CN103121981B - The method of propylene liquid-phase oxidation propylene oxide - Google Patents
The method of propylene liquid-phase oxidation propylene oxide Download PDFInfo
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- CN103121981B CN103121981B CN201110369705.7A CN201110369705A CN103121981B CN 103121981 B CN103121981 B CN 103121981B CN 201110369705 A CN201110369705 A CN 201110369705A CN 103121981 B CN103121981 B CN 103121981B
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- propylene
- propylene oxide
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- Y—GENERAL 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
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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
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Abstract
The present invention relates to a kind of method of propylene liquid-phase oxidation propylene oxide, mainly solve the unexposed α-MoO that there is specific high reactivity crystal face and expose of prior art
3crystal can be used for the problem of propylene liquid-phase oxidation propylene oxide reaction.The present invention is by adopting with organo-peroxide and propylene as raw material, in the presence of solvent, be 5 ~ 10 at propylene and organo-peroxide mol ratio, temperature of reaction is 60 ~ 110 DEG C, reaction pressure is under the condition of 0.8 ~ 3MPa, and reaction raw materials and catalyst exposure generate propylene oxide; Wherein, described catalyzer is the α-MoO of rhombic system, the exposure of high reactivity crystal face
3crystal, described high reactivity crystal face is (100) and (010) crystal face; The add-on of catalyzer preferably resolves this problem with the technical scheme that molybdenum/organo-peroxide mol ratio is 1/100 ~ 5/100, can be used in the industrial production of propylene liquid-phase oxidation propylene oxide.
Description
Technical field
The present invention relates to a kind of method of propylene liquid-phase oxidation propylene oxide.
Background technology
Propylene oxide is very important basic organic chemical industry raw material, is the second largest derivative of propylene.The maximum purposes of propylene oxide is for the production of polyether glycol, accounts for 60% of its total quantity consumed, and processing polyether glycol can produce the important intermediate-urethane of synthetic plastics and fiber further.In recent years, urethane demand sharply increases the significantly increase that result also in propylene oxide demand.The second largest purposes of propylene oxide is for the production of propylene glycol, alcohol ether, propylene carbonate, and then can manufacture storage tank, bathroom fittings, shell etc.
The existing production technique of propylene oxide is mainly chlorohydrination and conjugated oxidation (also known as 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 performance that high-melting-point, high conductivity, high strength etc. are excellent.Two kinds of form MoO are had 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-type semiconductor, can be used as catalyzer in the reaction that some aerobics participate in.Molybdenum element has very strong ability of appraising at the current rate, and therefore, in Selective Oxidation, 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) describes outside surface for { the cobalt oxide nano bar-shape structure of 110} crystal face, wherein, { 110} crystal face has the active Co of high density
3+, this crystal face is the high reactivity crystal face in CO oxidizing reaction.This cobalt oxide material shows very high CO conversion rate under low temperature (-77 DEG C).
Summary of the invention
Technical problem to be solved by this invention is the unexposed α-MoO having specific high reactivity crystal face and expose of prior art
3crystal can be used for the reaction of propylene liquid-phase oxidation propylene oxide, provides a kind of method of new propylene liquid-phase oxidation propylene oxide.The method has the high feature of propylene oxide selectivity.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of propylene liquid-phase oxidation propylene oxide, with organo-peroxide and propylene for raw material, in the presence of solvent, be 5 ~ 10 at propylene and organo-peroxide mol ratio, temperature of reaction is 60 ~ 110 DEG C, and reaction pressure is under the condition of 0.8 ~ 3MPa, and reaction raw materials and catalyst exposure generate propylene oxide; Wherein, described catalyzer is the α-MoO of rhombic system, the exposure of high reactivity crystal face
3crystal, described high reactivity crystal face is (100) and (010) crystal face; The add-on of catalyzer with molybdenum/organo-peroxide mol ratio for 1/100 ~ 5/100.
In technique scheme, described catalyzer pattern is homogeneous cubic club shaped structure, and single cubic club shaped structure length is 1 ~ 10 μm, 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.
The preparation method of catalyzer used in the present invention comprises the following steps: inorganic molybdenum source is dissolved in acidic solution or 30 % by weight superoxol in; Molybdenum solution after dissolving completely is at 150 ~ 180 DEG C, and hydrothermal recrystallization method 24 ~ 48 hours, obtains described oxidation catalyst of cyclopropene through being separated, washing; Wherein, described inorganic molybdenum source is selected from least one in molybdenum oxide or Ammonium Heptamolybdate, and described acidic solution is selected from hydrochloric acid or nitric acid.
α-the MoO that the inventive method exposes by adopting rhombic system, high reactivity crystal face
3crystal is epoxidation catalyst, be 1/6 at propylene and hydrogen phosphide cumene mol ratio, the consumption of catalyzer is for 2/100 with molybdenum/organo-peroxide mol ratio, react 2 hours under 90 DEG C of conditions, the transformation efficiency of hydrogen phosphide cumene (CHP) is 97%, propylene oxide is 57% to the selectivity of CHP, and the selectivity of propylene, more than 99%, achieves good technique effect.
Accompanying drawing explanation
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 nanometer four directions club shaped structure.
Fig. 4 is the two-dimensional crystal lattice schematic diagram of (100) crystal face in rhombic system alpha-molybdenum oxide.
Fig. 5 is the two-dimensional crystal lattice schematic diagram of (010) crystal face in 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 rhombic system alpha-molybdenum oxide, the position of 12 ° of diffraction peaks and intensity change, and this represents rhombic system molybdenum oxide (010) crystal face and hexagonal system is distinguished to some extent; In addition, all there is certain change in the highest peak in rhombic system alpha-molybdenum oxide and time strong peak, and this is because rhombic system alpha-molybdenum oxide is the club shaped structure of monocrystalline, has special crystal face exposure, thus causes crystallographic plane diffraction peak to change a lot.
In Fig. 2, display be nanometer four directions bar-shaped side scanning electron microscope (SEM) photograph, this side is (100) outside surface of rhombic system alpha-molybdenum oxide, and width is 40nm.
In Fig. 3, display be nanometer four directions club shaped structure scanning electron microscope (SEM) photograph, illustrate that rhombic system alpha-molybdenum oxide single crystal structure grows with [001] direction.
In Fig. 4, the two-dimensional crystal lattice schematic diagram of (100) crystal face in display rhombic system alpha-molybdenum oxide.Wherein, bead represents Mo atom, large ball represention oxygen atom.Lattice size is
lattice angle is 90 °.
In Fig. 5, the two-dimensional crystal lattice schematic diagram of (010) crystal face in display rhombic system alpha-molybdenum oxide.Wherein, bead represents Mo atom, large ball represention oxygen atom.Lattice size is
lattice angle is 90 °.
Below by embodiment, the present invention is further elaborated, but application of the present invention is not by the restriction of these embodiments.
Embodiment
[embodiment 1]
Commodity molybdenum oxide powder joins 30%H
2o
2solution in, stirring at room temperature 3 days, then gets 70 ml solns and transfers in hydrothermal reaction kettle, keeps 24 hours at 180 DEG C of baking ovens.Then take out, centrifugation, adopt deionized water wash 3 times, then washing with alcohol 3 times, oven drying at low temperature obtains white powder.
[embodiment 2]
The hydrochloric acid of 2M is dropwise joined in Ammoniun Heptamolybdate Solution, stirring at room temperature 3 days, then get 70 ml solns and transfer in hydrothermal reaction kettle, keep 24 hours at 180 DEG C of baking ovens.Then take out, centrifugation, adopt deionized water wash 3 times, then washing with alcohol 3 times, oven drying at low temperature obtains white powder.
[embodiment 3]
Commodity molybdenum oxide powder joins 30%H
2o
2solution in, stirring at room temperature 3 days, then adds 2 grams of macroporous silica gels, 50 DEG C stir 2 hours, get 70 ml solns and transfer in hydrothermal reaction kettle, keep 24 hours at 180 DEG C of baking ovens.Then take out, centrifugation, adopt deionized water wash 3 times, then washing with alcohol 3 times, oven drying at low temperature obtains white powder.
[embodiment 4]
Above-mentioned molybdenum oxide catalyst good for compression molding is got 1.0 grams, carries out epoxidation of propylene evaluation and test.
The activity of catalyzer adopts method described below to evaluate: be the isopropyl benzene hydroperoxide (CHP) 190 grams of 27.2% by weight fraction, solvent (isopropyl benzene) 90 grams and 1.0 grams of catalyzer join in the PARR autoclave of 1 liter, then high-pressure liquid propylene is passed through to autoclave, propylene/CHP mol ratio is 2/100, then be heated to certain temperature, and keep certain reaction times.After reaction terminates, product analysis is divided into two parts, a part of product under elevated pressure conditions by online Agilent6820 gas chromatographic analysis, the polar column that the pillar of use is DB-WAX; Another part product is in atmospheric conditions by the transformation efficiency of titration measuring superoxide.
Evaluation result is in table 1.Wherein, transformation efficiency is the transformation efficiency of dicumyl peroxide, and the selectivity of propylene oxide calculates with 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 (1)
1. a method for propylene liquid-phase oxidation propylene oxide, is characterized in that commodity molybdenum oxide powder to join 30%H
2o
2solution in, stirring at room temperature 3 days, then gets 70 ml solns and transfers in hydrothermal reaction kettle, keeps 24 hours at 180 DEG C of baking ovens; Then take out, centrifugation, adopt deionized water wash 3 times, then washing with alcohol 3 times, oven drying at low temperature obtains white powder; Above-mentioned molybdenum oxide catalyst good for compression molding is got 1.0 grams, carries out epoxidation of propylene evaluation and test;
The activity of catalyzer adopts method described below to evaluate: be isopropyl benzene hydroperoxide CHP190 gram of 27.2% by weight fraction, solvent isopropyl benzene 90 grams and 1.0 grams of catalyzer join in the PARR autoclave of 1 liter, then high-pressure liquid propylene is passed through to autoclave, propylene/CHP mol ratio is 2/100, then be heated to 90 DEG C, and keep 2 hours; After reaction terminates, product analysis is divided into two parts, a part of product under elevated pressure conditions by online Agilent6820 gas chromatographic analysis, the polar column that the pillar of use is DB-WAX; Another part product is in atmospheric conditions by the transformation efficiency of titration measuring superoxide;
Wherein, evaluation result is: the transformation efficiency of dicumyl peroxide is 97%, and the selectivity of propylene oxide is calculated as 57% with dicumyl peroxide effective rate of utilization.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| 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 |
| 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 |
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 |
| 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 |
-
2011
- 2011-11-18 CN CN201110369705.7A patent/CN103121981B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| The molybdenum species of MoO3/SiO2 and their catalytic activities for the epoxidation of propylene with cumene hydroperoxide;Yongxia Miao等;《Journal of Industrial and Engineering Chemistry》;20100125;第16卷;第45-50页 * |
| 一维三氧化钼纳米材料的合成、结构与性能研究;祁琰媛;《中国博士学位论文全文数据库 工程科技I辑》;20070630;第29-32、50页 * |
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