CN103121981A - Method for preparing epoxypropane through propylene liquid phase oxidation - Google Patents
Method for preparing epoxypropane through propylene liquid phase oxidation Download PDFInfo
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- CN103121981A CN103121981A CN2011103697057A CN201110369705A CN103121981A CN 103121981 A CN103121981 A CN 103121981A CN 2011103697057 A CN2011103697057 A CN 2011103697057A CN 201110369705 A CN201110369705 A CN 201110369705A CN 103121981 A CN103121981 A CN 103121981A
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- propylene
- phase oxidation
- propylene oxide
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- peroxide
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a method for preparing epoxypropane through propylene liquid phase oxidation and mainly aims to solve the problem that no alpha-MoO3 crystals with exposed high-activity specific crystal faces, which can be used for the reaction for preparing epoxypropane through propylene liquid phase oxidation, are disclosed in the prior art. The problem is better solved by using the technical scheme that an organic peroxide and propylene serving as raw materials come into contact with a catalyst to generate epoxypropane in the presence of a solvent and under the conditions that the molar ratio of the propylene to the organic peroxide is 5 to 10, the reaction temperature ranges from 60 DEG C to 110 DEG C and the reaction pressure ranges from 0.8MPa to 3MPa, wherein the catalyst is of an orthorhombic crystal system and is a alpha-MoO3 crystal with exposed high-activity crystal faces which are a (100) and (010) crystal faces, and the addition amount of the catalyst is calculated according to the molar ratio of molybdenum to the organic peroxide being 1/100 to 5/100. The method can be used for industrial production of epoxypropane prepared through propylene liquid phase oxidation.
Description
Technical field
The present invention relates to the method for a kind of propylene liquid-phase oxidation propylene oxide processed.
Background technology
Propylene oxide is very important basic organic chemical industry raw material, is the second largest derivative of propylene.The purposes of propylene oxide maximum is for the production of polyether glycol, accounts for 60% of its total quantity consumed, further processes important intermediate-urethane that polyether glycol can be produced synthetic plastics and fiber.In recent years, the urethane demand sharply increases the significantly increase that has also caused the propylene oxide demand.The second largest purposes of propylene oxide is for the production of propylene glycol, alcohol ether, propylene carbonate, and then can make storage tank, bathroom fittings, shell etc.
The existing production technique of propylene oxide is mainly chlorohydrination and conjugated oxidation (claiming again peroxidation method or indirect oxidation method).Wherein, Mo is catalyst based has important purposes in co-oxidation legal system propylene oxide process.Molybdenum is a kind of very important transition metal, has the excellent performance such as high-melting-point, high conductivity, high strength.Two kinds of form MoO are arranged in the oxide compound of molybdenum
2And MoO
3, wherein, α-MoO
3Crystalline form is the most stable.Molybdenum oxide is a kind of broad stopband N-shaped semi-conductor, can be used as catalyzer in the reaction that some aerobics participate in.Molybdenum element has the very strong ability of appraising at the current rate, and therefore, in Selective Oxidation, the molybdenum based compound has good catalytic performance.In addition, the oxide compound of molybdenum has excellent optics, electrochromism, catalysis, surface tissue and electrical property, has broad application prospects in fields such as catalyzer, sensor, flat-panel monitor, smart window, electrochromic devices.
For heterogeneous catalyst, the outside surface of catalyzer is the generation place of catalyzed reaction.Therefore, specific high reactivity outside surface crystal can significantly improve catalyst utilization and reaction efficiency.Document (Nature 458 (2009), 746) has been introduced outside surface for { the cobalt oxide nano bar-shape structure of 110} crystal face, wherein, { the 110} crystal face has the active Co of high density
3+, this crystal face is the high reactivity crystal face in the CO oxidizing reaction.This cobalt oxide material is in the very high CO conversion rate of the lower demonstration of low temperature (77 ℃).
Summary of the invention
Technical problem to be solved by this invention is the unexposed α-MoO with specific high reactivity crystal face exposure of prior art
3Crystal can be used for the reaction of propylene liquid-phase oxidation propylene oxide processed, and a kind of method of new propylene liquid-phase oxidation propylene oxide processed is provided.The method has the high characteristics of propylene oxide selectivity.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the method for a kind of propylene liquid-phase oxidation propylene oxide processed, take organo-peroxide and propylene as raw material, under solvent exists, be 5～10 at propylene and organo-peroxide mol ratio, temperature of reaction is 60～110 ℃, and reaction pressure is under the condition of 0.8～3MPa, and reaction raw materials contacts with catalyzer and generates propylene oxide; Wherein, described catalyzer is α-MoO that rhombic system, high reactivity crystal face expose
3Crystal, described high reactivity crystal face are (100) and (010) crystal face; The add-on of catalyzer is take molybdenum/organo-peroxide mol ratio as 1/100～5/100.
In technique scheme, described catalyzer pattern is the cubic club shaped structure of homogeneous, and single cubic club shaped structure length is 1～10 μ m, and wide is 100～200nm, and height is 20～40nm; Described cubic club shaped structure is the growth of [001] direction, and outside surface is (100) and (010) crystal face of rhombic system.Described organo-peroxide preferred version is for being selected from ethylbenzene hydroperoxide or isopropyl benzene hydroperoxide.Described solvent preferred version is for being selected from ethylbenzene or isopropyl benzene.The weight ratio preferable range of solvent and organo-peroxide is 1/2～1/5.
In the present invention, the preparation method of catalyzer used comprises the following steps: inorganic molybdenum source is dissolved in the superoxol of acidic solution or 30 % by weight; Molybdenum solution after the dissolving is under 150～180 ℃ fully, and hydrothermal recrystallization method 24～48 hours obtains described oxidation catalyst of cyclopropene through separating, washing; Wherein, described inorganic molybdenum source is selected from least a in molybdenum oxide or Ammonium Heptamolybdate, and described acidic solution is selected from hydrochloric acid or nitric acid.
α-the MoO of the inventive method by adopting rhombic system, high reactivity crystal face to expose
3Crystal is epoxidation catalyst, be 1/6 at propylene and hydrogen phosphide cumene mol ratio, the consumption of catalyzer is take molybdenum/organo-peroxide mol ratio as 2/100, under 90 ℃ of conditions, reaction is 2 hours, the transformation efficiency of hydrogen phosphide cumene (CHP) is 97%, propylene oxide is 57% to the selectivity of CHP, and the selectivity of propylene has obtained technique effect preferably more than 99%.
Description of drawings
Fig. 1 is the XRD figure spectrum of not isomorphous system alpha-molybdenum oxide.
Fig. 2 is the scanning electron microscope (SEM) photograph of bar-shaped side, nanometer four directions.
Fig. 3 is the scanning electron microscope (SEM) photograph of the cubic club shaped structure of nanometer.
Fig. 4 is the two-dimensional crystal lattice schematic diagram of (100) crystal face in the rhombic system alpha-molybdenum oxide.
Fig. 5 is the two-dimensional crystal lattice schematic diagram of (010) crystal face in the rhombic system alpha-molybdenum oxide.
In Fig. 1, a is the XRD figure spectrum of hexagonal system alpha-molybdenum oxide, and b is the XRD figure spectrum of rhombic system alpha-molybdenum oxide in the present invention.In the rhombic system alpha-molybdenum oxide, the position of 12 ° of diffraction peaks and intensity change, and this is representing that rhombic system molybdenum oxide (010) crystal face and hexagonal system distinguish to some extent; In addition, certain variation all appears in the highest peak in the rhombic system alpha-molybdenum oxide and time strong peak, and this is to be the club shaped structure of monocrystalline due to the rhombic system alpha-molybdenum oxide, has special crystal face exposure, thereby causes the crystal face diffraction peak to change a lot.
In Fig. 2, demonstration be the scanning electron microscope (SEM) photograph of bar-shaped side, nanometer four directions, this side is (100) outside surface of rhombic system alpha-molybdenum oxide, width is 40nm.
In Fig. 3, demonstration be the scanning electron microscope (SEM) photograph of nanometer four directions club shaped structure, illustrate that rhombic system alpha-molybdenum oxide single crystal structure grows with [001] direction.
In Fig. 4, show the two-dimensional crystal lattice schematic diagram of (100) crystal face in the rhombic system alpha-molybdenum oxide.Wherein, bead represents the Mo atom, large ball represention oxygen atom.The lattice size is
The lattice angle is 90 °.
In Fig. 5, show the two-dimensional crystal lattice schematic diagram of (010) crystal face in the rhombic system alpha-molybdenum oxide.Wherein, bead represents the Mo atom, large ball represention oxygen atom.The lattice size is
The lattice angle is 90 °.
The present invention is further elaborated below by embodiment, but application of the present invention is not subjected to the restriction of these embodiment.
Embodiment
[embodiment 1]
Commodity molybdenum oxide powder joins 30%H
2O
2Solution in, then stirring at room 3 days is got 70 ml solns and is transferred in hydrothermal reaction kettle, keeps 24 hours at 180 ℃ of baking ovens.Then take out, centrifugation is adopted deionized water wash 3 times, and then washing with alcohol is 3 times, and oven drying at low temperature obtains white powder.
[embodiment 2]
The hydrochloric acid of 2M is dropwise joined in Ammoniun Heptamolybdate Solution, and then stirring at room 3 days is got 70 ml solns and is transferred in hydrothermal reaction kettle, keeps 24 hours at 180 ℃ of baking ovens.Then take out, centrifugation is adopted deionized water wash 3 times, and then washing with alcohol is 3 times, and oven drying at low temperature obtains white powder.
[embodiment 3]
Commodity molybdenum oxide powder joins 30%H
2O
2Solution in, then stirring at room 3 days adds 2 gram macroporous silica gels, 50 ℃ were stirred 2 hours, got 70 ml solns and transferred in hydrothermal reaction kettle, kept 24 hours at 180 ℃ of baking ovens.Then take out, centrifugation is adopted deionized water wash 3 times, and then washing with alcohol is 3 times, and oven drying at low temperature obtains white powder.
[embodiment 4]
The above-mentioned molybdenum oxide catalyst that compression molding is good is got 1.0 grams, carries out the epoxidation of propylene evaluation and test.
The activity of catalyzer adopts method described below to estimate: be that 27.2% isopropyl benzene hydroperoxide (CHP) 190 grams, solvent (isopropyl benzene) 90 grams and 1.0 gram catalyzer join in the PARR autoclave of 1 liter with weight fraction, then pass through the high-pressure liquid propylene to autoclave, propylene/CHP mol ratio is 2/100, then be heated to certain temperature, and keep certain reaction times.After reaction finished, product analysis was divided into two parts, and by online Agilent6820 gas chromatographic analysis, the pillar that uses is the polar column of DB-WAX to a part of product under condition of high voltage; Another part product passes through the transformation efficiency of titration measuring superoxide under condition of normal pressure.
Evaluation result sees Table 1.Wherein, transformation efficiency is the transformation efficiency of dicumyl peroxide, and the selectivity of propylene oxide is calculated with the dicumyl peroxide effective rate of utilization.
[comparative example]
With [embodiment 4], just used catalyst is business product molybdenum oxides.The results are shown in Table 1.
Table 1
Claims (5)
1. the method for a propylene liquid-phase oxidation propylene oxide processed, take organo-peroxide and propylene as raw material, under solvent exists, be 5～10 at propylene and organo-peroxide mol ratio, temperature of reaction is 60～110 ℃, reaction pressure is under the condition of 0.8～3MPa, and reaction raw materials contacts with catalyzer and generates propylene oxide; Wherein, described catalyzer is α-MoO that rhombic system, high reactivity crystal face expose
3Crystal, described high reactivity crystal face are (100) and (010) crystal face; The add-on of catalyzer is take molybdenum/organo-peroxide mol ratio as 1/100～5/100.
2. the method for propylene liquid-phase oxidation propylene oxide processed according to claim 1, is characterized in that described catalyzer pattern is the cubic club shaped structure of homogeneous, and single cubic club shaped structure length is 1～10 μ m, and wide is 100～200nm, and height is 20～40nm; Described cubic club shaped structure is the growth of [001] direction, and outside surface is (100) and (010) crystal face of rhombic system.
3. the method for propylene liquid-phase oxidation propylene oxide processed according to claim 1, is characterized in that described organo-peroxide is selected from ethylbenzene hydroperoxide or isopropyl benzene hydroperoxide.
4. the method for propylene liquid-phase oxidation propylene oxide processed according to claim 1, is characterized in that described solvent is selected from ethylbenzene or isopropyl benzene.
5. the method for propylene liquid-phase oxidation propylene oxide processed according to claim 1, the weight ratio that it is characterized in that solvent and organo-peroxide is 1/2～1/5.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230854A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Cumyl hydroperoxide and propylene epoxidation method for preparing epoxypropane |
| CN104557787A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing epoxy chloropropane |
| CN104557781A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing propylene oxide |
| CN104557780A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of epoxypropane |
| CN104557779A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Production method of epoxy propane |
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| US5349072A (en) * | 1993-07-06 | 1994-09-20 | Texaco Chemical Company | Staged epoxidation of propylene with recycle |
| CN1762831A (en) * | 2005-09-01 | 2006-04-26 | 武汉理工大学 | Molybdenum trioxide laminated nanometer bar and preparation method |
| CN101497045A (en) * | 2009-03-11 | 2009-08-05 | 华东理工大学 | Catalyst for producing epoxypropane by liquid phase one-step oxidation of propylene and preparation method |
| CN102139227A (en) * | 2011-02-25 | 2011-08-03 | 华东理工大学 | Catalyst for preparing epoxy propane by propylene liquid-phase epoxidation reaction and preparation method thereof |
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2011
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Patent Citations (4)
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| US5349072A (en) * | 1993-07-06 | 1994-09-20 | Texaco Chemical Company | Staged epoxidation of propylene with recycle |
| CN1762831A (en) * | 2005-09-01 | 2006-04-26 | 武汉理工大学 | Molybdenum trioxide laminated nanometer bar and preparation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230854A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Cumyl hydroperoxide and propylene epoxidation method for preparing epoxypropane |
| CN104557787A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing epoxy chloropropane |
| CN104557781A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing propylene oxide |
| CN104557780A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of epoxypropane |
| CN104557779A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Production method of epoxy propane |
| CN104557787B (en) * | 2013-10-28 | 2017-04-19 | 中国石油化工股份有限公司 | Method for preparing epoxy chloropropane |
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