CN116462589A - Treatment method of byproduct tar in cyclohexyl methacrylate production - Google Patents

Treatment method of byproduct tar in cyclohexyl methacrylate production Download PDF

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Publication number
CN116462589A
CN116462589A CN202310436228.4A CN202310436228A CN116462589A CN 116462589 A CN116462589 A CN 116462589A CN 202310436228 A CN202310436228 A CN 202310436228A CN 116462589 A CN116462589 A CN 116462589A
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reaction
tar
ozone
hydrogen
mixed gas
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郑京涛
温道宏
曹文健
刘若楠
梁海涛
商先永
李俊平
乔小飞
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/30Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/675Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/716Esters of keto-carboxylic acids or aldehydo-carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00Systems containing only non-condensed rings
    • C07C2601/12Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14The ring being saturated
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a method for treating byproduct tar in the production of cyclohexyl methacrylate, which can decompose the tar into cyclohexyl 2-oxo-propionate and cyclohexyl 2-hydroxy-propionate through ozone oxidation reaction and hydrogenation reaction, thereby improving the added value of the product.

Description

Treatment method of byproduct tar in cyclohexyl methacrylate production
Technical Field
The invention relates to the field of chemical synthesis, in particular to a method for treating tar as a byproduct in the production of cyclohexyl methacrylate.
Background
The cyclohexyl methacrylate is a special methacrylate monomer with a special structure, the structure of the cyclohexyl methacrylate contains a cyclic group and double bonds, and the cyclohexyl methacrylate can be used as a monomer or a comonomer for solution polymerization or suspension polymerization, and a polymerization product of the cyclohexyl methacrylate has the advantages of high refractive index, excellent water resistance, wear resistance, chemical resistance, heat resistance, low shrinkage, high hardness and the like, so the cyclohexyl methacrylate is used as an active cross-linking agent and a diluent with excellent quality and has been widely applied to the aspects of automobile shell coating, solvent-based coating, high-solid coating, powder coating, water-soluble resin, polymeric flocculant, textile auxiliary agent, petroleum pour point depressant, medical material and the like.
The main process of industrial production of the cyclohexyl methacrylate is that the cyclohexyl methacrylate is directly obtained by transesterification of methyl methacrylate and cyclohexanol, the product separation is refined by a rectifying tower, the cyclohexyl methacrylate is easy to polymerize at high temperature, tar containing the cyclohexyl methacrylate can be produced in the high-temperature rectifying process, the reduction of the product yield and the increase of raw material unit consumption are caused, about 800 tons of waste tar is produced by a production device of 10000 tons/year cyclohexyl methacrylate as an example, the components are difficult to separate and recycle by conventional rectification due to complex components and higher boiling points, and the waste tar is generally burnt and treated industrially, so that great waste is caused.
How to recycle tar and improve the added value of the process is a problem to be solved at present.
Disclosure of Invention
The invention aims to provide a method for treating tar which is a byproduct in the production of cyclohexyl methacrylate, which breaks carbon-carbon double bonds of a cyclohexyl methacrylate polymer by adopting ozone oxidation, hydrogenation and other modes to generate products such as high-added-value 2-oxo-cyclohexyl propionate, 2-hydroxy-cyclohexyl propionate and the like, so that the tar production amount is greatly reduced, and the added value of the products is improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for treating byproduct tar in the production of cyclohexyl methacrylate comprises the following steps:
(1) Adding a solvent into tar, and uniformly mixing;
(2) Introducing ozone-oxygen mixed gas into the solution until the reaction is complete;
(3) Stopping introducing the ozone-oxygen mixed gas, and replacing by adopting a reaction inert gas;
(4) The reaction liquid after ozone oxidation reacts with hydrogen in the presence of a catalyst.
In the invention, the tar is the tar containing the polymethyl methacrylate which is generated in the rectification process of the rectifying tower after the transesterification reaction of the methyl methacrylate and the cyclohexanol.
In the invention, in the step (1), the solvent is one or more of benzene, toluene, xylene or ethylbenzene, and the mass ratio of the solvent to tar is 1-15:1, preferably 3-10:1;
in the step (2), the mass fraction of ozone in the ozone-oxygen mixed gas is 3-15%, and the mass fraction of oxygen is 85-97%; the reaction is carried out at normal pressure and 10-50 ℃.
In the invention, in the step (2), the reaction tail gas is connected with an ozone gas concentration detector, and the ozone concentration is unchanged and represents complete reaction.
In the invention, in the step (3), the reaction inert gas is continuously introduced into the solution for replacement until ozone and formaldehyde are not detected in the tail gas, and the replacement is completed.
In the present invention, the reaction is preferably performed with nitrogen.
In the invention, in the step (4), the catalyst is a palladium-carbon catalyst, and the content of palladium accounts for 1-10% of the mass of the catalyst, preferably 4-10%;
in the step (4), the reaction temperature is 10-50 ℃, preferably 20-40 ℃;
in the step (4), the reaction pressure is 2-10MPaG; preferably 3-8MPaG;
in the step (4), the feeding mass space velocity of the reaction liquid is 0.3-3h -1 The hydrogen is preferably added in the form of a mixed gas of hydrogen and nitrogen, and the volume space velocity of the mixed gas of hydrogen and nitrogen is 50-500h -1 The mass fraction of the hydrogen in the mixed gas is 20-60%.
In the invention, the reaction liquid can remove the solvent through rectification, and further rectification is carried out to obtain the pure products of the cyclohexyl 2-oxo-propionate and the cyclohexyl 2-hydroxy-propionate.
The invention has the beneficial effects that:
1. the invention solves the problem that byproduct waste tar can not be utilized in the production of cyclohexyl methacrylate. 60% -80% of tar can be converted into 2-oxo-cyclohexyl propionate and 2-hydroxy cyclohexyl propionate with high added values through the steps of ozonization, hydrogenation and the like, and the recycling rate of the tar is high, so that the method is economical and environment-friendly.
2. The invention can adjust the reaction conditions such as the addition amount of hydrogen, airspeed and the like according to the requirements, and the reaction is carried out under the conditions of high reaction flexibility and convenient operation.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification, and to any novel one, or any novel combination, of the steps of the method or process disclosed.
1. The main raw material sources in the examples are:
1. waste tar: a pilot plant for cyclohexyl methacrylate of Wanhua chemical group Co., ltd is prepared through transesterification of methyl methacrylate and cyclohexanol, and rectifying the tar containing cyclohexyl methacrylate by rectifying tower.
2. Ozone is oxygen which is self-made by an ozone generator;
3. palladium carbon catalyst: liaoning Heitai technology development Co.Ltd
4. Toluene, analytical grade, the company of the sciences, west Long;
5. ethylbenzene, analytical grade, the company of the sciences, cyLong, inc.;
2. product analysis method in the examples:
1. gas chromatography is used for analyzing the components and contents of reaction liquid and products, and correction factor method is used, and instrument manufacturer and model are: island fluid 1020-plus.
Example 1
Preparing benzene solution of waste tar, wherein the mass of benzene is 3 times of that of tar. Mixing uniformly, mixing ozone and oxygenAnd introducing a gas mixture (wherein the mass fraction of ozone is 10% and the mass fraction of oxygen is 90%) into the solution, wherein the reaction pressure is normal pressure, the reaction temperature is 50 ℃, and the ventilation is stopped when the ozone concentration detector detects that the ozone concentration in the reaction tail gas is unchanged. And (3) introducing nitrogen into the solution until no ozone and formaldehyde are detected in the tail gas. Continuously introducing the intermediate solution subjected to ozone oxidation into a fixed bed reactor, and continuously introducing a mixed gas of hydrogen and nitrogen (the mass fraction of the hydrogen in the mixed gas is 20%), wherein a catalyst used by the fixed bed is a palladium-carbon catalyst, the palladium content is 4%, the reaction temperature is 20 ℃, the reaction pressure is 3MPa, and the mass airspeed of the reaction solution is 0.3h -1 The volume space velocity of hydrogen and nitrogen is 50h -1 . And rectifying the reacted liquid, and removing the solvent to obtain the 2-oxo-propionic acid cyclohexyl ester and the 2-hydroxy-propionic acid cyclohexyl ester, wherein a small amount of tar is not reacted.
2-Oxopropionic acid cyclohexyl ester
Hydrogen spectrum: 1 H NMR(500MHz,CDCl 3 )δ7.43(m,2H),7.29(m,3H),2.17(s,3H).
carbon spectrum: 13 C NMR(125MHz,CDCl 3 )δ197.73,158.95,151.26,129.74,125.77,121.64,25.04.
2-Hydroxypropionic acid cyclohexyl ester
Hydrogen spectrum: 1 H NMR(500MHz,CDCl 3 )δ7.47–7.33(m,3H),7.08(dd,J=7.4,1.4Hz,2H),4.29(q,J=5.8Hz,1H),2.60(s,1H),1.50(d,J=5.8Hz,3H).
carbon spectrum: 13 C NMR(125MHz,CDCl 3 )δ173.86,151.17,129.88,125.58,122.09,66.87,19.83.
the specific results of the reaction are shown in Table 1;
example 2
Preparing benzene solution of waste tar, wherein the quality of ethylbenzene is 10 times of that of tar. After mixing uniformly, introducing mixed gas of ozone and oxygen (wherein the mass fraction of ozone is 15% and the mass fraction of oxygen is 85%) into the solution, wherein the reaction pressure is normal pressure, the reaction temperature is 10 ℃, and when the ozone concentration detector detects that the ozone concentration in the reaction tail gas is unchanged, stopping ventilation. Nitrogen is introduced into the solution to ensure that,until no ozone and formaldehyde are detected in the tail gas. Continuously introducing the intermediate solution subjected to ozone oxidation into a fixed bed reactor, and continuously introducing a mixed gas of hydrogen and nitrogen (the mass fraction of the hydrogen in the mixed gas is 60%), wherein a catalyst used by the fixed bed is a palladium-carbon catalyst, the palladium content is 10%, the reaction temperature is 40 ℃, the reaction pressure is 8MPa, and the mass airspeed of the reaction solution is 3h -1 The volume space velocity of hydrogen and nitrogen is 500h -1 . And rectifying the reacted liquid, removing the solvent, and obtaining the cyclohexyl 2-oxo-propionate and cyclohexyl 2-hydroxy-propionate, wherein a small amount of tar is not reacted. The specific results of the reaction are shown in Table 1;
example 3
Preparing benzene solution of waste tar, wherein the mass of toluene is 5 times of that of the tar. After uniformly mixing, introducing mixed gas of ozone and oxygen (wherein the mass fraction of ozone is 7.5 percent and the mass fraction of oxygen is 92.5 percent) into the solution, wherein the reaction pressure is normal pressure, the reaction temperature is 30 ℃, and when the ozone concentration detector detects that the ozone concentration in the reaction tail gas is unchanged, stopping ventilation. And (3) introducing nitrogen into the solution until no ozone and formaldehyde are detected in the tail gas. Continuously introducing the intermediate solution subjected to ozone oxidation into a fixed bed reactor, and continuously introducing a mixed gas of hydrogen and nitrogen (the mass fraction of the hydrogen in the mixed gas is 50%), wherein a catalyst used by the fixed bed is a palladium-carbon catalyst, the palladium content is 8%, the reaction temperature is 30 ℃, the reaction pressure is 6MPa, and the mass airspeed of the reaction solution is 3h -1 The volume space velocity of hydrogen and nitrogen is 250h -1 . And rectifying the reacted liquid, removing the solvent, and obtaining the cyclohexyl 2-oxo-propionate and cyclohexyl 2-hydroxy-propionate, wherein a small amount of tar is not reacted. The specific results of the reaction are shown in Table 1;
example 4
Preparing benzene solution of waste tar, wherein the mass of toluene is 6 times of that of the tar. After being uniformly mixed, the mixed gas of ozone and oxygen (wherein the mass fraction of the ozone is 5 percent and the mass fraction of the oxygen is 95 percent) is introduced into the solution, the reaction pressure is normal pressure, the reaction temperature is 30 ℃, and an ozone concentration detector detects that the concentration of the ozone in the reaction tail gas is unchangedWhen this occurs, ventilation is stopped. And (3) introducing nitrogen into the solution until no ozone and formaldehyde are detected in the tail gas. Continuously introducing the intermediate solution subjected to ozone oxidation into a fixed bed reactor, and continuously introducing a mixed gas of hydrogen and nitrogen (the mass fraction of the hydrogen in the mixed gas is 50%), wherein a catalyst used by the fixed bed is a palladium-carbon catalyst, the palladium content is 5%, the reaction temperature is 30 ℃, the reaction pressure is 4MPa, and the mass airspeed of the reaction solution is 1h -1 The volume space velocity of hydrogen and nitrogen is 250h -1 . And rectifying the reacted liquid, removing the solvent, and obtaining the cyclohexyl 2-oxo-propionate and cyclohexyl 2-hydroxy-propionate, wherein a small amount of tar is not reacted. The specific results of the reaction are shown in Table 1;
example 5
Preparing benzene solution of waste tar, wherein the quality of ethylbenzene is 7 times of that of tar. After uniformly mixing, introducing mixed gas of ozone and oxygen (wherein the mass fraction of ozone is 5% and the mass fraction of oxygen is 95%) into the solution, wherein the reaction pressure is normal pressure, the reaction temperature is 25 ℃, and when the ozone concentration detector detects that the ozone concentration in the reaction tail gas is unchanged, stopping ventilation. And (3) introducing nitrogen into the solution until no ozone and formaldehyde are detected in the tail gas. Continuously introducing the intermediate solution subjected to ozone oxidation into a fixed bed reactor, and continuously introducing a mixed gas of hydrogen and nitrogen (the mass fraction of the hydrogen in the mixed gas is 40%), wherein a catalyst used by the fixed bed is a palladium-carbon catalyst, the palladium content is 5%, the reaction temperature is 30 ℃, the reaction pressure is 4MPa, and the mass airspeed of the reaction solution is 1.8h -1 The volume space velocity of hydrogen and nitrogen is 150h -1 . And rectifying the reacted liquid, removing the solvent, and obtaining the cyclohexyl 2-oxo-propionate and cyclohexyl 2-hydroxy-propionate, wherein a small amount of tar is not reacted. The specific results of the reaction are shown in Table 1;
example 6
Preparing benzene solution of waste tar, wherein the mass of toluene is 10 times of that of the tar. After being uniformly mixed, the mixed gas of ozone and oxygen (wherein the mass fraction of the ozone is 5 percent and the mass fraction of the oxygen is 95 percent) is introduced into the solution, the reaction pressure is normal pressure, the reaction temperature is 35 ℃, and the ozone concentration is detectedAnd stopping ventilation when the instrument detects that the concentration of ozone in the reaction tail gas is unchanged. And (3) introducing nitrogen into the solution until no ozone and formaldehyde are detected in the tail gas. Continuously introducing the intermediate solution subjected to ozone oxidation into a fixed bed reactor, and continuously introducing a mixed gas of hydrogen and nitrogen (the mass fraction of the hydrogen in the mixed gas is 35%), wherein a catalyst used by the fixed bed is a palladium-carbon catalyst, the palladium content is 5%, the reaction temperature is 30 ℃, the reaction pressure is 6MPa, and the mass airspeed of the reaction solution is 2.5h -1 The volume space velocity of hydrogen and nitrogen is 100h -1 . And rectifying the reacted liquid, removing the solvent, and obtaining the cyclohexyl 2-oxo-propionate and cyclohexyl 2-hydroxy-propionate, wherein a small amount of tar is not reacted. The specific results of the reaction are shown in Table 1.
TABLE 1 Tar conversion and selectivity to various products for the examples
Sequence number Conversion% Cyclohexyl 2-oxopropionate selectivity% Cyclohexane 2-Hydroxypropionate selectivity%
Example 1 78.2 8.9 91.1
Example 2 64.4 10.3 89.7
Example 3 73.7 7.9 92.1
Example 4 75.6 8.6 91.4
Example 5 68.4 11.9 88.1
Example 6 66.9 13.7 86.3

Claims (8)

1. A method for treating byproduct tar in the production of cyclohexyl methacrylate is characterized by comprising the following steps:
(1) Adding a solvent into tar, and uniformly mixing;
(2) Introducing ozone-oxygen mixed gas into the solution until the reaction is complete;
(3) Stopping introducing the ozone-oxygen mixed gas, and replacing by adopting a reaction inert gas;
(4) The reaction liquid after ozone oxidation reacts with hydrogen in the presence of a catalyst.
2. The method according to claim 1, wherein the tar is a tar containing poly (cyclohexyl methacrylate) produced during the transesterification of methyl methacrylate and cyclohexanol and then rectifying the tar through a rectifying tower.
3. The process according to claim 1, wherein in step (1), the solvent is one or more of benzene, toluene, xylene or ethylbenzene and the mass ratio of solvent to tar is 1-15:1, preferably 3-10:1.
4. The method according to claim 1, wherein in the step (2), the mass fraction of ozone in the ozone-oxygen mixed gas is 3 to 15% and the mass fraction of oxygen is 85 to 97%; the reaction is carried out at normal pressure and 10-50 ℃.
5. The treatment method according to claim 1, wherein in the step (3), the reaction inert gas is continuously introduced into the solution for replacement until ozone and formaldehyde are not detected in the tail gas, and the replacement is completed;
preferably, the inert gas is nitrogen.
6. The process according to claim 1, wherein in step (4), the catalyst is palladium on carbon catalyst, and the palladium content is 1-10% by mass, preferably 4-10% by mass.
7. The process according to claim 1, wherein in step (4), the reaction temperature is 10-50 ℃, preferably 20-40 ℃;
preferably, in the step (4), the reaction pressure is 2-10MPaG; preferably 3-8MPaG;
in the step (4), the feeding mass space velocity of the reaction liquid is 0.3-3h -1
8. The process according to claim 1, wherein the hydrogen is added as a mixed gas of hydrogen and nitrogen, and the volume space velocity of the mixed gas of hydrogen and nitrogen is 50 to 500 hours -1 The mass fraction of the hydrogen in the mixed gas is 20-60%.
CN202310436228.4A 2023-04-23 2023-04-23 Treatment method of byproduct tar in cyclohexyl methacrylate production Pending CN116462589A (en)

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