CN112079691A - Method for improving quality of phenol product - Google Patents
Method for improving quality of phenol product Download PDFInfo
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- CN112079691A CN112079691A CN202010979796.5A CN202010979796A CN112079691A CN 112079691 A CN112079691 A CN 112079691A CN 202010979796 A CN202010979796 A CN 202010979796A CN 112079691 A CN112079691 A CN 112079691A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/86—Purification; separation; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/88—Use of additives, e.g. for stabilisation
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for improving the quality of phenol products, which designs a resin bed into 3 wet substrate resin beds which are connected in series and contain resin Xfj-02D (T-311) type and have the water content of 40-50%; wherein, the resin filled in the first sub-resin bed and the second sub-resin bed is 2 tons, the resin filled in the third sub-resin bed is 4.5 tons, the inlet temperature of the sub-resin beds is controlled at 90-110 ℃, and the ratio of the phenol feeding amount to the dry resin amount on each sub-resin bed is 3, thereby ensuring the removal effect of carbonyl impurities and ensuring that the impurities are completely removed; in addition, in the rectification process, the temperature of a sensitive plate at the top of the AMS tower is increased to 135-138 ℃ by reducing the reflux of the top of the AMS tower, the water content in a phenol product is reduced to be below 200PPm, and the crystallization point of the phenol is higher than 40.8 ℃; and finally, adding a corrosion inhibitor (citric acid) into the phenol, so that the phenol product is effectively kept from changing color for a long time, and the quality of the phenol product is comprehensively improved.
Description
Technical Field
The invention relates to the field of phenol post-treatment methods, in particular to a method for improving the quality of phenol products produced in a phenol and acetone production line by combining a cumene oxidation method.
Background
The existing phenol-acetone plant is built since 1996, and the production capacity of phenol reaches 12 ten thousand tons every year. The industrial process from cumene to phenol is well known and comprises a two-step synthesis: cumene is air oxidized to a Cumene Hydroperoxide (CHP) intermediate, which is then decomposed (cleaved) with acid to yield phenol and acetone as the major products. However, in addition to the desired product, the resulting crude cleavage product mixture contains a certain amount of various by-products including alpha-methylstyrene, acetophenone, cumylphenol, unreacted cumene, and trace amounts of various carbonyl-type impurities including hydroxyacetone, mesityl oxide, and aldehydes. In subsequent purification steps, these unwanted by-products and impurities must be removed from the final phenol and acetone products by various separation methods, including extraction, distillation, and catalytic chemical treatments.
Most of impurities in phenol rectification feed, such as Acetophenone (ACP), Cumylphenol (CPH) and phenol tar-containing materials, have higher boiling points than phenol and are easily removed by rectification. However, some acetone derivatives have boiling points close to that of phenol, and cannot be removed from phenol by rectification alone, and in order to ensure the production of high-quality phenol, the crude phenol needs to be chemically treated by adding methyl amylene diamine (or hexamethylene diamine). In the chemical treatment reactor, impurities are converted to compounds that are easily removed by rectification by adding methylpentylene diamine (or hexamethylene diamine) to the crude phenol, the chemical treatment reaction equation is as follows:
typically, a trace of 25mg/kg of benzofuran (MBF) and dimethyl benzofuran (2MBF) will form during decomposition; in addition, MBF and 2MBF are also accumulated circularly in the rectification process, and the chemical treatment has no effect on the impurities. In order to remove carbonyl impurities such as MBF, 2MBF, mesityl oxide (MEO) and the like, an ion exchange resin (IXRT) is arranged in front of a refined phenol product tower, and as MBF, 2MBF, MEO and the like react in an IX resin bed to become heavy components, the heavy components are separated after entering the refined phenol product tower.
Other high-activity organic compound impurities are polymerized into heavy components under the catalysis of resin, such as a-methyl styrene (AMS) reaction to form dimer heavy components, and similarly phenol derivatives generated in the decomposition process, and the active components are reacted to form the heavy components.
Although the principle of removing phenol impurities is well known, the phenol products produced by the existing domestic main phenol acetone production plants still have the problems of more impurities, high moisture content (about 400PPm), low crystallization point (40.6-40.7 ℃) and easy discoloration, the color number is more than 20, the product quality can only reach the resin grade, and the requirements of special applications cannot be met, for example: can not meet the quality requirement of the polycarbonate-grade phenol required by engineering plastics and functional plastics. The high content of carbonyl impurities such as 2-methylbenzofuran in phenol is considered to be caused by the following reasons:
(1) the loss of active points of the resin is caused when the resin catalyzes the polymerization reaction of impurities;
(2) methyl amylene diamine (or hexamethylene diamine) and trace amine compounds are also added in the process of removing impurities in the resin bed, and the compounds neutralize the acidity of the resin, so that the catalytic capability of the resin is reduced or the catalytic action of the resin is lost;
(3) the resin bed residence time is short and if hydroxyacetone is present in the phenol stream, the 2-methylbenzofuran treatment efficiency is affected or even rendered ineffective.
Disclosure of Invention
In view of the above technical problems and disadvantages, the present invention aims to provide a method for improving the quality of phenol products, which ensures the removal effect of carbonyl impurities through the modification of a resin bed, so that the removal of the impurities is complete; in addition, in the rectification process, the temperature of a sensitive plate at the top of the AMS tower is increased to 135-138 ℃ by reducing the reflux of the top of the AMS tower, the water content in a phenol product is reduced to be below 200PPm, and the crystallization point of the phenol is higher than 40.8 ℃; and finally, adding a corrosion inhibitor (citric acid) into the phenol, so that the phenol product is effectively kept from changing color for a long time, and the quality of the phenol is comprehensively improved.
In order to realize the purpose, the invention is realized by adopting the following technical scheme;
a method for upgrading a phenol product comprising the steps of:
4, feeding the material from the third sub-resin bed into a phenol rectifying tower, and extracting a product phenol from a side line of the phenol rectifying tower, wherein the crystallization point of the phenol is more than 40.8 ℃, and the water content is less than 200 PPm;
More preferably, the cumene topping tower is used for removing cumene in crude phenol, and the tar tower is used for removing tar in crude phenol; the AMS tower is used for removing AMS in crude phenol; the resin bed set is used for removing carbonyl impurities in crude phenol.
The invention has the advantages and beneficial effects that:
(1) the invention reduces the reflux quantity of the AMS tower top, improves the temperature of the sensitive plate at the AMS tower top to 135-138 ℃, reasonably changes the technological parameters of the AMS tower top, reduces the water content of the phenol product to below 200PPm, and greatly improves the quality of the phenol product, wherein the crystallization point of the phenol reaches above 40.8 ℃.
(2) The method can effectively remove impurities in the phenol by utilizing the three resin beds connected in series, ensures the removal effect of carbonyl impurities, and ensures that the impurities are completely removed, so that the quality requirement of the polycarbonic phenol is met.
(3) In order to solve the problem of phenol oxidation and ensure that the appearance of a phenol product does not change color for a long time and the crystallization point is more than 40.8 ℃, the invention tries the multiple antioxidants, and unexpectedly discovers that the phenol product can be effectively kept from changing color for a long time by adding a corrosion inhibitor (citric acid) into the phenol, and the crystallization point is stably higher than 40.8 ℃.
Drawings
FIG. 1 is a flow chart of a lifting method of the present invention;
FIG. 2 is a mass spectrum of a feed analysis before resin bed set;
FIG. 3 is a feed analysis chromatogram prior to resin bed set;
FIG. 4 is a post bed bleed analysis chromatogram of the resin bed of example 1;
FIG. 5 is a mass spectrum of a post-draw analysis of the resin bed of comparative example 1;
FIG. 6 is a post-bed discharge analysis chromatogram of the resin bed of comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Referring to fig. 1, the present invention provides a method for improving the quality of phenol product, comprising the following steps:
4, feeding the material from the third sub-resin bed into a phenol rectifying tower for further impurity removal, and then extracting pure product phenol from the side line of the phenol rectifying tower;
the cumene topping tower is used for removing cumene in the crude phenol, and the tar tower is used for removing tar in the crude phenol; the AMS tower is used for removing AMS in crude phenol; the resin bed set is used for removing carbonyl impurities in crude phenol.
And (3) detecting a phenol product:
the method comprises the following steps: the crystallization point of phenol was measured (GB/T339), and the moisture content of the phenol product was measured by Karl Fischer method (see Allied V-17-FR).
As a result: the crystallization point of phenol was 40.81 ℃ and the phenol moisture content was 162 PPm.
Example 2
A method for improving the quality of phenol products, which is different from the method in the embodiment 1:
And (3) detecting a phenol product:
the method comprises the following steps: the crystallization point of phenol was measured (GB/T339), and the moisture content of the phenol product was measured by Karl Fischer method (see Allied V-17-FR).
As a result: the crystallization point of phenol was 40.81 ℃ and the phenol moisture content was 191 PPm.
Example 3
In order to solve the problem of phenol oxidation, ensure that the appearance of a phenol product does not change color for a long time, and ensure that the crystallization point is greater than 40.8 ℃, five corrosion inhibitors with the crystallization point of more than 40.8 ℃ are selected in the embodiment, 0.5 g of each corrosion inhibitor is added into 1000g of phenol product for test, and the specific test data is as shown in table one:
Phenol corrosion inhibitor 48 hours test
Phenol corrosion inhibitor 72 hour test
From the above test results, it can be seen that the addition of 2-hydroxypropane-1, 2, 3-tricarboxylic acid (citric acid) to phenol effectively keeps the phenol product from discoloring for a long time and the crystallization point is stabilized to 40.8 ℃ or higher. Therefore, the technical problem that phenol is easy to discolor can be effectively solved by adding the corrosion inhibitor (citric acid, 500 g is added in each ton of phenol) into the finished phenol product.
Comparative example 1
A method for upgrading phenol, which differs from example 1 in that: step 3, pumping the tower bottom liquid of the alpha-methyl styrene tower to a resin bed group through an alpha-methyl styrene tower bottom pump, and treating by using the resin bed group; the resin bed group comprises 2 sub-resin beds which are connected in series and contain resin Xfj-02D (T-311), the sub-resin beds are all wet-based resin with the water content of 40-50%, the inlet temperature of the sub-resin beds is controlled at 90-110 ℃, the resin content of the first sub-resin bed and the second sub-resin bed is 2 tons, and the ratio of the phenol feeding amount to the dry resin amount on each sub-resin bed is 3.
The mass spectrograms of the resin bed groups before and after analysis are shown in FIGS. 2 and 5, the chromatograms are shown in FIGS. 3 and 6, and the impurity compositions are shown in Table 1.
TABLE 1 resin bed set front and rear impurity composition
The results show that: after resin adsorption, 2-methylbenzofuran is not eliminated, and heavy component indene is changed very little; therefore, the resin bed group for removing carbonyl impurities in phenol has low treatment efficiency and high content of characteristic substance 2-methylbenzofuran.
Comparative example 2
A method for upgrading phenol, which differs from example 1 in that: step 2, cooling the tower top material of the tar tower by a tar tower adjusting cooler and a tar tower cooler, entering a tar tower receiving tank, and entering an alpha-methyl styrene (AMS) tower from a tower top pump of the tar tower; wherein the reflux quantity of the top of the alpha-methyl styrene tower is controlled to be 25m3The temperature at the top of the column was controlled at 130 ℃ per hour.
And (3) detecting a phenol product:
the method comprises the following steps: the crystallization point of phenol was measured (GB/T339), and the moisture content of the phenol product was measured by Karl Fischer method (see Allied V-17-FR).
As a result: the phenol crystallization point was 40.4 ℃ and the phenol moisture content was 396 PPm.
Claims (2)
1. A method for improving the quality of phenol products is characterized by comprising the following steps:
step 1, pumping crude phenol from the bottom of a crude acetone tower to a cumene topping tower through a tower bottom pump when the cumene method is used for producing phenol-acetone, adding methyl pentamethylene diamine into a chemical processor by a chemical injection pump to the bottom of the cumene topping tower, and pumping the bottom of the cumene topping tower to a tar tower through the tower bottom pump;
step 2, cooling the tower top material of the tar tower by a tar tower adjusting cooler and a tar tower cooler, entering a tar tower receiving tank, and entering the alpha-methyl styrene tower by a tar tower top pump; wherein the reflux quantity of the top of the alpha-methyl styrene tower is controlled to be 20-23m3Per hour, top of the columnThe temperature is controlled to be 135-138 ℃;
step 3, pumping the tower bottom liquid of the alpha-methyl styrene tower to a resin bed group through an alpha-methyl styrene tower bottom pump, and treating by using the resin bed group; the resin bed group comprises 3 sub-resin beds which are connected in series and filled with resin of Xfj-02D (T-311), wherein the sub-resin beds are all wet base resin with the water content of 40-50%, the inlet temperature of the sub-resin beds is controlled to be 90-110 ℃, the resin filled in the first sub-resin bed and the second sub-resin bed is 2 tons, and the resin filled in the third sub-resin bed is 4.5 tons; the ratio of the phenol feed to the dry resin on each sub-resin bed was 3;
4, feeding the material from the third sub-resin bed into a phenol rectifying tower, and extracting a product phenol from a side line of the phenol rectifying tower, wherein the crystallization point of the phenol is more than 40.8 ℃, and the water content is less than 200 PPm;
step 5, adding a corrosion inhibitor into the phenol product, storing the phenol product into a phenol product tank, wherein the phenol product is kept from changing color for a long time by adding the corrosion inhibitor, and the crystallization point is stable and reaches above 40.8 ℃; the corrosion inhibitor is 2-hydroxypropane-1, 2, 3-tricarboxylic acid, and the weight ratio of the corrosion inhibitor to phenol is 1: 2000.
2. The method of claim 1, wherein the cumene topping column is used to remove cumene from the crude phenol, and the tar column is used to remove tar from the crude phenol; the AMS tower is used for removing AMS in crude phenol; the resin bed set is used for removing carbonyl impurities in crude phenol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010979796.5A CN112079691A (en) | 2020-09-17 | 2020-09-17 | Method for improving quality of phenol product |
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| CN202010979796.5A CN112079691A (en) | 2020-09-17 | 2020-09-17 | Method for improving quality of phenol product |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114797999A (en) * | 2022-04-08 | 2022-07-29 | 英颇瑞智能科技(上海)有限公司 | Method for prolonging service life of phenol refined resin in phenol-acetone synthesis |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1155879A (en) * | 1994-06-06 | 1997-07-30 | 联合讯号公司 | Phenol with low levels of methylbenzofuran |
| CN102060653A (en) * | 2002-12-16 | 2011-05-18 | 埃克森美孚化学专利公司 | Co-production of phenol, acetone, alpha-methylstyrene and propylene oxide, and catalyst therefor |
| CN105669383A (en) * | 2016-03-10 | 2016-06-15 | 张殿豪 | Method for removing acid in phenol-acetone device decomposition liquid |
| CN107848925A (en) * | 2015-10-22 | 2018-03-27 | 株式会社Lg化学 | Phenol purifying method |
| CN109534952A (en) * | 2018-12-17 | 2019-03-29 | 实友化工（扬州）有限公司 | A kind of phenol preparation method can reduce by-product tar yield |
| CN110156570A (en) * | 2019-07-10 | 2019-08-23 | 东莞三江港口储罐有限公司 | The method for preventing and treating phenol xanthochromia |
-
2020
- 2020-09-17 CN CN202010979796.5A patent/CN112079691A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1155879A (en) * | 1994-06-06 | 1997-07-30 | 联合讯号公司 | Phenol with low levels of methylbenzofuran |
| CN102060653A (en) * | 2002-12-16 | 2011-05-18 | 埃克森美孚化学专利公司 | Co-production of phenol, acetone, alpha-methylstyrene and propylene oxide, and catalyst therefor |
| CN107848925A (en) * | 2015-10-22 | 2018-03-27 | 株式会社Lg化学 | Phenol purifying method |
| CN105669383A (en) * | 2016-03-10 | 2016-06-15 | 张殿豪 | Method for removing acid in phenol-acetone device decomposition liquid |
| CN109534952A (en) * | 2018-12-17 | 2019-03-29 | 实友化工（扬州）有限公司 | A kind of phenol preparation method can reduce by-product tar yield |
| CN110156570A (en) * | 2019-07-10 | 2019-08-23 | 东莞三江港口储罐有限公司 | The method for preventing and treating phenol xanthochromia |
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| Title |
|---|
| 姜国玉: "苯酚产品质量改进的研究", 《吉林省第八届科学学技术学术年会论文集》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114797999A (en) * | 2022-04-08 | 2022-07-29 | 英颇瑞智能科技(上海)有限公司 | Method for prolonging service life of phenol refined resin in phenol-acetone synthesis |
| CN114797999B (en) * | 2022-04-08 | 2023-11-10 | 英颇瑞智能科技(上海)有限公司 | Method for prolonging service life of phenol refined resin in phenol-acetone synthesis |
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