferably 0.5～1 times.
Contain PX, water, TA, acetate, catalyzer and a small amount of byproduct of reaction in the mother liquor after the washing, after phase-splitting is handled, but upper strata PX mutually Returning reacting system continue to recycle, lower floor's water contains acetate and catalyzer, can be used for preparing the catalyst solution that the PX oxidation is used, or reclaim catalyzer wherein.
Then, above-mentioned through the washed crude terephthalic acid crystallization of mixed solvent, again with water washing, in the crude terephthalic acid crystallization, go up water, and liquid level should be higher than the crude terephthalic acid crystal surface.The limit bevelling filters with pressurization or pressure reducing mode.This washing process is usually between room temperature to 100 ℃, carry out under the normal pressure.Also can be earlier with water to the washing of pulling an oar through the washed crude terephthalic acid crystallization of mixed solvent, and then wash with water with aforesaid method.The consumption of washing water can be with reference to the consumption of mixed solvent.Washing water are recyclable to be utilized again.As for attached to a small amount of p-Xylol on the crystal of washing back, when its content is very low, can not influence later unifining process, generally control it and be lower than 5%.
To promptly can be used as the charging of hydrofining operation through the crude terephthalic acid crystal of two step washings with after water mixes by a certain percentage.
Embodiment 1
Get the slurry of PX oxidation reactor product after part acetate is removed in flash distillation, get filter cake 120 grams after the filtration, the moisture percentage of controlling this filter cake is 18～22%.With 60 gram mixed solvent making beating washings, the mixed solvent proportioning is: PX 40 grams, water 20 grams.Wash conditions is: normal pressure, 70～90 ℃.Washing back B suction filtration under 200～400mmHg vacuum tightness.With 120 gram water displacement washing gained filter cakes, promptly in the crude terephthalic acid crystallization, go up water, and the liquid level of water should be higher than the crude terephthalic acid crystal surface then.Wash conditions is: normal pressure, 70～90 ℃.Limit bevelling suction filtration.Gained filter cake and the charging that promptly can be used as the hydrofining operation after water mixes by suitable proportion.The results are shown in Table 1.
Embodiment 2～7
In embodiment 1, change the consumption of mixed solvent and water, and change mode of washing, the results are shown in Table 1.
Embodiment 8
The PX 40 that consists of that changes mixed solvent in embodiment 1 restrains, water 10 grams, acetate 10 grams, C washing in the above described manner.The results are shown in Table 2.
Table 1
| Embodiment No. | ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | ??7 |
| Mode of washing * | ??A | ??A | ??A | ??B | ??B | ??B | ??C |
| The mixed solvent consumption * | ??0.6 | ??1.0 | ??0.3 | ??0.6 | ??1.0 | ??0.3 | ??0.6 |
| Filter cake after the mixed solvent washing | Acetic acid content % | ??3.6 | ??2.4 | ??4.1 | ??3.3 | ??2.6 | ?4.0 | ?3.5 | |
| PX content % | ??3.5 | ??3.6 | ??3.5 | ??3.7 | ??3.4 | ?3.9 | ?3.8 | ||
| Cobaltous diacetate ppm | ??46.3 | ??35.2 | ??60.5 | ??55.9 | ??46.9 | ?73.8 | ?44.5 | ||
| Manganese acetate ppm | ??25.0 | ??18.5 | ??36.5 | ??37.9 | ??27.1 | ?48.7 | ?25.8 | ||
| The washing water consumption | ??1.2 | ??2.0 | ??0.6 | ??1.2 | ??2.0 | ?0.6 | ?1.2 ** | ||
| Washing back filter cake | Acetic acid content % | ??0 | ??0 | ??0.1 | ??0 | ??0 | ?0.1 | ?0 | |
| PX content % | ??0.5 | ??0.4 | ??0.7 | ??0.5 | ??0.4 | ?0.7 | ?0.3 | ||
| Cobaltous diacetate ppm | ??1.1 | ??0.8 | ??2.0 | ??1.2 | ??0.5 | ?2.3 | ?0.8 | ||
| Manganese acetate ppm | ??0 | ??0 | ??0.1 | ??0 | ??0 | ?0.1 | ?0 | ||
| Ash content ppm | ??14 | ??13 | ??20 | ??15 | ??13 | ?20 | ?14 | ||
Annotate
*: mixed solvent consumption and washing water consumption refer to the weight ratio of solvent or washing water and thick TA.
Mode of washing: A-with mixed solvent making beating washing, filters the back with the water displacement washing earlier.
B-filters the back with the water displacement washing earlier with the mixed solvent displacement washing.
C-filters the back with water making beating washing, again with the water displacement washing earlier with mixed solvent making beating washing.
*: earlier with 0.4 times of water making beating washing, again with 0.8 times of water displacement washing.
Ash content refers to the ash oontent after the filter cake oven dry.
Table 2
| The mixed solvent consumption | Mixed solvent washing back filter cake | Water consumption | Filter cake after the water washing | |||||||
| Acetate % | PX ％ | Cobaltous diacetate ppm | Manganese acetate ppm | Acetate % | PX ％ | Cobaltous diacetate ppm | Manganese acetate ppm | Ash content ppm | ||
| 0.6 | 6.9 | 3.1 | 26.1 | ??12.2 | 1.2 | 0 | 0.8 | 0.4 | 0 | ??12 |
The mixed solvent of the present invention by p-Xylol (PX), water and acetate configuration, washing is by the CTA crystallization that contains acetate and catalyzer through the solid-liquid separation gained of the acetate slurry of the terephthalic acid of PX oxidation system para-phthalic acid (pta) oxidation reactor institute output.Without operations such as the drying of terephthalic acid, storages, the acetate mixed volume is few in the final washing water, and has overcome previously presentedly with the big shortcoming of washing water consumption in the water washing CTA technology, can effectively reduce the Production of Terephthalic Acid cost.
Claims (9)
1. the method for a solvent wash method primary purification crude terephthalic acid, it is characterized in that: use the mixed solvent by p-Xylol, water and acetate configuration, washing is by the phthalic acid crystallization that contains acetate and catalyzer through the solid-liquid separation gained of the acetate slurry of the terephthalic acid of p xylene oxidation system para-phthalic acid (pta) oxidation reactor institute output.
2. the method for solvent wash method primary purification crude terephthalic acid according to claim 1, it is characterized in that, crystallization after the washing directly mixes with water, as the hydrorefined charging of pure terephthalic acid, no longer needs to remove through the crude terephthalic acid drying process of acetate.
3. according to the method for the solvent wash method primary purification crude terephthalic acid of claim 1 or 2, its feature also is, use the crude terephthalic acid crystallization that contains acetate and catalyzer by the mixed solvent making beating washing of p-Xylol, water and acetate preparation, used mixed solvent is by p-Xylol: 10-95%, water: 10-90%, acetate: 0-80% is formulated, and changes with crude terephthalic acid crystalline moisture percentage and to adjust.
4. according to the method for the solvent wash method primary purification crude terephthalic acid of claim 3, it is characterized in that, use the crude terephthalic acid crystallization that contains acetate and catalyzer by the mixed solvent displacement washing of p-Xylol, water and acetate preparation, used mixed solvent is by p-Xylol: 10-95%, water: 10-90%, acetate: 0-80% is formulated, and changes with crude terephthalic acid crystalline moisture percentage and to adjust.
5. according to the method for the solvent wash method primary purification crude terephthalic acid of claim 4, its feature also is, to be mixed to proper concn with water then and deliver to pure terephthalic acid's device by the washed terephthalic acid crystals water of the mixed solvent displacement washing of p-Xylol, water and acetate preparation.
6. according to the method for claim 5 solvent wash method primary purification crude terephthalic acid, it is characterized in that, to be mixed to proper concn with water then and deliver to pure terephthalic acid's device by the washed terephthalic acid crystals water making beating of the mixed solvent washing of p-Xylol, water and acetate preparation.
7. according to the method for the solvent wash method primary purification crude terephthalic acid of claim 6, its feature also is, with the washed mother liquor of mixed solvent after phase-splitting is handled, the upper strata p-Xylol has the part Returning reacting system mutually at least, and lower floor's water has the solvent of a part as the preparation catalyzer at least.
8. according to method according to claim 3 or 4 or 5 or 6 solvent wash method primary purification crude terephthalic acids, its feature also is, mixed solvent that is used to wash and water can also be divided into two portions to be used, and a part is used for the making beating washing, and another part is used for displacement washing.
9. according to method according to claim 8 solvent wash method primary purification crude terephthalic acid, its feature also is, the acetate slurry of the terephthalic acid of crude terephthalic acid device p xylene oxidation reactor output can be earlier with acetate or acetic acid water solution making beating washing through the crude terephthalic acid crystallization that contains acetate and catalyzer of solid-liquid separation gained, pass through (3), (4), (5), (6) process again, thereby further reduce Co, Mn catalyst residue amount in (5), the crystallization of (6) process gained crude terephthalic acid, reduce Co, Mn catalyst consumption.
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| CNA021585571A CN1510023A (en) | 2002-12-26 | 2002-12-26 | Process for primary refining coarse p-phthalic acid by solvent washing process |
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| CNA021585571A CN1510023A (en) | 2002-12-26 | 2002-12-26 | Process for primary refining coarse p-phthalic acid by solvent washing process |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040513A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing aqueous paste of terephthalic acid through solvent displacement |
| CN103030554A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Method of solvent replacement for crude terephthalic acid oxidation slurry |
| CN103804172A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Method for improving organic acid product quality |
| CN104817454A (en) * | 2014-01-30 | 2015-08-05 | 株式会社日立制作所 | Preparation method for refining terephthalic acid |
-
2002
- 2002-12-26 CN CNA021585571A patent/CN1510023A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040513A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing aqueous paste of terephthalic acid through solvent displacement |
| CN103030554A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Method of solvent replacement for crude terephthalic acid oxidation slurry |
| CN103030554B (en) * | 2011-09-30 | 2015-04-08 | 中国石油化工股份有限公司 | Method of solvent replacement for crude terephthalic acid oxidation slurry |
| CN103804172A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Method for improving organic acid product quality |
| CN103804172B (en) * | 2012-11-08 | 2015-11-18 | 中国石油化工股份有限公司 | A kind of method improving organic acid production quality |
| CN104817454A (en) * | 2014-01-30 | 2015-08-05 | 株式会社日立制作所 | Preparation method for refining terephthalic acid |
| CN104817454B (en) * | 2014-01-30 | 2017-01-04 | 株式会社日立制作所 | The manufacture method of purified terephthalic |
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