CN109970686A - A kind of method of aldehyde ketone ester impurities in low-temperature plasma modified material removal propylene oxide reaction solution - Google Patents
A kind of method of aldehyde ketone ester impurities in low-temperature plasma modified material removal propylene oxide reaction solution Download PDFInfo
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- CN109970686A CN109970686A CN201910342529.4A CN201910342529A CN109970686A CN 109970686 A CN109970686 A CN 109970686A CN 201910342529 A CN201910342529 A CN 201910342529A CN 109970686 A CN109970686 A CN 109970686A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
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- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
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- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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Abstract
The present invention provides a kind of method of aldehyde ketone ester impurities removing in propylene oxide reaction solution, access free amino on the surface of the material using low-temperature plasma modified method, the aldehyde ketone ester impurities in propylene oxide reaction solution can effectively be removed, 95% or more aldehyde ketone ester impurities removal efficiency, simple process, propylene oxide loss are low.
Description
Technical field
The invention belongs to technical field of petrochemical industry, and it is anti-to be related to a kind of low-temperature plasma modified material removal propylene oxide
The method for answering aldehyde ketone ester impurities in liquid.
Background technique
Propylene oxide (Propylene Oxide, PO) is to be only second to the polyacrylic second largest acryloyl derivative, is very heavy
The basic organic chemical raw material wanted mainly for the production of polyether polyol, and then manufactures polyurethane, it may also be used for production the third two
Alcohol, propenyl, isopropanolamine etc..Existing industrialized preparing process mainly includes chlorohydrination, conjugated oxidation (Halcon method) and mistake
Hydrogen oxide direct oxidation method (HPPO method).HPPO method uses hydrogen peroxide Direct Epoxidation propylene using Titanium Sieve Molecular Sieve as catalyst
Synthesizing epoxypropane, overcomes chloropropyl alcohol method equipment seriously corroded, and waste liquid, the disadvantages of waste residue is more, also there is no conjugated oxidations to join
Disadvantage more than product is the method for a kind of cleaning of technique, environmental-friendly production propylene oxide.
HPPO technique, which produces propylene oxide, has very high hydrogen peroxide conversion ratio and propylene oxide selectivity, but the technique is logical
A large amount of methanol is often used as solvent, inevitably generated in product a small amount of aldehyde ketone ester impurities (formaldehyde, acetaldehyde,
Propionic aldehyde, acetone, methyl formate etc.).And propylene oxide is mainly for the production of polyether polyol, and then for producing polyurethane foam
Material, aldehyde ketone ester impurities content has to be lower than 100ppm in these application requirement propylene oxide, and these aldehyde ketone ester impurities
Boiling point is close with propylene oxide, it is difficult to thoroughly be separated them with propylene oxide with the method for conventional distillation.
The prior art mostly uses multistage rectification, adsorbing separation, solvent to add the aldehyde ketone ester in the methods of hydrogen removing HPPO technique
Class impurity.Multistage rectification be remove HPPO technique in aldehyde ketone ester impurities conventional method, but this method high energy consumption and efficiency it is low,
Separation loss is high, high production cost.Patent CN01804651.7 discloses a kind of mode with water isopolarity solvent extraction rectifying
To the method that product propylene is refined, but it can not effectively remove aldehyde ketone ester impurities.Patent CN200380103986.5
A kind of method with the compound extracting rectifying propylene oxide containing unsubstituted amido is disclosed, this method can effectively remove product
Middle aldehyde ketone impurity, but the hydrazone class product that the compound and aldehyde ketone generate, generate high nitrogenous effluent, it is difficult to handle.Patent
CN201180017377.2 discloses a kind of method with aldehyde in amino-functionalization resin removing propylene oxide, patent
CN201110434173.0 discloses a kind of method with basic resin removing aldehyde ketone, and patent CN201610115263.6 is disclosed
A method of aldehyde type impurities being removed with resin and ethanol amine/hydrazine hydrate combination, but propylene oxide has one to macromolecule resin
Determine swelling action, causes high propylene oxide loss, mechanical strength of resin reduction and broken problem.Patent CN201610473450.1 is public
A kind of method with modified molecular screen absorption propylene oxide aldehyde type impurities is opened, although the problem of the method overcome resin swellings,
But it is influenced by molecular sieve adsorption efficiency, regeneration is frequent.
" the industrial propylene oxide of GB/T 14491-2015 ", which is made that the aldehyde type impurities content in propylene oxide, clearly to be wanted
It asks (qualified product≤200ppm, high-class product≤50ppm), even requirement≤10ppm in a few high-end application.And in industrial production,
HPPO reaction solution aldehyde ketone ester impurities are often as high as 100-2000ppm, it is necessary to effectively be removed to the impurity in reaction solution
It just can ensure that product quality.
Summary of the invention
Low-temperature plasma modified is under conditions of using applied voltage by polymeric gas (N2、O2、CO H2、Ar、
NH3Deng) molecule breakdown, and by-NH2, the groups such as-OH or ion introduce the method for modifying of material surface.It newly introduces and newly generated
Free radical changes the surface property of material on can also being connected by chemical bonding mode with some molecules of material surface,
So that material obtains new surface property.When with Low Temperature Plasma Treating sample, various active particles can pass through radiation, particle
The modes such as stream and material surface collide, and the processes such as energy exchange, electric charge transfer, molecule decomposition or compound, electron adsorption occur, draw
The corresponding physics of material surface or chemical reaction are played, chemical crosslinking or reagentia is generated on the surface of the material, changes to reach
Become the purpose of material surface property.And low temperature plasma acts only on several nm deeps of material surface, to material base
Matter not will cause damage, therefore be suitable for material surface modifying
The object of the present invention is to provide the methods that aldehyde ketone ester impurities in a kind of propylene oxide reaction solution remove, and use low temperature
The method of plasma modification accesses free amino on the surface of the material, can effectively remove the aldehyde ketone in propylene oxide reaction solution
Ester impurities, 95% or more aldehyde ketone ester impurities removal efficiency.
Aldehyde ketone ester impurities in a kind of low-temperature plasma modified material removal propylene oxide reaction solution provided by the invention
Method, specifically includes the following steps:
(1) material to be modified is put into low-temperature plasma processing instrument cavity, closes cavity mouth, open vacuum pump, taken out true
After vacuum degree is down to 50Pa or less in sky to cavity, gas flow valve is opened, is passed through modified gas, then open high frequency electric source,
After handling a period of time under certain power, cavity is opened, takes out the material that is modified；
(2) by it is above-mentioned it is low-temperature plasma modified after material be fitted into fixed bed reactors, by the ring in HPPO technique
Ethylene Oxide reaction solution is pumped into above-mentioned fixed bed reactors with certain air speed under certain temperature and pressure, removes epoxy third
The impurity such as the aldehyde ketone esters in alkane reaction solution.
Material to be modified described in above-mentioned steps (1) is high-molecular organic material or inorganic material, preferably be selected from polyethylene,
One of polypropylene, polytetrafluoroethylene (PTFE), polyurethane, silicon carbide, active carbon, silica, ceramics and aluminium oxide etc. are a variety of
Combination；
Modified gas described in above-mentioned steps (1) is nitrogen and ammonia, molar ratio 1:(4~6 of nitrogen and ammonia)；
The modified power of low-temperature plasma described in above-mentioned steps (1) is 60~200W, and modification time is 60~600s；
The temperature of fixed bed reactors described in above-mentioned steps (2) is 20~80 DEG C, and pressure is 0.1~3MPa；
The air speed that propylene oxide reaction solution described in above-mentioned steps (2) passes through fixed bed reactors is 1~10h-1；
Compared with prior art, the present invention having the advantage that
(1) removal efficiency is high: the present invention uses the aldehyde in low-temperature plasma modified material removal propylene oxide reaction solution
The free amine group of ketone ester impurities, modified material surface can be acted on aldehyde ketone ester impurities, aldehyde ketone ester impurities removal efficiency
95% or more.
(2) propylene oxide loss is low: the material after low-temperature plasma modified has good anti-propylene oxide swelling behavior,
During removing aldehyde ketone ester impurities, propylene oxide loss is low.
(3) simple process: the present invention loads low-temperature plasma modified material removal epoxy third using fixed bed reactors
Aldehyde ketone ester impurities in alkane, simple process, strong operability.
Specific embodiment
The following examples are illustrated in more detail the present invention, rather than limitation of the invention further.It removes
Non- to be otherwise noted, " % " therein is " quality % ".
Propylene oxide reaction solution preparation process in the present invention containing aldehyde ketone ester impurities is as follows: by hydrogen peroxide, propylene and
Solvent methanol is pumped into the fixed bed reactors for being filled with Titanium Sieve Molecular Sieve simultaneously with the ratio of molar ratio 1:3.5:10, and control is anti-
To answer temperature be 35 DEG C, pressure 3.5MPa, obtains reaction solution.It is complete comprising unreacted propylene, water, a small amount of unreacted in reaction solution
Hydrogen peroxide, solvent methanol, propylene oxide and formaldehyde, acetaldehyde, propionic aldehyde, dimethoxym ethane, acetone, the impurity such as methyl formate.It is above-mentioned anti-
Liquid is answered to enter in the fixed bed reactors of low-temperature plasma modified mixture after propylene separation, reaction solution oxypropylene
Content 17.50%, content of formaldehyde 23ppm, acetaldehyde 395ppm, propionic aldehyde content 17ppm, content of acetone 14ppm, dimethoxym ethane
16ppm, methyl formate 25ppm, total aldehyde ketone ester impurities content are 500ppm.
Embodiment 1 prepares low-temperature plasma modified material
(1) low-temperature plasma modified polyethylene
Polyethylene is put into low-temperature plasma processing instrument cavity, cavity mouth is closed, vacuum pump is opened, is evacuated to cavity
After interior vacuum degree is down to 50Pa or less, nitrogen and ammonia gas flow valve are opened, control is passed through nitrogen and the molar ratio of ammonia is
1:4, then high frequency electric source is opened, after handling 500s under the conditions of 80W, obtain modified polythene material.
(2) low-temperature plasma modified polytetrafluoroethylene (PTFE)
Polytetrafluoroethylene (PTFE) is put into low-temperature plasma processing instrument cavity, cavity mouth is closed, vacuum pump is opened, is evacuated to
After vacuum degree is down to 50Pa or less in cavity, nitrogen and ammonia gas flow valve are opened, control is passed through mole of nitrogen and ammonia
Than for 1:5, then high frequency electric source is opened, after handling 360s under the conditions of 120W, obtains modified polytetrafluoroethylene material.
(3) low-temperature plasma modified active carbon
Active carbon is put into low-temperature plasma processing instrument cavity, cavity mouth is closed, vacuum pump is opened, is evacuated to cavity
After interior vacuum degree is down to 50Pa or less, nitrogen and ammonia gas flow valve are opened, control is passed through nitrogen and the molar ratio of ammonia is
1:5, then high frequency electric source is opened, after handling 200s under the conditions of 160W, obtain modified absorbent charcoal material.
(4) low-temperature plasma modified silicon carbide
Silicon carbide is put into low-temperature plasma processing instrument cavity, cavity mouth is closed, vacuum pump is opened, is evacuated to cavity
After interior vacuum degree is down to 50Pa or less, nitrogen and ammonia gas flow valve are opened, control is passed through nitrogen and the molar ratio of ammonia is
1:6, then high frequency electric source is opened, after handling 100s under the conditions of 200W, obtain modified carbofrax material.
Embodiment 2 removes the aldehyde ketone ester impurity in propylene oxide reaction solution
By the four kinds of low-temperature plasma modified mixtures prepared in embodiment 1 into fixed bed reactors, by HPPO
The propylene oxide reaction solution of technique, with mass space velocity 8h at 40 DEG C, 1.5MPa-1By being equipped with low-temperature plasma modified material
Fixed bed reactors in, detection fixed bed discharging reaction solution oxypropylene concentration and aldehyde ketone ester impurities content, evaluation change
Property material service life (inactivation index be aldehyde ketone ester impurities removal efficiency be lower than 95%), experimental result is shown in Table 1.
Aldehyde ketone ester impurity result in the low-temperature plasma modified material removal propylene oxide reaction solution of table 1
Content of the present invention is not limited in embodiment content of the present invention.
Specific case used herein is expounded structure of the invention and embodiment, the explanation of above embodiments
It is merely used to help understand the core idea of the present invention.It should be pointed out that for those skilled in the art,
Without departing from the principles of the invention, can be with several improvements and modifications are made to the present invention, these improvement and modification are also fallen
Enter in the protection scope of the claims in the present invention.
Claims (8)
1. a kind of method of aldehyde ketone ester impurities in low-temperature plasma modified material removal propylene oxide reaction solution, including it is following
Step:
(1) material to be modified is put into low-temperature plasma processing instrument cavity, closes cavity mouth, opened vacuum pump, be evacuated to
After vacuum degree is down to 50Pa or less in cavity, gas flow valve is opened, modified gas is passed through, then open high frequency electric source, certain
Power under handle a period of time after, open cavity, taking-up is modified material；
(2) by it is above-mentioned it is low-temperature plasma modified after material be fitted into fixed bed reactors, by the epoxy third in HPPO technique
Alkane reaction solution is pumped into above-mentioned fixed bed reactors with certain air speed under certain temperature and pressure, and removing propylene oxide is anti-
Answer the impurity such as the aldehyde ketone esters in liquid.
2. aldehyde ketone esters in a kind of low-temperature plasma modified material removal propylene oxide reaction solution according to claim 1
The method of impurity, which is characterized in that the material to be modified in the step (1) is high-molecular organic material or inorganic material.
3. aldehyde ketone esters in a kind of low-temperature plasma modified material removal propylene oxide reaction solution according to claim 2
The method of impurity, which is characterized in that the high-molecular organic material is in polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyurethane
One or more combinations.
4. aldehyde ketone esters in a kind of low-temperature plasma modified material removal propylene oxide reaction solution according to claim 2
The method of impurity, which is characterized in that the inorganic material is in silicon carbide, active carbon, silica, ceramics and aluminium oxide
One or more combinations.
5. aldehyde ketone esters in a kind of low-temperature plasma modified material removal propylene oxide reaction solution according to claim 1
The method of impurity, which is characterized in that modified gas described in the step (1) is nitrogen and ammonia, and nitrogen and ammonia rub
You are than 1:(4~6).
6. aldehyde ketone esters in a kind of low-temperature plasma modified material removal propylene oxide reaction solution according to claim 1
The method of impurity, which is characterized in that the modified power of low-temperature plasma described in the step (1) is 60~200W, when modified
Between be 60~600s.
7. aldehyde ketone esters in a kind of low-temperature plasma modified material removal propylene oxide reaction solution according to claim 1
The method of impurity, which is characterized in that the temperature of fixed bed reactors described in the step (2) is 20~80 DEG C, and pressure is
0.1~3Mpa.
8. aldehyde ketone esters in a kind of low-temperature plasma modified material removal propylene oxide reaction solution according to claim 1
The method of impurity, which is characterized in that the air speed that propylene oxide reaction solution described in the step (2) passes through fixed bed reactors
For 1~10h-1。
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| CN201910342529.4A CN109970686B (en) | 2019-04-26 | 2019-04-26 | Method for removing aldehyde ketone ester impurities in epoxypropane reaction liquid by using low-temperature plasma modified material |
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Citations (6)
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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 |
| CN1714087A (en) * | 2002-11-26 | 2005-12-28 | 德古萨股份公司 | 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 |
| CN102884055A (en) * | 2010-04-01 | 2013-01-16 | 莱昂德尔化学技术公司 | Purification of propylene oxide |
| CN106117165A (en) * | 2016-06-27 | 2016-11-16 | 中触媒新材料股份有限公司 | A kind of purification process of expoxy propane |
-
2019
- 2019-04-26 CN CN201910342529.4A patent/CN109970686B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1714087A (en) * | 2002-11-26 | 2005-12-28 | 德古萨股份公司 | 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 |
| CN102884055A (en) * | 2010-04-01 | 2013-01-16 | 莱昂德尔化学技术公司 | Purification of propylene oxide |
| CN106117165A (en) * | 2016-06-27 | 2016-11-16 | 中触媒新材料股份有限公司 | A kind of purification process of expoxy propane |
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