CN109970686B - Method for removing aldehyde ketone ester impurities in epoxypropane reaction liquid by using low-temperature plasma modified material - Google Patents
Method for removing aldehyde ketone ester impurities in epoxypropane reaction liquid by using low-temperature plasma modified material Download PDFInfo
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- CN109970686B CN109970686B CN201910342529.4A CN201910342529A CN109970686B CN 109970686 B CN109970686 B CN 109970686B CN 201910342529 A CN201910342529 A CN 201910342529A CN 109970686 B CN109970686 B CN 109970686B
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- C07—ORGANIC CHEMISTRY
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- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
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Abstract
The invention provides a method for removing aldehyde ketone ester impurities in a propylene oxide reaction liquid, wherein free amino is introduced on the surface of a material by using a low-temperature plasma modification method, so that the aldehyde ketone ester impurities in the propylene oxide reaction liquid can be effectively removed, the removal rate of the aldehyde ketone ester impurities is over 95 percent, the process is simple, and the loss of propylene oxide is low.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and relates to a method for removing aldehyde ketone ester impurities in epoxypropane reaction liquid by using a low-temperature plasma modified material.
Background
Propylene Oxide (PO) is the second largest Propylene derivative next to polypropylene, is a very important basic organic chemical raw material, is mainly used for producing polyether polyol to further produce polyurethane, and can also be used for producing Propylene glycol, allyl alcohol, isopropanolamine and the like. The existing industrial production methods mainly comprise a chlorohydrin method, a co-oxidation method (Halcon method) and a hydrogen peroxide direct oxidation method (HPPO method). The HPPO method takes a titanium-silicon molecular sieve as a catalyst, uses hydrogen peroxide to directly epoxidize propylene to synthesize the propylene oxide, overcomes the defects of serious corrosion of chloropropanol method equipment, more waste liquid and waste residue and the like, does not have the disadvantage of more co-oxidation method combined products, and is a method for producing the propylene oxide with clean process and environment-friendliness.
The propylene oxide produced by the HPPO process has high hydrogen peroxide conversion rate and propylene oxide selectivity, but the process usually uses a large amount of methanol as a solvent, and a small amount of aldehyde ketone ester impurities (formaldehyde, acetaldehyde, propionaldehyde, acetone, methyl formate and the like) are inevitably generated in the product. The propylene oxide is mainly used for producing polyether polyol and further used for producing polyurethane foam materials, and the application requires that the content of aldehyde ketone ester impurities in the propylene oxide is required to be lower than 100ppm, and the boiling point of the aldehyde ketone ester impurities is close to that of the propylene oxide, so that the aldehyde ketone ester impurities and the propylene oxide are difficult to be thoroughly separated by using a common rectification method.
In the prior art, methods such as multistage rectification, adsorption separation, solvent hydrogenation and the like are mostly adopted to remove aldehyde ketone ester impurities in the HPPO process. Multistage rectification is a conventional method for removing aldehyde ketone ester impurities in the HPPO process, but the method has the advantages of high energy consumption, low efficiency, high separation loss and high production cost. Patent CN01804651.7 discloses a method for refining propylene oxide product by using polar solvent such as water for extractive distillation, but aldehyde ketone ester impurities cannot be effectively removed. Patent CN200380103986.5 discloses a method for extractive distillation of propylene oxide by using a compound containing unsubstituted amine groups, which can effectively remove aldehyde ketone impurities in the product, but hydrazone products generated by the compound and aldehyde ketone generate high nitrogen-containing wastewater, which is difficult to treat. Patent CN201180017377.2 discloses a method for removing aldehyde in propylene oxide by using amine functional resin, patent CN201110434173.0 discloses a method for removing aldehyde ketone by using alkaline resin, patent CN201610115263.6 discloses a method for removing aldehyde impurities by using resin and ethanolamine/hydrazine hydrate combination, but propylene oxide has a certain swelling effect on high polymer resin, so that the problems of high propylene oxide loss, resin strength reduction and breakage are caused. Patent CN201610473450.1 discloses a method for adsorbing propylene oxide aldehyde impurities by using a modified molecular sieve, which overcomes the problem of resin swelling, but is affected by the adsorption efficiency of the molecular sieve, and the regeneration is frequent.
GB/T14491-2015 industrial propylene oxide makes clear requirements on the content of aldehyde impurities in the propylene oxide (qualified products are less than or equal to 200ppm, superior products are less than or equal to 50ppm), and even less than or equal to 10ppm in a few high-end applications. In industrial production, the aldehyde ketone ester impurities in the HPPO reaction liquid are often as high as 100-2000ppm, and the product quality can be ensured only by effectively removing the impurities in the reaction liquid.
Disclosure of Invention
The low-temperature plasma modification is to use non-polymeric gas (N) under the condition of applied voltage2、O2、CO H2、Ar、NH3Etc.) breakdown of molecules and convert-NH2and-OH group or ion is introduced into the surface of the material. The newly introduced and generated free radicals can also be connected with some molecules on the surface of the material in a chemical bonding mode to change the surface property of the material, so that the material obtains new surface property. When a sample is treated by low-temperature plasma, various active particles collide with the surface of a material in the modes of radiation, particle flow and the like, and the processes of energy exchange, charge transfer, molecular decomposition or recombination, electron adsorption and the like are generated, so that the corresponding physical or chemical reaction of the surface of the material is caused, and the chemical crosslinking or reaction effect is generated on the surface of the material, thereby achieving the purpose of changing the surface property of the material. Moreover, the low-temperature plasma only acts on the surface of the material to a plurality of nanometer depths, and does not damage the material substrate, so the method is suitable for modifying the surface of the material
The invention aims to provide a method for removing aldehyde ketone ester impurities in an epoxy propane reaction liquid, wherein free amino is introduced to the surface of a material by using a low-temperature plasma modification method, so that the aldehyde ketone ester impurities in the epoxy propane reaction liquid can be effectively removed, and the removal rate of the aldehyde ketone ester impurities is over 95 percent.
The invention provides a method for removing aldehyde ketone ester impurities in propylene oxide reaction liquid by using a low-temperature plasma modified material, which specifically comprises the following steps:
(1) putting a material to be modified into a cavity of a low-temperature plasma treatment instrument, closing a cavity opening, opening a vacuum pump, vacuumizing until the vacuum degree in the cavity is reduced to below 50Pa, opening a gas flow valve, introducing modified gas, then opening a high-frequency power supply, treating for a period of time at a certain power, opening the cavity, and taking out the modified material;
(2) and (3) loading the material modified by the low-temperature plasma into a fixed bed reactor, pumping the epoxypropane reaction liquid in the HPPO process into the fixed bed reactor at a certain temperature and pressure at a certain airspeed, and removing impurities such as aldehyde ketone esters in the epoxypropane reaction liquid.
The material to be modified in the step (1) is an organic polymer material or an inorganic material, preferably one or a combination of more of polyethylene, polypropylene, polytetrafluoroethylene, polyurethane, silicon carbide, activated carbon, silicon dioxide, ceramic, alumina and the like;
the modified gas in the step (1) is nitrogen and ammonia, and the molar ratio of the nitrogen to the ammonia is 1: (4-6);
the low-temperature plasma modification power in the step (1) is 60-200W, and the modification time is 60-600 s;
the temperature of the fixed bed reactor in the step (2) is 20-80 ℃, and the pressure is 0.1-3 MPa;
the airspeed of the epoxypropane reaction liquid passing through the fixed bed reactor in the step (2) is 1-10 h-1；
Compared with the prior art, the invention has the following advantages:
(1) the removal rate is high: according to the invention, the low-temperature plasma modified material is used for removing aldehyde ketone ester impurities in the epoxypropane reaction liquid, free amino on the surface of the modified material can act with the aldehyde ketone ester impurities, and the removal rate of the aldehyde ketone ester impurities is over 95%.
(2) Low loss of propylene oxide: the material modified by the low-temperature plasma has good anti-propylene oxide swelling performance, and the loss of propylene oxide is low in the process of removing aldehyde ketone ester impurities.
(3) The process is simple: the invention adopts the fixed bed reactor to be filled with the low-temperature plasma modified material to remove the aldehyde ketone ester impurities in the propylene oxide, and has simple process and strong operability.
Detailed Description
The following examples are intended to illustrate the invention in more detail, but are not intended to limit the invention further. In the above description, "%" is "% by mass" unless otherwise specified.
The preparation process of the propylene oxide reaction solution containing the aldehyde ketone ester impurities comprises the following steps: simultaneously pumping hydrogen peroxide, propylene and a solvent methanol into a fixed bed reactor filled with a titanium-silicon molecular sieve in a molar ratio of 1:3.5:10, and controlling the reaction temperature to be 35 ℃ and the pressure to be 3.5MPa to obtain a reaction solution. The reaction liquid contains unreacted propylene, water, a small amount of unreacted hydrogen peroxide, solvent methanol, propylene oxide, formaldehyde, acetaldehyde, propionaldehyde, methylal, acetone, methyl formate and other impurities. The reaction liquid is separated from propylene and then enters a fixed bed reactor filled with a low-temperature plasma modified material, wherein the propylene oxide content in the reaction liquid is 17.50 percent, the formaldehyde content is 23ppm, the acetaldehyde content is 395ppm, the propionaldehyde content is 17ppm, the acetone content is 14ppm, the methylal content is 16ppm, the methyl formate content is 25ppm, and the total content of aldehyde ketone ester impurities is 500 ppm.
Example 1 preparation of Low temperature plasma modified Material
(1) Low temperature plasma modified polyethylene
Putting polyethylene into a low-temperature plasma treatment instrument cavity, closing a cavity opening, opening a vacuum pump, vacuumizing until the vacuum degree in the cavity is reduced to below 50Pa, opening a nitrogen and ammonia gas flow valve, and controlling the mole ratio of introduced nitrogen and ammonia to be 1: and 4, turning on a high-frequency power supply, and treating for 500s under the condition of 80W to obtain the modified polyethylene material.
(2) Low-temperature plasma modified polytetrafluoroethylene
Putting polytetrafluoroethylene into a low-temperature plasma treatment instrument cavity, closing a cavity opening, opening a vacuum pump, vacuumizing until the vacuum degree in the cavity is reduced to below 50Pa, opening a nitrogen and ammonia gas flow valve, and controlling the mole ratio of introduced nitrogen and ammonia to be 1: and 5, turning on a high-frequency power supply, and processing for 360s under the condition of 120W to obtain the modified polytetrafluoroethylene material.
(3) Low-temperature plasma modified activated carbon
Putting activated carbon into a cavity of a low-temperature plasma treatment instrument, closing a cavity opening, opening a vacuum pump, vacuumizing until the vacuum degree in the cavity is reduced to below 50Pa, opening a nitrogen and ammonia gas flow valve, and controlling the mole ratio of introduced nitrogen and ammonia to be 1: and 5, turning on a high-frequency power supply, and treating for 200s under the condition of 160W to obtain the modified activated carbon material.
(4) Low-temperature plasma modified silicon carbide
Putting silicon carbide into a low-temperature plasma treatment instrument cavity, closing a cavity opening, opening a vacuum pump, vacuumizing until the vacuum degree in the cavity is reduced to below 50Pa, opening a nitrogen and ammonia gas flow valve, and controlling the mole ratio of introduced nitrogen and ammonia to be 1: and 6, turning on a high-frequency power supply, and treating for 100s under the condition of 200W to obtain the modified silicon carbide material.
Example 2 removal of aldehyde ketone ester impurities from propylene oxide reaction liquid
The four low-temperature plasma modified materials prepared in the example 1 are filled into a fixed bed reactor, and the propylene oxide reaction liquid of the HPPO process is filled at the mass space velocity of 8h at the temperature of 40 ℃ and the pressure of 1.5MPa-1The propylene oxide concentration and the aldehyde ketone ester impurity content in the discharged reaction liquid of the fixed bed are detected in the fixed bed reactor filled with the low-temperature plasma modified material, the service life of the modified material is evaluated (the inactivation index is that the removal rate of the aldehyde ketone ester impurities is lower than 95%), and the experimental results are shown in table 1.
TABLE 1 results of removing aldehyde ketone ester impurities from propylene oxide reaction solution by using low-temperature plasma modified material
The invention is not limited to the embodiments of the invention described.
The structure and the implementation of the present invention are described herein by using specific examples, and the above description of the examples is only used to help understand the core idea of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (4)
1. A method for removing aldehyde ketone ester impurities in propylene oxide reaction liquid by using a low-temperature plasma modified material comprises the following steps:
(1) putting a material to be modified into a cavity of a low-temperature plasma treatment instrument, closing a cavity opening, opening a vacuum pump, vacuumizing until the vacuum degree in the cavity is reduced to below 50Pa, opening a gas flow valve, introducing modified gas, then opening a high-frequency power supply, treating for a period of time at a certain power, opening the cavity, and taking out the modified material;
(2) the material modified by the low-temperature plasma is loaded into a fixed bed reactor, propylene oxide reaction liquid in the HPPO process is pumped into the fixed bed reactor at a certain temperature and pressure and a certain airspeed to remove aldehyde ketone ester impurities in the propylene oxide reaction liquid,
the material to be modified in the step (1) is an organic polymer material or an inorganic material, the organic polymer material is selected from one or more of polyethylene, polypropylene, polytetrafluoroethylene and polyurethane, the inorganic material is selected from one or more of silicon carbide, silicon dioxide, ceramic and alumina, the modifying gas in the step (1) is nitrogen and ammonia, and the molar ratio of the nitrogen to the ammonia is 1: (4-6).
2. The method for removing the aldehyde ketone ester impurities in the propylene oxide reaction solution by using the low-temperature plasma modified material as claimed in claim 1, wherein the low-temperature plasma modification power in the step (1) is 60-200W, and the modification time is 60-600 s.
3. The method for removing the aldehyde ketone ester impurities in the propylene oxide reaction solution by using the low-temperature plasma modified material as claimed in claim 1, wherein the temperature of the fixed bed reactor in the step (2) is 20-80 ℃, and the pressure is 0.1-3 Mpa.
4. The method for removing the aldehyde ketone ester impurities in the propylene oxide reaction solution by using the low-temperature plasma modified material as claimed in claim 1, wherein the space velocity of the propylene oxide reaction solution passing through the fixed bed reactor in the step (2) is 1-10 h-1。
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| US4772732A (en) * | 1986-05-08 | 1988-09-20 | Basf Corporation | Method for purification of butylene oxide |
| US5187287A (en) * | 1992-02-20 | 1993-02-16 | Arco Chemical Technology, L.P. | Lower alkylene oxide purification |
| EP1424332A1 (en) * | 2002-11-26 | 2004-06-02 | Degussa AG | Process for the purification of crude propene oxide |
| CN101549281A (en) * | 2009-04-08 | 2009-10-07 | 南京师范大学 | Method for improving adsorption property of active carbon fiber to formaldehyde |
| US8080678B2 (en) * | 2010-04-01 | 2011-12-20 | Lyondell Chemical Technology, L.P. | Purification of propylene oxide |
| CN106117165B (en) * | 2016-06-27 | 2019-03-22 | 中触媒新材料股份有限公司 | A kind of purification process of propylene oxide |
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