CN102850195B - Method for oxidizing propylene - Google Patents
Method for oxidizing propylene Download PDFInfo
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- CN102850195B CN102850195B CN201110183218.1A CN201110183218A CN102850195B CN 102850195 B CN102850195 B CN 102850195B CN 201110183218 A CN201110183218 A CN 201110183218A CN 102850195 B CN102850195 B CN 102850195B
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Abstract
The invention provides a method for oxidizing propylene. The method includes allowing contact of propylene and oxidant under oxidation reaction condition, wherein the oxidant is an ozone-containing gas. The method can oxidize propylene to acrolein without adding catalyst by adopting ozone as oxidant, and the method has simple process, and can well control reaction degree without adding extra initiator and/or inhibitor in the reaction system; and on above basis, the invention has high selectivity of target product.
Description
Technical field
The present invention relates to a kind of method of propylene oxidation.
Background technology
Propenal is the simplest unsaturated aldehyde, and chemical formula is C
3h
4o, be water white liquid under normal conditions, its steam has very strong pungency and tearing property.Propenal can dissolve each other with water section, and under 20 DEG C of conditions, the solubleness of propenal in water is 20.6 % by weight, and the solubleness of water in propenal is 6.8 % by weight.Propenal also can be as miscible in dimethylbenzene, toluene, methyl alcohol, chloroform, ethanol, acetaldehyde, acetic acid, acetone, vinylformic acid, ethyl acetate and paraffinic hydrocarbon (normal hexane, octane, pentamethylene) etc. with majority of organic solvent.Propenal is synthetic intermediate very important in chemical industry, is widely used in production of resins and organic synthesis.Be placed in light and air, or propenal is easily polymerized under strong acid, highly basic exist, generate propylene dimer aldehyde and other products and become translucent yellow sticky solid, therefore propenal generally adds the Resorcinol used as stabilizers of about 0.2% when storing.
Propenal is prepared in the industrial gaseous oxidation mainly through propylene, the method is under bismuth molybdate and BiPMo series catalysts exist, the mixed gas (mol ratio of propylene and oxygen is 6-8: 1) of propylene and air is passed in fixed bed or fluidized-bed reactor, temperature of reaction is 300-400 DEG C, pressure is 0.2-0.3MPa, react except generation propenal, also have a small amount of acetaldehyde, acetic acid, propionic aldehyde, acetone and vinylformic acid to produce.Reaction gas absorbs through cooling, washing, water and after stripping fractionation, just can obtain pure propenal.In addition to the method described above, also have the research of glycerine and sal enixum or boric acid, potassium sulfate, aluminum chloride hot preparation propenal altogether at temperature is 215-235 DEG C.Meanwhile, glycerine being heated to 280 DEG C of decomposition generation propenal is also a kind of method preparing propenal.
As can be seen here, existing acrolein manufacturing processes temperature of reaction high (more than 200 DEG C), and also the catalyzer used (as bismuth molybdate and BiPMo series catalysts) non-ambient is friendly.Therefore, how to develop a kind of can carrying out under lower temperature of reaction, and the environment-friendly method preparing propenal that technique is simple, with low cost, acrolein selectivity is high will be the emphasis direction in the future researched and developed.
Summary of the invention
The object of this invention is to provide a kind of can carrying out under lower temperature of reaction, and technique is simple, with low cost, target product selectivity is high, the method for eco-friendly propylene oxidation.
The above-mentioned variety of problems that the method preparing propenal to overcome prior art exists, the present inventor is through long-term effort, finally find, ozone is adopted to carry out the defects such as propylene oxide can overcome the severe reaction conditions (temperature high, catalyzer non-ambient friendly) of aforementioned existence and target product yield is low as oxygenant, simultaneously, unexpected discovery, when carrying out in the presence of a titanium-containing catalyst, there is significant change in the distribution of reaction product, the selectivity of its oxypropylene is improved largely.The present invention is completed based on this discovery.
The invention provides a kind of method of propylene oxidation, the method comprises, and under oxidation reaction condition, by propylene and oxidising agent, wherein, described oxygenant is the gas containing ozone.
Propylene oxidation can be namely target product as oxygenant without the need to adding catalyzer by adopting ozone by method of the present invention, and the method technological process is simple, just can the degree of good control reaction without the need to introducing extra initiator, inhibitor in reaction system; On the basis of the above, the selectivity of target product of the present invention is also higher.Under preferable case of the present invention, the transformation efficiency of reactant and the yield of target product can be improved further by introducing catalyzer in system; Particularly preferably in situation, adopt preferred catalyst of the present invention, the preferred solvent of the present invention, method of the present invention can improve the transformation efficiency of reactant and the yield of target product further.
Compared to traditional method, method of the present invention has simple, the with low cost and efficiency advantages of higher of technological process.
Embodiment
The invention provides a kind of method of propylene oxidation, the method comprises, and under oxidation reaction condition, by propylene and oxidising agent, wherein, described oxygenant is the gas containing ozone.
Adopt the gas containing ozone as oxygenant according to method of the present invention.(have another name called three atomic oxygens, be commonly called as " good fortune oxygen, super oxygen, oxygen of living ", molecular formula is O to ozone
3), at normal temperatures and pressures, for being nattier blue gas.The present inventor finds in research process, adopt the gas containing ozone directly propylene oxidation can be become target product propenal as oxygenant, and ozone can disintegrate be oxygen at normal temperatures, can not produce and such as use hydrogen peroxide to carry out the shortcoming such as processing to the solution containing hydrogen peroxide as the needs faced during oxygenant.Therefore, according to the inventive method environmental friendliness.
According to method of the present invention, the described gas containing ozone can be ozone, can also be the mixed gas of ozone and diluent gas.According to method of the present invention, the described gas containing ozone is preferably the mixed gas of ozone and diluent gas, can regulate the concentration of ozone easily like this, thus controls the severe degree of reaction better.
In the present invention, when the described gas containing ozone is the mixed gas of ozone and diluent gas, in described mixed gas, the concentration of ozone can carry out appropriate selection according to concrete oxidation reaction condition.Preferably, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 1 more than volume %.More preferably, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 5 more than volume %.Usually, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone can be 5-80 volume %, is preferably 5-50 volume %, is more preferably 5-30 volume %.
The present invention is not particularly limited for the kind of described diluent gas, and described diluent gas can be such as at least one in oxygen, carbonic acid gas, nitrogen, argon gas, helium, neon and air.Preferably, described diluent gas is at least one in oxygen, carbonic acid gas, helium and air.
One according to the present invention preferred embodiment in, the described gas containing ozone is the mixed gas of ozone or ozone and diluent gas, and with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 1 more than volume %, and described diluent gas is at least one in oxygen, carbonic acid gas, nitrogen, argon gas, helium, neon and air.One according to the present invention more preferred embodiment in, with the cumulative volume of described mixed gas for benchmark, in described mixed gas, the content of ozone is 5 more than volume %, and described diluent gas is at least one in oxygen, carbonic acid gas, helium and air.
According to method of the present invention, as long as adopt described ozone can realize object of the present invention as oxygenant, the present invention to the mol ratio of the ozone in described propylene and oxygenant without particular requirement, improve further to make the yield of the transformation efficiency of propylene and target product propenal, under preferable case, the mol ratio of the ozone in described propylene and oxygenant is 1: 0.1-10, is more preferably 1: 0.2-5.
According to method of the present invention, wherein, under preferable case, described contact is carried out in the presence of a titanium-containing catalyst, and in titanium dioxide, the mol ratio of described titanium-containing catalyst and propylene is 1: 0.1-200, is more preferably 1: 1-100, is particularly preferably 1: 1-50.
According to method of the present invention, the present invention to described titanium-containing catalyst without particular requirement, containing titanium in described catalyzer, under preferable case, described titanium-containing catalyst is be selected from least one in molecular sieve containing titanium, the preformed catalyst of molecular sieve containing titanium, amorphous silicon titanium and titanium dioxide, is wherein preferably the preformed catalyst of molecular sieve containing titanium and/or molecular sieve containing titanium.
In order to enable the selectivity of the more effective goal of regulation and control product of method of the present invention and make the transformation efficiency of reactant propylene higher, under preferable case, described molecular sieve containing titanium is the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS of hexagonal structure is (as Ti-MCM-41, Ti-SBA-15), the HTS (as Ti-MOR) of MOR structure, at least one in the HTS (as Ti-TUN) of TUN structure and the HTS (as Ti-ZSM-48) of other structures, be more preferably the HTS (as TS-1) of MFI structure.
More preferably described HTS is MFI structure, and crystal grain is hollow structure, and the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.
According to method of the present invention, under preferable case, described contact is carried out in the presence of solvent, and the mol ratio of propylene and solvent can be 1: 1-150, is preferably 1: 1-80; Described solvent can be at least one in water, alcoholic solvent, ketone solvent, nitrile solvent and organic acid solvent, is preferably at least one in the organic acid solvent of water, the alcoholic solvent of C1-C10, the ketone solvent of C3-C10, the nitrile solvent of C2-C8 and C1-C6; Further, the present inventor finds unexpectedly in research process, when described solvent is at least one in the ketone of water, the nitrile of C2-C6, C3-C8, when being preferably selected from least one in water, acetonitrile, acetone and butanone, can improve further the yield of realize target product.
According to method of the present invention, the present invention is to described oxidation reaction condition without particular requirement, and can be conventional oxidation reaction condition, under preferable case, the temperature that described oxidation reaction condition comprises contact be 0-180 DEG C, is preferably 20-150 DEG C; Pressure is 0.1-3MPa, is preferably 0.1-2MPa; Time is 0.1-10 hour, is preferably 1-5 hour.It should be noted that, when at said temperatures, when can produce required pressure, described pressure can be autogenous pressure, when at said temperatures, when the pressure that described temperature produces does not reach required pressure, described pressure can apply pressure to realize by the external world, this is technology well known in the art, no longer describes in detail at this.
Method provided by the invention, can adopt periodical operation, also can operate continuously etc., and feed way also can be any suitable way well known by persons skilled in the art, and the present invention, does not repeat at this all without particular requirement one by one to this.
Following embodiment will be further described the present invention, but therefore not limit content of the present invention.
In embodiment, if not otherwise specified, used reagent is commercially available analytical reagent.
Ozone used provides for the NLO-15 type ozonizer produced by Fujian New Continent Environmental Protection Technology Co., Ltd, and ozone concn is adjustable, and maximum volume concentration can reach 80%.In following examples if not otherwise specified, source of oxygen is all used to prepare ozone.
In embodiment, HTS (TS-1) catalyzer used is by document [Zeolites, 1992, Vol.12 943-950 page] described in (TS-1) sieve sample of preparing of method, titanium oxide content is 2.5 % by weight.
(Hunan Jian Chang company manufactures the Industrial products of HTS described in hollow HTS HTS former powder system CN1301599A used in embodiment, be the HTS of MFI structure through X-ray diffraction analysis, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, crystal grain is hollow crystal grain and the radical length of chamber portion is 15-180 nanometer; This sieve sample at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recorded under the adsorption time condition of 1 hour is 78 milligrams/gram), titanium oxide content is 2.5 % by weight.
In the present invention, adopt gas-chromatography to carry out the analysis of each composition in system, being undertaken quantitatively, all can refer to prior art and carrying out by correcting normalization method, calculating the evaluation index such as the transformation efficiency of reactant, the selectivity of product on this basis.
In embodiment and comparative example:
Embodiment 1
Temperature be 60 DEG C, under pressure is 0.5MPa, using the mixed gas (ozone concn is 15 volume %) of ozone and oxygen as oxygenant, by propylene, ozone and solvent acetone according to 1: 1: 1 mol ratio send in autoclave and react.React 2 hours: propylene conversion is 42%, propylene oxide selectivity is 11%, acrolein selectivity is 81%.
Embodiment 2
The oxygenant used in the present embodiment is the mixed gas containing ozone, this mixed gas is prepared (wherein by using air as the source of oxygen of ozonizer, with the total amount of this mixed gas for benchmark, the content of ozone is 15 volume %), temperature be 20 DEG C, under pressure is 1.5MPa, by propylene, ozone and solvent butanone according to 1: 1: 5 mol ratio send in autoclave and react.React 5 hours: propylene conversion is 39%, propylene oxide selectivity is 21%, acrolein selectivity is 72%.
Embodiment 3
Temperature be 80 DEG C, under pressure is 0.2MPa, using the mixed gas (ozone concn is 5 volume %) of ozone and oxygen as oxygenant, by propylene, ozone and solvent acetonitrile according to 1: 2: 10 mol ratio send in autoclave and react.React 2 hours: propylene conversion is 46%, propylene oxide selectivity is 16%, acrolein selectivity is 70%.
Embodiment 4
Temperature be 40 DEG C, under pressure is 0.1MPa, using the mixed gas of ozone and oxygen as (ozone concn is 15 volume %) oxygenant, by propylene, ozone and solvent acetone according to 1: 4: 50 mol ratio send in autoclave and react.React 3 hours: propylene conversion is 84%, propylene oxide selectivity is 15%, acrolein selectivity is 74%.
Embodiment 5
The oxygenant used in the present embodiment is the mixed gas containing ozone, this mixed gas is prepared (wherein by using air as the source of oxygen of ozonizer, with the total amount of this mixed gas for benchmark, the content of ozone is 10 volume %), temperature be 50 DEG C, under pressure is 1.0MPa, by propylene, ozone and aqueous solvent according to 1: 0.3: 3 mol ratio send in autoclave and react.The result of reacting 4 hours is as follows: propylene conversion is 18%, propylene oxide selectivity is 21%, acrolein selectivity is 62%.
Embodiment 6
Temperature be 120 DEG C, under pressure is 1.0MPa, with the mixed gas of ozone, carbon dioxide and oxygen, (ozone concn is 10 volume %, all the other are isopyknic carbon dioxide and oxygen) as oxygenant, propylene, ozone and solvent acetone are reacted according in the mol ratio feeding autoclave of 1: 0.7: 25.React 3 hours: propylene conversion is 34%, propylene oxide selectivity is 18%, acrolein selectivity is 71%.
Embodiment 7
Identical with the method for embodiment 6, carry out under TS-1 molecular sieve catalyst exists unlike reaction, and the mol ratio of TS-1 and propylene is 1: 50.
React 3 hours: propylene conversion is 42%; Propylene oxide selectivity is 34%; Acrolein selectivity is 51%.
Embodiment 8
Identical with the method for embodiment 7, replaced by HTS unlike TS-1, react 3 hours: propylene conversion is 45%, propylene oxide selectivity is 38%, acrolein selectivity is 55%.
Embodiment 9
Identical with the method for embodiment 7, unlike, TS-1 by Ti-MCM-41 (according to prior art Corma etc. at Chem.Commun., 1994, method preparation described in 147-148, titanium oxide content is 3 % by weight) replace, react 3 hours: propylene conversion is 29%, propylene oxide selectivity is 21%, acrolein selectivity is 65%.
Embodiment 10
Identical with the method for embodiment 7, unlike, TS-1 by Ti-Beta (according to prior art TakashiTatsumi etc. at J.Chem.Soc.Chem.Commun.1997, method preparation described in 677-678, titanium oxide content is 2.6 % by weight) replace, react 3 hours: propylene conversion is 32%, propylene oxide selectivity is 24%, acrolein selectivity is 63%.
Embodiment 11
Identical with the method for embodiment 7, unlike, TS-1 is by TiO
2(Beijing chemical reagents corporation, Detitanium-ore-type) replaces, and reacts 3 hours: propylene conversion is 38%, propylene oxide selectivity is 24%, acrolein selectivity is 61%.
Embodiment 12
Identical with the method for embodiment 7, unlike, solvent is acetic acid, reacts 3 hours: propylene conversion is 40%, propylene oxide selectivity is 19%, acrolein selectivity is 42%.
Embodiment 13
Identical with the method for embodiment 1, be ethanol unlike solvent, react 3 hours: propylene conversion is 33%, propylene oxide selectivity is 23%, acrolein selectivity is 58%.
Embodiment 14
Identical with the method for embodiment 13, unlike, do not carry out in the presence of solvent, react 3 hours: propylene conversion is 12%, propylene oxide selectivity is 11%, acrolein selectivity is 24%.
Comparative example 1
The method identical with embodiment 7 is adopted to prepare propenal, unlike, use oxygen as oxygenant.React 3 hours: propylene conversion is 4%, propylene oxide selectivity is 3%, acrolein selectivity is 11%.
Comparative example 2
The method identical with embodiment 1 is adopted to prepare propenal, unlike, use oxygen as oxygenant.React 3 hours: propylene conversion is 2%, propylene oxide selectivity is 0%, acrolein selectivity is 14%.
Claims (11)
1. a propylene oxidation prepares the method for propenal, the method comprises, under oxidation reaction condition, by propylene and oxidising agent, it is characterized in that, described oxygenant is the gas containing ozone, described contact is carried out in the presence of a titanium-containing catalyst, and in titanium dioxide, the mol ratio of described titanium-containing catalyst and propylene is 1:0.1-200, wherein, described titanium-containing catalyst is be selected from least one in molecular sieve containing titanium, the preformed catalyst of molecular sieve containing titanium, amorphous silicon titanium and titanium dioxide.
2. method according to claim 1, wherein, the mol ratio of the ozone in described propylene and oxygenant is 1:0.1-10.
3. method according to claim 1, wherein, the described gas containing ozone is the mixed gas of ozone or ozone and diluent gas, and with the cumulative volume of mixed gas for benchmark, in described mixed gas, the content of ozone is 1 more than volume %, and described diluent gas is be selected from least one in oxygen, carbonic acid gas, nitrogen, argon gas, helium, neon and air.
4. method according to claim 3, wherein, with the cumulative volume of mixed gas for benchmark, in described mixed gas, the content of ozone is 5 more than volume %, and described diluent gas is at least one in oxygen, carbonic acid gas, helium and air.
5. method according to claim 1, wherein, described molecular sieve containing titanium is at least one in the HTS of the HTS of MFI structure, the HTS of MEL structure, the HTS of BEA structure, the HTS of MWW structure, the HTS of MOR structure, the HTS of TUN structure and two-dimentional hexagonal structure.
6. method according to claim 5, wherein, described HTS is MFI structure, and HTS crystal grain is hollow structure, and the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.
7. according to the method in claim 1-4 described in any one, wherein, described contact is carried out in the presence of solvent, and the mol ratio of propylene and solvent is 1:1-150.
8. method according to claim 7, wherein, described solvent is at least one in the organic acid of water, the alcohol of C1-C10, the ketone of C3-C10, the nitrile of C2-C8 and C1-C6.
9. method according to claim 8, wherein, described solvent is at least one in water, the ketone of C3-C8 and the nitrile of C2-C6.
10. method according to claim 9, wherein, described solvent is be selected from least one in acetonitrile, acetone, butanone and water.
11. according to the method in claim 1-4 described in any one, and wherein, described oxidation reaction condition comprises, and the temperature of contact is 0-180 DEG C, and pressure is 0.1-3MPa, and the time is 0.1-10 hour.
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| CN201110183218.1A CN102850195B (en) | 2011-06-30 | 2011-06-30 | Method for oxidizing propylene |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1132735A (en) * | 1994-09-08 | 1996-10-09 | Basf公司 | Catalytic gas-phase oxidation of propene to acrolein |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1132735A (en) * | 1994-09-08 | 1996-10-09 | Basf公司 | Catalytic gas-phase oxidation of propene to acrolein |
Non-Patent Citations (1)
| Title |
|---|
| "Gas-Phase Epoxidation of Propylene and Ethylene";Torsten Berndt, et al.;《Ind. Eng. Chem. Res.》;20050119;第44卷(第4期);645-650 * |
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