CN1332145A - Benzoic acid recovering process for terephthalic acid oxygenating residue - Google Patents
Benzoic acid recovering process for terephthalic acid oxygenating residue Download PDFInfo
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- CN1332145A CN1332145A CN 01127075 CN01127075A CN1332145A CN 1332145 A CN1332145 A CN 1332145A CN 01127075 CN01127075 CN 01127075 CN 01127075 A CN01127075 A CN 01127075A CN 1332145 A CN1332145 A CN 1332145A
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- terephthalic acid
- oxidation residua
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Abstract
The production of benzoic acid by using terephthalic acid oxygenating residue as raw material can reduce environmental pollution and raise economic benefits. The terephthalic acid oxygenating residue is first water dissolved and then vacuum filtered, and through cooling crystallization of the filtrate, centrifugal separation of the crystallized material, drying of filter cake to obtain coarse product and refining, pure benzoic acid is obtained. The refining includes the heating melting in melt tank, vacuum refining in rectifying tank and final condensation in condensator.
Description
One, technical field
The present invention is a kind of benzoic method of purifying that reclaims from terephthalic acid (TA) oxidation residua.
Two, background technology
Benzoic industrial process mainly contains 3 kinds, i.e. toluene liquid-phase air oxidation, and the toluene dichloride hydrolysis method, Tetra hydro Phthalic anhydride decarboxylation method in addition, also has benzyl oxychlorination method.Phenylformic acid is the important chemical product, mainly as the sanitas of food and medicine, makes Chemicals such as all right synthetic pesticide intermediate Benzoyl chloride of raw material, dyestuff intermediate M-NITROBENZOIC ACID, plastic plasticizer dibenzoic diglycol laurate with phenylformic acid.Produce in the process of terephthalic acid (TA) in p-Xylol (PX) oxidation, there is certain side reaction to produce, influence the quality of product in order to prevent by product from accumulating in system, the mother liquor that needs extraction about 10% is through further discharging with the oxidation residua form behind the evaporation recovery acetic acid.One cover is produced 450000 tons PTA device per year, and the annual emissions of TA oxidation residua is 2400～3000 tons.Since TA oxidation residua complicated component, separation difficulty.The oxidation residua that domestic PTA device is discharged is except that reclaiming catalyst cobalt, manganese, substantially as waste sludge discharge.The discharging of a large amount of TA oxidation residuas has caused the serious environmental pollution.
TA oxidation residua component complexity is formed often variation.Mainly contain phenylformic acid, p-methylbenzoic acid, terephthalic acid, phthalic acid etc.Wherein phenylformic acid is 25%～50%, and the content of phthalic acid is 45%～70%.Because the molecular structure of main ingredient is similar in the raw material, content is more or less the same, so isolating difficulty is bigger.For many years, the TA oxidation residua all is not utilized effectively.
Three, summary of the invention
It is raw material with the terephthalic acid oxidation residua that purpose of the present invention just provides a kind of, reduces environmental pollution, increase economic efficiency to reclaim benzoic method in the terephthalic acid oxidation residua.
The present invention is a raw material with the oxidation residua of PTA device discharging, utilizes the different of phenylformic acid and the solubleness of phthalic acid in water, takes the way of extracting and separating recrystallization to purify, and obtaining crude benzol formic acid purity is about 80%, phthalic acid about 90%.Then crude benzol formic acid is carried out the phenylformic acid that refinement treatment gets purity 〉=98%.Concrete working method is: adopt dissolving and crystalline method earlier with terephthalic acid oxidation residua and water dissolution, carry out vacuum filtration then, filtrate is carried out crystallisation by cooling, again the material behind the crystallisation by cooling is carried out centrifugation, filter cake is the phenylformic acid crude product after drying, is the pure product of phenylformic acid after making with extra care.The process for purification of phenylformic acid crude product is: at first with phenylformic acid crude product heating and melting in molten-bath, vacuum suction rectifying still is refining then, obtains the pure product of phenylformic acid by condenser condenses at last.Temperature with water dissolution terephthalic acid oxidation residua is 50～100 ℃, and the temperature of crystallisation by cooling is a room temperature.The temperature of molten-bath is 120 ℃～140 ℃.
The present invention has following significant advantage:
1. adopting the TA oxidation residua is that raw material reclaims phenylformic acid, belongs to environmental protection comprehensive utilization project.Not only greatly reduce production cost, improved economic benefit, and reduced environmental pollution.
2. reclaim phenylformic acid and adopt first extracting and separating, the back is refining separates, and can obtain the phenylformic acid of higher degree.Processing condition control is steady, and production unit is simple, less investment.
3. products benzene formic acid is suitable with the product that adopts the toluene liquid-phase air oxidation to make at present.The phenylformic acid that makes with the toluene liquid-phase oxidation generally also adopt conventional distillation or under the low pressure of 93.3Kpa rectifying get the technical grade phenylformic acid.Impurity such as some phenyl aldehyde that is difficult for removing, phenylcarbinol and biphenyl make product be little Huang or little green in the benzoic process of toluene oxidation system.
4. this technical grade product can be used for producing softening agent, Synolac, Benzoyl chloride etc.
Four, the specific embodiment
Embodiment of the present invention are as follows:
1) extract and separate
TA oxidation residua and a certain amount of water are dropped in the reactor, be heated with stirring to 90 ℃ of left sides The right side after insulation a period of time, is put into filtering ponds with material from the reactor bottom. Filtrate is passed through vacuum The suction settling tank carries out crystallisation by cooling. Filter cake namely gets phthalic acid crude product, purity after drying About 90%. Material behind the crystallisation by cooling carries out centrifugation filtrate and returns reactor, the filter cake warp Be the benzoic acid crude product after the drying, as the raw material of refining usefulness.
2) the refining separation
Be about 80% through the benzoic acid purity after the extract and separate. In have about 20% to benzene Dioctyl phthalate, M-phthalic acid and p-methylbenzoic acid etc. At first this crude benzol formic acid is dropped into melting Still, heating and melting. With vacuum suction rectifying still, (gauge pressure approximately under the decompression normality after material melted Be 0.096MPa) to make with extra care, benzoic acid gets after tying sheet by condenser condenses by flaker To white plates technical grade benzoic acid, purity is about 98%.
Example 1:
Three mouthfuls of round-bottomed flasks of 3000mL are with thermometer, temperature probe, agitator. In flask Drop into 529gTA oxidation residua and 2116g water, start and stir, begin heating, temperature is risen to About 90 ℃, after stirring a period of time, filter while hot. The filtrate crystallisation by cooling. Filter cake after drying Crude benzol dioctyl phthalate 297/g (be former slag weight 56%). Carried out behind the mother liquor crystallisation by cooling Filter, filter cake is crude benzol formic acid, 233g weighs to get. Terephthalic acid (TPA) and the benzoic acid branch of taking a sample respectively Analyse acid number. The acid number of crude benzol dioctyl phthalate is: 635.48mgKOH/g, content are 90%; The crude benzol first The acid number of acid is 489.51mgKOH/g, and content is 79%. Crude benzol formic acid drops into reactor to carry out Refining, the efficient wire packing of metal is housed in the tower, theoretical cam curve is 10. Distill at 500mL Drop into 220g crude benzol formic acid in the still, be heated to 150 ℃, be evacuated to then 0.098MPa (gauge pressure). Continue to be heated to the cat head discharging, tower top temperature is controlled between 160 ℃～180 ℃. Sample analysis benzoic acid purity is 98%.
Example 2:
(water capacity is 46.1%, so theoretical amount of solid is: 431g) to get TA oxidation residua 800g Put into the large beaker of 4000mL, the hot water that adds about 85 ℃ of 3200mL carries out stirring and dissolving, And heating is kept this temperature a period of time. Filter while hot. The filtrate crystallisation by cooling. The filter cake drying After crude benzol dioctyl phthalate 164.75g (be former slag weight 38%). Carry out behind the mother liquor crystallisation by cooling Filter, filter cake is crude benzol formic acid, weigh 233g (for former slag weight 54%). Total recovery is 92%. Terephthalic acid (TPA) and benzoic acid be the sample analysis acid number respectively. The acid number of crude benzol dioctyl phthalate For: 632.41mgKOH/g, content are 89%; Thick benzoic acid number is 479.96mgKOH/g, Content is: 77.73%. Crude benzol formic acid drops into reactor and makes with extra care, and it is efficient that metal is housed in the tower Wire packing, theoretical cam curve are 10. In the 500mL distillation still, drop into 220g crude benzol formic acid, Be heated to 150 ℃, be evacuated to then 0.098MPa (gauge pressure). Continue to be heated to cat head Discharging, tower top temperature are controlled between 160 ℃～180 ℃. Sample analysis benzoic acid purity is 98.5%.
Example 3:
Get TA oxidation residua 1000kg (water capacity is 65.4%, so theoretical amount of solid is: 346Kg) put into the reactor of 5000L, the hot water that adds about 85 ℃ of 4000L stirs Dissolving, and heat holding temperature after 90 ℃ of a period of times, open the still bottom valve, material is put into taken out The filter tank, with mother liquor suction settling tank, filter cake takes out from filtering ponds by vacuum, gets filter cake to be 322kg (water capacity is 25%). Carry out centrifugation behind the mother liquor crystallisation by cooling. It is thick to get benzoic acid Product are 148Kg (water capacity is 30%). It is 81.2% that the benzoic acid crude product records content by analysis.
Crude benzol formic acid drops into reactor and makes with extra care, and the wavy metal wire packing is housed, theory in the tower The number of plates is 30. In the 500L distillation still, drop into 220Kg crude benzol formic acid, be heated to 150 ℃, be evacuated to then 0.098MPa (gauge pressure). Continue to be heated to the cat head discharging, the cat head temperature Degree is controlled between 160 ℃～180 ℃. Sample analysis benzoic acid purity is 98.3%.
Claims (4)
1. one kind is reclaimed benzoic method from the terephthalic acid oxidation residua, it is characterized in that adopting dissolving and crystalline method earlier with terephthalic acid oxidation residua and water dissolution, carry out vacuum filtration then, filtrate is carried out crystallisation by cooling, again the material behind the crystallisation by cooling is carried out centrifugation, filter cake is the phenylformic acid crude product after drying, is the pure product of phenylformic acid after making with extra care.
2. according to claim 1ly it is characterized in that to reclaim benzoic method in the terephthalic acid oxidation residua temperature with water dissolution terephthalic acid oxidation residua is 50～100 ℃, the temperature of crystallisation by cooling is a room temperature.
3. reclaim benzoic method in the terephthalic acid oxidation residua according to claim 1 and 2, the process for purification that it is characterized in that the phenylformic acid crude product is: at first with phenylformic acid crude product heating and melting in molten-bath, vacuum suction rectifying still is refining then, obtains the pure product of phenylformic acid by condenser condenses at last.
4. according to claim 3ly reclaim benzoic method from the terephthalic acid oxidation residua, the temperature that it is characterized in that molten-bath is 120 ℃～140 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01127075 CN1332145A (en) | 2001-08-07 | 2001-08-07 | Benzoic acid recovering process for terephthalic acid oxygenating residue |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01127075 CN1332145A (en) | 2001-08-07 | 2001-08-07 | Benzoic acid recovering process for terephthalic acid oxygenating residue |
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| CN1332145A true CN1332145A (en) | 2002-01-23 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402563B (en) * | 2008-05-15 | 2011-11-30 | 厦门海湾化工有限公司 | Steam stripping processing method for CTA draff in PTA production |
| CN101402564B (en) * | 2008-05-15 | 2011-11-30 | 厦门海湾化工有限公司 | Dissolution processing method for CTA draff in PTA production |
| CN101268034B (en) * | 2005-08-11 | 2012-07-11 | 奇派特石化有限公司 | Process for removal of benzoic acid from an oxidizer purge stream |
| CN102701959A (en) * | 2012-06-05 | 2012-10-03 | 山东大学 | Novel method for extracting benzoic acid from TA (Terephthalic Acid) residues |
| CN102863330A (en) * | 2012-09-29 | 2013-01-09 | 仪征市茂瑞化工有限公司 | Method for separating and refining industrial benzoic acid from PTA (pure terephthalic acid) process wastewater |
| CN108358407A (en) * | 2018-02-12 | 2018-08-03 | 常州德诚环境科技有限公司 | PTA oxidation residuas and comprehensive utilization of mud system and method |
| CN112920044A (en) * | 2021-03-12 | 2021-06-08 | 湖南弘润化工科技有限公司 | Device and method for recycling benzoic acid from biphenyl substances |
| CN113493376A (en) * | 2020-04-08 | 2021-10-12 | 中国石油化工股份有限公司 | Method for comprehensively recycling PTA oxidation residues |
-
2001
- 2001-08-07 CN CN 01127075 patent/CN1332145A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101268034B (en) * | 2005-08-11 | 2012-07-11 | 奇派特石化有限公司 | Process for removal of benzoic acid from an oxidizer purge stream |
| CN101402563B (en) * | 2008-05-15 | 2011-11-30 | 厦门海湾化工有限公司 | Steam stripping processing method for CTA draff in PTA production |
| CN101402564B (en) * | 2008-05-15 | 2011-11-30 | 厦门海湾化工有限公司 | Dissolution processing method for CTA draff in PTA production |
| CN102701959A (en) * | 2012-06-05 | 2012-10-03 | 山东大学 | Novel method for extracting benzoic acid from TA (Terephthalic Acid) residues |
| CN102701959B (en) * | 2012-06-05 | 2014-07-02 | 山东大学 | Novel method for extracting benzoic acid from TA (Terephthalic Acid) residues |
| CN102863330A (en) * | 2012-09-29 | 2013-01-09 | 仪征市茂瑞化工有限公司 | Method for separating and refining industrial benzoic acid from PTA (pure terephthalic acid) process wastewater |
| CN108358407A (en) * | 2018-02-12 | 2018-08-03 | 常州德诚环境科技有限公司 | PTA oxidation residuas and comprehensive utilization of mud system and method |
| CN108358407B (en) * | 2018-02-12 | 2021-08-31 | 常州德诚环境科技有限公司 | PTA oxidation residue and sludge comprehensive utilization system and method |
| CN113493376A (en) * | 2020-04-08 | 2021-10-12 | 中国石油化工股份有限公司 | Method for comprehensively recycling PTA oxidation residues |
| CN112920044A (en) * | 2021-03-12 | 2021-06-08 | 湖南弘润化工科技有限公司 | Device and method for recycling benzoic acid from biphenyl substances |
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