CN1031402C - Refinement of acetic acid by ethyl aldehyde oxidation process - Google Patents
Refinement of acetic acid by ethyl aldehyde oxidation process Download PDFInfo
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- CN1031402C CN1031402C CN 92108442 CN92108442A CN1031402C CN 1031402 C CN1031402 C CN 1031402C CN 92108442 CN92108442 CN 92108442 CN 92108442 A CN92108442 A CN 92108442A CN 1031402 C CN1031402 C CN 1031402C
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Abstract
The present invention relates to a method for refining acetic acid prepared by an acetaldehyde oxidation method. A refining process is mainly completed by two rectifying towers connected in series. Low-boiling objects are removed by the first rectifying tower and high-boiling objects are removed by the second rectifying tower. The method is characterized in that refined acetic acid products are discharged from a siding liquid phase on the upper part of the second rectifying tower for removing the high-boiling objects, and thus, the influence of the low-boiling objects decomposed in the process of removing the high-boiling objects for the refined acetic acid products is avoided. The reduction time of potassium permanganate for the refined acetic acid products reaches 140 min, and simultaneously, the energy consumption of the second rectifying tower for removing the high-boiling objects is greatly reduced.
Description
The invention belongs to the process for purification of acetic acid, a kind of more precisely process for purification by the prepared thick acetic acid of oxidation of acetaldehyde.
Producing acetic acid by the acetaldehyde catalyzed oxidation, for example is catalyzer with the manganese acetate, and acetic acid is produced in acetaldehyde and pure oxygen reaction, has been the industrialization acetic acid production method of technology maturation.Be characterized in that technology is comparatively simple, cost is lower, and the direct usually acetic acid purity by the oxidizing reaction gained can reach 95%.And in order to obtain the product of higher commercial value, generally also further thick acetic acid is made with extra care, so that purity is brought up to more than 99%.The process for purification of shown in Figure 1 is a kind of existing acetic acid of producing by acetaldehyde oxidation, 1 is to take off the low-boiling-point substance tower among the figure, the 2nd, take off the high boiling material tower, 4,5 is respectively the tower bottom reboiler of two towers, the thick acetic acid A1 advanced person of oxidation gained takes off the low-boiling-point substance tower, discharge lower-boiling impurity A4 by cat head, tower stilling part A2 advances to take off high boiling material tower 2.The tower still of tower 2 is discharged the high-boiling-point impurity A5 catalyst recovery system Separation and Recovery catalyzer that contains catalyzer, the cat head fraction A3 acetic acid that gets product after condenser 7 condensations.Low-boiling-point substance A4 then goes dehydration tower 3 Separation and Recovery after condenser 6 condensations, in dehydration tower, tower middle part side line is extracted the aqueous first and second mixing acid A7 out, and cat head is isolated the waste water A 8 that contains dilute acetic acid, and the tower still must reclaim acetic acid A6 (generally returning in the distillation system again).8 and 9 are respectively dehydration column overhead condenser and tower bottom reboiler among the figure.
In the acetic acid quality index after refining, except that purity, the content of reducing impurity also be one than important index.For ease of test, the content of the reducing impurity in the finished product acetic acid is used potassium permanganate recovery time secondary indication always on the industrial production.By the acetic acid that acetaldehyde oxidation is produced, the potassium permanganate recovery time of product is generally 5min～10min.
By the principal reaction of oxidation of acetaldehyde system acetic acid as can be known, low-boiling-point substance mainly comprises unreacted acetaldehyde, formaldehyde, formic acid, water, ritalin etc., high boiling material then mainly is the ethylidene diacetate, and what wherein influence the potassium permanganate oxidation time mainly is reducing impurity acetaldehyde, formaldehyde.Generally speaking, through taking off the low-boiling-point substance tower, do not contain low-boiling-point substances such as acetaldehyde, formaldehyde in the product substantially.But because high boiling material ethylidene diacetate at high temperature easily resolves into aceticanhydride and acetaldehyde, therefore boil in the tower taking off height, produced lower boiling reducing impurity acetaldehyde again again.The reason that the acetate products potassium permanganate recovery time that Here it is makes with existing acetic acid process for purification is short.To taking off the analysis revealed that gas-liquid two-phase is formed on each column plate of high boiling material tower, the content of the ethylidene diacetate on each column plate in the liquid phase progressively rises from top to bottom, and the acetaldehyde in the gas phase then is progressively to rise from bottom to top, and this has also confirmed this point.
In prior art, other has a kind of process for refining of acetic acid can avoid producing reducing impurity acetaldehyde in taking off the process of high boiling material, be that thick acetic acid removes high boiling material through distillation earlier, and then the distillation remove low-boiling-point substance, the acetaldehyde that produces in taking off the high boiling material process will be removed in second rectifying tower in the lump with original low-boiling-point substance like this.But because automatic oxidation reaction device to the second rectifying tower, container inner pressure reduces gradually, therefore in the required energy consumption of the first rectifying tower heating and gasifying total overall reaction product acetic acid than at the required energy consumption height of the second rectifying tower heating and gasifying reaction product acetic acid, angle from economy, obviously the latter is irrational, and its production cost will improve.
The purpose of this invention is to provide a kind of process for purification of the new acetic acid of producing by oxidation of acetaldehyde, compare, do not improve production cost, and the reducing impurity in the product reduces greatly with aforesaid first kind of process for purification.
Acetic acid process for purification provided by the invention, its treating process is still finished by two rectifying tower, still earlier remove low-boiling-point substance in first rectifying tower, the back removes high boiling material in second rectifying tower, and the first method in whole process flow and the aforementioned prior art is basic identical.It is characterized in that the finished product are changed into by the cat head gas phase discharging of taking off the high boiling material tower and taking off the top side line liquid phase discharging of high boiling material tower, the cat head fraction is then through being back in the tower after the condenser condenses.In order to prevent the accumulation of low-boiling-point substance, part is led to recovery system in the condensed fraction, and control of reflux ratio is in (10～40): 1
The selection of discharge port position should be considered lower-boiling impurity and the two influence to product of high-boiling-point impurity simultaneously.When the position was too high, the low boiling mixture content that newly decomposites was higher, and when high boiling material content is crossed when low with higher in the position, general ideal discharge port position should be at the 3rd block of column plate below the trim the top of column liquid inlet between the 3rd block of column plate more than the opening for feed.
Accompanying drawing 1 is the acetic acid rectification flow sketch of prior art;
Accompanying drawing 2 is acetic acid rectification flow sketches of the present invention.
Further describe details of the present invention below in conjunction with accompanying drawing 2.
In Fig. 2, the 10th, thick acetic acid medial launder, the 11st, evaporimeter, 12 and 13 is two essences Heat up in a steamer tower, be respectively applied to remove low-boiling-point substance and high-boiling components, 16,17 be two rectifying columns again The device that boils, 18,19 is overhead condensers of two rectifying columns. The 14th, recovery tower, the 20th, return Receive Tata top condenser, the 21st, the recovery tower reboiler.
The thick acetic acid A9 of oxidation gained is introduced into medial launder 10, is admitted to then evaporimeter 11, Catalyst and part high-boiling components are removed in flash distillation, and evaporimeter heats with steam. Acetic acid, low boiling Enter tower by the middle part of taking off low-boiling-point substance tower 12 behind thing and the most of high-boiling components A10 heating and gasifying In, the catalyst that base of evaporator is discharged and part high-boiling components A13 are through cooler 15 coolings After remove catalyst recovery system. In tower 12, cat head discharge unreacted micro-acetaldehyde, The low-boiling-point substance A14 such as water, methyl acetate, formic acid, formaldehyde contain the acetic acid of high-boiling-point impurity A11 utilizes between tower pressure reduction to send into from tower reactor to take off high-boiling components tower 13. Bottom discharging from tower 13 Contain the vinegar stock A16 of trace catalyst and high-boiling components, acetate products A12 is by on the tower The side line liquid phase discharging of section. Product can directly be obtained from column plate, also can two blocks of column plates it Between a seal pot is set, the acetic acid of top column plate overflows into seal pot from plate hole, product then from Seal pot is obtained. Reflux in cat head fraction A15 condensation rear section, for avoiding low boiling impurity Accumulate in tower, a part is sent recovery tower 14, and reflux ratio is (10～40): 1. Reclaim Tower 14 separates recovery in order to the cat head fraction A14 to tower 12, tower 13 with A15, by Cat head is isolated spirit of vinegar waste water A 19, and tower middle part moisture first, the second of lateral line withdrawal function is mixed Acid A18 obtains recovery of acetic acid A17 by tower reactor, and recovery of acetic acid A17 is back to evaporimeter 10 are used as spray.
The present invention has avoided the influence to product of low-boiling-point substance that acetic acid decomposited effectively in taking off the high boiling material process, quality product obviously improves, and the recovery time of potassium permanganate can reach 60min～140min.In addition, because the finished product are taking off the high boiling material tower directly with the liquid phase discharging, the steam economy that takes off the high boiling material tower also greatly reduces.
Embodiment:
The flow process for the treatment of process as shown in Figure 2, wherein taking off low-boiling-point substance tower 12 has 64 blocks of column plates, distance between plates is 500mm, take off high boiling material tower 13 35 blocks of column plates are arranged, distance between plates is 500mm, and opening for feed is positioned at from cat head the 33rd column plate place down, and outlet for product is positioned at down the 5th column plate place of trim the top of column import.129 ℃ of vaporizer 11 still temperature are taken off 134 ℃ of low-boiling-point substance Tata still temperature, 115 ℃ of tower top temperatures, and cat head fraction reflux ratio is (15～20): 1, take off 123 ℃ of high boiling material Tata still temperature, 117 ℃ of tower top temperatures, cat head fraction reflux ratio is (10～40): 1.
Main quality index of product such as table 1 are listed.
Table 1:
| Purity (%) formic acid content (%) acetaldehyde (%) residue on evaporation (%) potassium permanganate recovery time (min) | 99.2 0.10 0.03 0.01 140 |
Comparative example:
The flow process for the treatment of process as shown in Figure 1, wherein taking off low-boiling-point substance tower 1 has 64 blocks of column plates, distance between plates is from being 500mm.Taking off high boiling material tower 2 has 35 blocks of column plates, and distance between plates is 500mm, and opening for feed is positioned at from cat head the 33rd column plate place down.Take off 135 ℃ of low-boiling-point substance Tata still temperature, 115 ℃ of tower top temperatures, cat head fraction reflux ratio is (15～20): 1.Take off 126 ℃ of high boiling material Tata still temperature, 118 ℃ of tower top temperatures, partial reflux after the condensation of cat head fraction, all the other are product acetic acid, and reflux ratio is 1: 1.
Main quality index of product such as table 2 are listed.
Table 2:
| Purity (%) formic acid content (%) acetaldehyde (%) residue on evaporation (%) potassium permanganate recovery time (min) | 99.1 0.11 0.05 0.02 5 |
Claims (2)
1, a kind of process for purification of the acetic acid by acetaldehyde oxidation preparation, FF mainly is made up of two placed in-line rectifying tower, thick acetic acid enters first rectifying tower by the tower middle part, its cat head is discharged lower-boiling impurity, the primary purification acetic acid that comes from the tower still enters second rectifying tower by the tower middle part, discharge high-boiling-point impurity by the tower still, it is characterized in that:
1) the second rectifying tower cat head fraction is after a condenser condenses, and a part leads to recovery system, and a part refluxes, and control of reflux ratio is in (10～40): 1
2) refining acetate products is by the second rectifying tower side line liquid phase discharging, discharge port at the 3rd block of column plate below the trim the top of column inlet between the 3rd block of column plate more than the opening for feed.
2, according to the described acetic acid process for purification of claim 1, the thick acetic acid that it is characterized in that the oxidation gained through a vaporizer laggard first rectifying tower that gasifies, is made spray from recovery acetic acid to the vaporizer of recovery system and is used earlier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92108442 CN1031402C (en) | 1992-06-03 | 1992-06-03 | Refinement of acetic acid by ethyl aldehyde oxidation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92108442 CN1031402C (en) | 1992-06-03 | 1992-06-03 | Refinement of acetic acid by ethyl aldehyde oxidation process |
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| Publication Number | Publication Date |
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| CN1079461A CN1079461A (en) | 1993-12-15 |
| CN1031402C true CN1031402C (en) | 1996-03-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 92108442 Expired - Fee Related CN1031402C (en) | 1992-06-03 | 1992-06-03 | Refinement of acetic acid by ethyl aldehyde oxidation process |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928212A (en) * | 2010-08-27 | 2010-12-29 | 南京扬池工业气体有限公司 | Method for intermittently recycling and separating light component waste in production of acetic acid |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR112019017941A2 (en) * | 2017-03-22 | 2020-05-19 | Daicel Corp | method to produce acetic acid |
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1992
- 1992-06-03 CN CN 92108442 patent/CN1031402C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928212A (en) * | 2010-08-27 | 2010-12-29 | 南京扬池工业气体有限公司 | Method for intermittently recycling and separating light component waste in production of acetic acid |
| CN101928212B (en) * | 2010-08-27 | 2012-11-21 | 南京扬池工业气体有限公司 | Method for intermittently recycling and separating light component waste in production of acetic acid |
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| Publication number | Publication date |
|---|---|
| CN1079461A (en) | 1993-12-15 |
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