CN1752060A - Recovery method of byproduct methyl acetate in paraphthalic acid production - Google Patents
Recovery method of byproduct methyl acetate in paraphthalic acid production Download PDFInfo
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- CN1752060A CN1752060A CN 200510019677 CN200510019677A CN1752060A CN 1752060 A CN1752060 A CN 1752060A CN 200510019677 CN200510019677 CN 200510019677 CN 200510019677 A CN200510019677 A CN 200510019677A CN 1752060 A CN1752060 A CN 1752060A
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- ritalin
- tower
- hydrolysis
- acetic acid
- methyl alcohol
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Abstract
A process for recovering the methyl acetate as the by-product generated in preparing terephthalic acid includes such steps as adsorbing the methyl acetate from tail gas by activated carbon, desorbing by low-pressure vapor, rectifying the desorbed liquid and the sewage containing the methyl acetate to obtain methyl acetate, and catalytic rectifying in the catalytic rectifying-hydrolyzing tower to decompose the methyl acetate into acetic acid and methanol.
Description
Technical field:
The present invention relates to a kind of recovery technology of ritalin.
Background technology:
With the p-Xylol be raw material to adopt acetic acid be that the high-temperature oxidation of solvent is produced in the process of terephthalic acid, it is one of main side reaction that the acetic acid incomplete combustion generates ritalin.This also is a higher major cause of acetic acid consumption and Production of Terephthalic Acid cost.The ritalin that generates is finally by following approach discharger: (1) enters atmosphere with oxidizing reaction tail gas; (2) enter atmosphere with solvent dehydration cat head non-condensable gas; (3) be expelled to the downstream waste disposal plant with solvent dehydration column overhead liquid phase (trade effluent), thereby cause the wasting of resources and environmental pollution.
For the ritalin of discharging with oxidizing reaction tail gas, it is to adopt the method for acetic acid washing to reclaim ritalin in high-pressure absorber that Mitsubishi changes into, and the Mitsui oiling then adopts the method for burning to handle organism in the waste gas.For the ritalin of discharging with solvent dehydration column overhead non-condensable gas, the mode of Am oco company employing compression condensation reclaims organism such as ritalin wherein.
For the ritalin the liquid phase of discharging from the acetic acid dehydration column overhead, Mitsubishi changes into and be provided with ritalin distillation recovery tower behind acetic acid dehydrating tower, and the ritalin in the dehydration column overhead waste water is reclaimed in distillation.DuPont also reclaims the ritalin in the azeotropic distillation dehydration overhead water, but the ritalin in the gas phase is not all reclaimed.
China raises sub-petro-chemical corporation and has then set up a ritalin rectifying tower.Utilize the organism in the gac device adsorption and oxidation reaction end gas, utilize low-pressure steam to resolve again, the desorbed solution that is rich in ritalin is sent into the ritalin rectifying tower; With the cooling of dehydration column overhead overhead product, washing, washings enters the ritalin rectifying tower to the non-condensable gas of solvent dehydration cat head mutually.Handle by the ritalin rectifying tower then and obtain the ritalin finished product.Many covers terephthalic acid production plant that China introduces does not then all reclaim the ritalin in the liquid phase.
Because the industrial use of ritalin is limited, general Production of Terephthalic Acid enterprise all is recycled to the ritalin that reclaims in the reactor, to suppress the generation of ritalin, reduces acetic acid consumption.But this can not fundamentally solve the problem of by-product ritalin in the Production of Terephthalic Acid process, and the ritalin in the reactor constantly accumulates, and finally has to discharge system in the mode of gas phase or liquid phase.
For this reason, Am oco company has proposed to reclaim the method for acetic acid with the method for catalytic distillation from ritalin, and has applied for patent, the patent No.: us005113015-001.This method utilizes ritalin under the effect of an acidic catalyst, and hydrolysis generates acetic acid and methyl alcohol, reclaims the acetic acid in the ritalin.But yet there are no industrialized report.
Summary of the invention:
The purpose of this invention is to provide a kind of ritalin depth hydrolysis and be decomposed into the recovery method of by-product methyl acetate in the Production of Terephthalic Acid of acetic acid and methyl alcohol generation.
Technical process of the present invention can be divided into ritalin and collect step and two parts of ritalin decomposition step.
(1) described ritalin collection step is as follows: the ritalin of being taken away by terephthalic acid synthesis system gas phase adopts absorption method to collect.To contain the oxidizing reaction tail gas and the absorption of the ritalin in the solvent of ritalin with sorbent material.After adsorbents adsorb was saturated, with the desorb of low-pressure water steam, stripping liquid obtained ritalin through distillation.
(2) described ritalin decomposition step is as follows: ritalin and water (plume 1 and 2) are heated to 40-55 ℃, heated ritalin and water difference (plume 1 and 2) are sent in the hydrolysis tower, to 70～85 ℃ of hydrolysis Tata still heating, the hydrolysis tower overhead vapours refluxes through condensed phlegma and enters hydrolysis tower; Hydrolysis Tata still output hydrolyzed solution (stream thigh 3).This hydrolyzed solution (stream thigh 3) is sent into hydrolyzed solution knockout tower rectifying separation, and hydrolyzed solution shunting Tata still obtains aqueous acetic acid (stream thigh 4).Hydrolysis knockout tower cat head distillates ritalin and the methanol mixed liquid (stream thigh 5) that contains small amount of methanol, this liquid (stream thigh 5) is sent into methanol distillation column, through rectifying separation, Methanol Recovery Tata still obtains methyl alcohol (stream thigh 6), and the Methanol Recovery column overhead distillates ritalin and methyl alcohol (stream thigh 7).
Advantage of the present invention is as follows:
(1) with being decomposed into bigger acetic acid of industrial use and methyl alcohol after the ritalin collection, both had an economic benefit, can reduce pollution again environment;
(2) employing has the license (patent No.: catalytic distillation equipment ZL02213024.1) and catalyst loading technology, catalyst loading convenience, catalytic efficiency height;
(3) can regulate the methyl acetate hydrolysis rate arbitrarily, reach the simplification recovery process, reduce the purpose that reclaims energy consumption and process cost;
(4) only need three towers just can realize that the hydrolysis of ritalin separates with product, flow process is simple, and investment and process cost are low.
(5) the inventive method can obtain pure methyl alcohol, and the acetic acid of recovery can be back to the production of terephthalic acid, and methyl alcohol can be used as commodity selling.
Description of drawings:
Fig. 1 is a process flow sheet of the present invention.
Embodiment:
(1) described ritalin collection step is as follows: the ritalin of being taken away by terephthalic acid synthesis system gas phase adopts absorption method to collect.To contain the oxidizing reaction tail gas and the absorption of the ritalin in the solvent of ritalin with sorbent materials such as gacs.After adsorbents adsorb is saturated, with the desorb of low-pressure water steam, the air distillation of stripping liquid process, 55 ℃ of tower top temperatures, 100 ℃ of tower still temperature obtain ritalin from cat head.
(2) described ritalin decomposition step is as follows: ritalin and water (plume 1 and 2) are heated to respectively about 50 ℃, send into continuously in the hydrolysis tower with pump, the tower still is heated to 70～85 ℃, the overhead vapours cooling water condensation, and phlegma refluxes and enters hydrolysis tower; Hydrolysis Tata still is 200 parts of/hour hydrolyzed solutions of output (stream thigh 3) continuously.This hydrolyzed solution (stream strand 3) is sent into hydrolyzed solution knockout tower rectifying separation, and hydrolyzed solution shunting Tata still obtains 164 parts/hour and contains 71.7 parts of acetic acid, moisture 923 parts aqueous acetic acid (stream strand 4).Hydrolysis knockout tower cat head distillates 40.0 parts of/hour liquid (stream thigh 5) that contain the mixed solution of methyl alcohol and ritalin, this liquid (stream thigh 5) is sent into methanol distillation column, through rectifying separation, Methanol Recovery Tata still obtains 37.02 parts of methyl alcohol (stream thigh 6), and the Methanol Recovery column overhead distillates 2.98 parts of ritalins and methyl alcohol (stream thigh 7).
Described ritalin gathering system is made up of adsorber and ritalin distillation tower.The ritalin of being taken away by terephthalic acid synthesis system gas phase adopts absorption method to collect.Under 30～45 ℃ of temperature, will contain the oxidizing reaction tail gas and the absorption of the ritalin in the solvent of ritalin with sorbent materials such as gacs.After adsorbents adsorb is saturated, with the desorb of low-pressure water steam, the distillation of stripping liquid process, 55 ℃ of tower top temperatures, 100 ℃ of tower still temperature obtain ritalin from cat head.
The ritalin applied catalysis distillation hydrolysis technology of collecting is decomposed.Send into the catalytic distillation hydrolysis tower by the ritalin that methyl ester distilled column overhead is come out, under appropriate processing condition, make ritalin carry out the depth hydrolysis and become acetic acid and methyl alcohol, hydrolyzed solution is sent into hydrolyzed solution knockout tower rectifying separation, acetic acid is from the extraction of tower still, methyl alcohol and undecomposed little acetic acid methyl esters distillate from cat head, are sent to methanol distillation column.The Methanol Recovery column overhead distillates ritalin and small amount of methanol (azeotropic that consists of methyl alcohol and ritalin is formed), sends the hydrolysis tower circulation back to and decomposes.Tower still extraction methyl alcohol is as product.
Embodiment 1
Contain 90 parts of ritalins, the water (stream thigh 2) of the ritalin that water is 10 parts (stream strand 1) and 104 parts/hour is heated to 50 ℃ respectively, sends in the hydrolysis tower continuously with pump.The heating of tower still, the overhead vapours cooling water condensation.Phlegma refluxes and enters hydrolysis tower.The tower still is 200 parts of/hour hydrolyzed solutions of output (stream thigh 3) continuously, and wherein each group component is as shown in table 1.This hydrolyzed solution is sent into hydrolyzed solution knockout tower rectifying separation, and the tower still obtains 164 parts/hour and contains 71.7 parts of acetic acid, moisture 923 parts aqueous acetic acid (stream thigh 4).Cat head distillates 40.0 parts of/hour mixing liquids (flowing thigh 5) that contain methyl alcohol and ritalin, sends into methanol distillation column, and through rectifying separation, the tower still obtains 37.02 parts of methyl alcohol (stream thigh 6), and cat head distillates 298 parts of ritalins and methyl alcohol (stream thigh 7).
Embodiment 2
Implementation process is with embodiment 1, and concrete data are as shown in table 1.
Table 1
| Embodiment 1 | Hydrolysis tower | The hydrolyzed solution knockout tower | Methanol distillation column |
| Charging (part/hour) stream strand 1:90 part methyl acetate+10 parts of water; Be heated to 50 ℃ of streams strand 2:104 part water, be heated to 50 ℃ of reaction temperatures: 54～82 ℃ of pressure: 0.1M Pa | Charging (part/hour): be | Charging (part/hour) is | |
| Discharging (part/hour) stream burst 4:164 part, wherein: 92.3 parts in 71.7 parts of water of acetic acid | Discharging (part/hour) stream burst 6:37.02 part, wherein: 0.18 part in 36.84 parts of water of methyl alcohol |
| Tower still discharging (part/hour): stream burst 3:204 part, wherein: 1.6 parts of 38.2 parts of ritalins of 92.5 parts of methyl alcohol of 71.7 parts of water of acetic acid | Stream burst 5:40 part, wherein: 0.2 part in 1.6 parts of water of 38.2 parts of ritalins of methyl alcohol | Stream burst 7:2.98 part, wherein: 0.02 part in 1.6 parts of water of 1.36 parts of ritalins of methyl alcohol | |
| Embodiment 2 | Charging (part/hour) stream strand 1:155 part methyl acetate+17 parts of water; Be heated to 50 ℃ of streams strand 2:175 part water, be heated to 50 ℃ of reaction temperatures: 54～82 ℃ of pressure: 0.1MPa | Charging (part/hour) | Charging (part/hour) |
| Discharging (part/hour) stream burst 4:276.8 part; Wherein: 155.2 parts of streams of 121.6 parts of water of acetic acid burst 5:70.2 part, wherein: 0.3 part in 5.1 parts of water of 64.8 parts of methyl acetates of methyl alcohol | Discharging (part/hour) stream burst 6:60.17 part; Wherein: 0.27 part of stream of 59.9 parts of water of methyl alcohol burst 7:10.03 part, wherein: 0.03 part in 5.1 parts of water of 4.9 parts of methyl acetates of methyl alcohol | ||
| Tower still discharging (part/hour): stream burst 3:347 part, wherein: 5.1 parts of 64.8 parts of ritalins of 155.5 parts of methyl alcohol of 121.6 parts of water of acetic acid |
Claims (2)
1, the recovery method of by-product methyl acetate in a kind of Production of Terephthalic Acid, it is characterized in that: send into the catalytic distillation hydrolysis tower by the ritalin that ritalin distillation tower cat head comes out, the depth hydrolysis becomes acetic acid and methyl alcohol, hydrolyzed solution is sent into hydrolyzed solution knockout tower rectifying separation acetic acid from the extraction of tower still, methyl alcohol and undecomposed little acetic acid methyl esters distillate from cat head, be sent to methanol distillation column, the Methanol Recovery column overhead distillates ritalin and small amount of methanol, sends the hydrolysis tower circulation back to and decomposes.
2, the recovery method of by-product methyl acetate in the Production of Terephthalic Acid according to claim 1 is characterized in that, technical process can be divided into ritalin and collect step and two parts of ritalin decomposition step, and its concrete processing step is as follows:
(1) described ritalin collection step is as follows: the ritalin of being taken away by terephthalic acid synthesis system gas phase adopts absorption method to collect.To contain the oxidizing reaction tail gas and the absorption of the ritalin in the solvent of ritalin with sorbent material.After adsorbents adsorb was saturated, with the desorb of low-pressure water steam, stripping liquid obtained ritalin through distillation;
(2) described ritalin decomposition step is as follows: ritalin and water are heated to 40-55 ℃, send into heated ritalin and water in the hydrolysis tower respectively, to 70～85 ℃ of hydrolysis Tata still heating, hydrolysis tower overhead vapours phlegma after condensation refluxes and enters hydrolysis tower; Hydrolysis Tata still output hydrolyzed solution; This hydrolyzed solution is sent into hydrolyzed solution knockout tower rectifying separation, and hydrolyzed solution fractionation Tata still obtains aqueous acetic acid; Hydrolysis knockout tower cat head distillates the mixed solution that contains methyl alcohol and little acetic acid methyl esters, and this liquid is sent into methanol distillation column, and through rectifying separation, Methanol Recovery Tata still obtains methyl alcohol, and the Methanol Recovery column overhead distillates ritalin and methyl alcohol.
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| CN 200510019677 CN1752060A (en) | 2005-10-24 | 2005-10-24 | Recovery method of byproduct methyl acetate in paraphthalic acid production |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186575B (en) * | 2007-12-04 | 2010-04-14 | 南京工业大学 | Methyl acetate catalysis rectification hydrolysis technique |
| CN101130482B (en) * | 2006-08-22 | 2010-12-08 | 翔鹭石化企业（厦门）有限公司 | Method and equipment for improving technique of methyl acetate hydrolyzation |
| CN101537299B (en) * | 2009-03-19 | 2011-12-28 | 绍兴远东石化有限公司 | Method for recycling organic matters in tail gas from production of terephthalic acid |
| CN109718634A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of pure terephthalic acid producing device generates the preprocess method of exhaust gas |
-
2005
- 2005-10-24 CN CN 200510019677 patent/CN1752060A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130482B (en) * | 2006-08-22 | 2010-12-08 | 翔鹭石化企业（厦门）有限公司 | Method and equipment for improving technique of methyl acetate hydrolyzation |
| CN101186575B (en) * | 2007-12-04 | 2010-04-14 | 南京工业大学 | Methyl acetate catalysis rectification hydrolysis technique |
| CN101537299B (en) * | 2009-03-19 | 2011-12-28 | 绍兴远东石化有限公司 | Method for recycling organic matters in tail gas from production of terephthalic acid |
| CN109718634A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of pure terephthalic acid producing device generates the preprocess method of exhaust gas |
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