CN101397282B - Method for preparing epoxypropane - Google Patents
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- CN101397282B CN101397282B CN2007101752782A CN200710175278A CN101397282B CN 101397282 B CN101397282 B CN 101397282B CN 2007101752782 A CN2007101752782 A CN 2007101752782A CN 200710175278 A CN200710175278 A CN 200710175278A CN 101397282 B CN101397282 B CN 101397282B
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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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Abstract
The invention discloses a method used for preparing propylene oxide. The method is characterized in that propylene, oxygen, hydrogen, a solvent and a catalyst are mixed for contact reaction at the temperature of 0 to 8 DEG C and the pressure of 0.1 to 3.0 MPa; the molar ratio between the propylene, the oxygen and the hydrogen is 1:(0.1 to 10):(0.1 to 10) and the mass ratio between the propylene and the catalyst is (0.1 to 50):1 and the mass ratio between the solvent and the catalyst is (10 to 1000):1; the catalyst appears as a palladium-loaded hollow titanium-silicate molecular sieve with MFI structure, and the radial length of the grain hollow cavity on the molecular sieve is between 5 and 300 nanometers; and benzene absorption is measured to be at least 70 milligram/gram under the conditions that the temperature is 25 DEG C, the P/P0 is equal to 0.10 and the absorption time is one hour; and a hysteresis loop exists between an absorption isotherm for cryogenic nitrogen absorption and a desorption isotherm. The method has high propylene conversion rate and high propylene oxide selectivity; especially the effective availability of hydrogen is higher and the stability of activity is better.
Description
Technical field
The present invention relates to a kind of method of catalytic oxidation propylene, the present invention relates to a kind of method of producing propylene oxide with the titanium molecular sieve catalysis epoxidation of propylene of supported palladium furtherly.
Background technology
Propylene oxide (PO) is large industrial chemicals, ranks among 50 kinds of chemical of global output maximum, is the third-largest organic chemical industry's product that output is only second to polypropylene and vinyl cyanide in the acryloyl derivative.PO because of its have tension force very big contain the oxygen three-membered ring, chemical property is very active, of many uses, be mainly used in and produce polyethers, propylene glycol, Yi Bingchunan, vinylcarbinol, non-polyether glycol etc., and then produce unsaturated polyester resin, urethane, tensio-active agent (oil field emulsion splitter, farm chemical emulgent and wetting agent) etc., be widely used in industries such as chemical industry, light industry, medicine, food, weaving, chemical industry and development and national economy are had far-reaching influence.Prosperity along with industries such as the continuous growth, particularly automobile of the expansion of PO purposes and downstream product consumption, building households increases considerably urethane and nonionogenic tenside demand, causes the market requirement of PO vigorous.
Present industrial production propylene oxide mainly adopts chlorohydrination and conjugated oxidation, and the throughput of these two kinds of methods accounts for more than 99% of world's overall throughput, and output almost respectively accounts for half.Chlorohydrination early is applied to produce, and this method is used chlorine, and seriously corroded also produces the chlorine-contained wastewater of a large amount of contaminate environment, does not meet the requirement of Green Chemistry and cleaner production, and therefore along with the raising day by day of environmental protection requirement, this technology will finally be eliminated.Conjugated oxidation mainly uses ethylbenzene superoxide or tertbutyl peroxide etc. as oxygen source, is PO with the propylene indirect oxidation.Conjugated oxidation has overcome shortcomings such as chlorohydrination contaminate environment and etching apparatus, is the production technique than the relative cleaning of chlorohydrination.But cheap byproducts such as the vinylbenzene that coproduction is a large amount of or the trimethyl carbinol, byproduct market are difficult to digestion, add that technology is tediously long, fundamental construction investment scale is big, and economic factors is the major cause of its development of restriction.
Domestic PO produces and all adopts chlorohydrination, the production corrosion contamination is serious, cost is high, low, the poor selectivity of transformation efficiency, and demand is increasing year by year, along with the existing technology of the raising day by day of environmental requirement also faces huge challenge for existence, it is extremely urgent therefore to seek a kind of eco-friendly green production process production PO.Be that oxygenant, HTS are that the method for catalyzer can have higher propylene conversion and PO selectivity with the hydrogen peroxide, for PO synthetic opened up a new way.This method is easy, and is free from environmental pollution, is the PO production process that has competitive power, meets the requirement of contemporary Green Chemistry and atom economy idea of development, and is considered to produce the novel environment-friendly process of PO.But, because H
2O
2Extremely unstable, meet heat, light, uneven surface, heavy metal and other impurity can decompose, and have corrodibility, will take special security measures in packing, storage, transportation.Be subjected to the limitation of cost and safety problem, and preparation H
2O
2Need the independent equipment and the recycle system, expensive bigger, the situ production expense is very high, and before not having stricter environmental regulation appearance, its industrialization has the certain economic obstacle.
Molecular oxygen is cheap and easy to get and pollution-free, is optimal oxygen source.Utilize H
2And O
2Directly synthetic H
2O
2, can solve and directly utilize H
2O
2The high problem of preparation PO cost.Pt, Pd are H
2And O
2Synthetic H
2O
2Active principle, have bibliographical information that it is loaded on the titanium silicalite material original position and generate H
2O
2Be used for the research of propylene gas-phase epoxidation reaction.As J.Catal., 176 (1998): 376-386 is that catalyzer is studied PROPENE IN GAS PHASE OXIDATION with Pt-Pd/TS-1; US 6867312B1 and US 6884898B1 etc. have also carried out the research of this respect.Because mild condition, selectivity good (can reach more than 95%), Lyondell company carries out the pilot scale checking, have in the near future industrial applications possibility (European Chemical News, 2004,80:31).But also there is low, the H of propylene conversion in this method
2Effective rate of utilization is low, catalyst deactivation is fast, be difficult for defectives such as regeneration and poor stability.Therefore, overcoming above-mentioned defective is to be the key that catalyzer carries out this technical study exploitation of PO with Pt-Pd/TS-1.
Summary of the invention
The inventor discloses a kind of MFI of having structure of hollow HTS first in CN1301599A, this molecular sieve has unique duct, and crystal grain is hollow structure.Because this molecular sieve has special shape and has less extra-framework titanium, thereby has good catalytic oxidation activity and activity stability.
The inventor further discovers by a large amount of experiments, in the propylene gas-phase epoxidation reaction, oxygen, hydrogen exist down, when the disclosed MFI of having structure of hollow HTS supported palladium is catalyzer in adopting CN1301599A, compare with the TS-1 HTS supported palladium of using routine, have under the situation of good propylene conversion and activity stability, especially the effective rate of utilization of hydrogen has had unexpected raising, makes that this hollow HTS is expected to be used in this green reaction process of propylene gas-phase epoxidation production propylene oxide.
Therefore, the purpose of this invention is to provide a kind of method that is the catalyst preparing epoxypropane by epoxidation of propene with novel hollow HTS supported palladium.
The method for preparing propylene oxide provided by the invention, it is characterized in that being 0～80 ℃ in temperature is under the condition of 0.1～3.0MPa with pressure, with propylene, oxygen, hydrogen, solvent and catalyst mix contact reacts, propylene and oxygen, the mol ratio of hydrogen is 1: (0.1～10): (0.1～10), the mass ratio of propylene and catalyzer is (0.1～50): 1, the mass ratio of solvent and catalyzer is (10～1000): 1, catalyzer be supported palladium have a MFI structure of hollow HTS, the cavity part radical length of this zeolite crystal is 5～300 nanometers, this molecular sieve is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is at least 70 milligrams/gram, has hysteresis loop between the adsorption isothermal line of cryogenic nitrogen absorption and the desorption isotherm.
In the method provided by the invention, that is adopted has a MFI structure of hollow HTS, discloses in CN1301599A, has hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen absorption of this molecular sieve and the desorption isotherm; Its crystal grain is one hollow crystal grain or the gathering crystal grain that is gathered into by a plurality of hollow crystal grain; The radical length of the cavity part of this hollow crystal grain is 5～300 nanometers; This sieve sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is at least 70 milligrams/gram.
In the method provided by the invention, the quality percentage composition of palladium is 0.05-10% in the catalyzer that is adopted, and the quality percentage composition of hollow HTS is 90-99.95%.
In the method provided by the invention, said palladium preferably is carried on the hollow HTS with the pickling process of routine.
In the method provided by the invention, said solvent is selected from alcohols or nitrile or their mixtures such as ketone such as acetone, butanone or acetonitrile such as water or methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, is preferably methyl alcohol and/or water.
In the method provided by the invention, the mol ratio of propylene and oxygen is preferably 1: (0.2～5.0), the mol ratio of propylene and hydrogen is preferably 1: (0.2～5.0), the mass ratio of solvent and catalyzer is preferably (20～500): 1.
In the method provided by the invention, preferred reaction conditions is 20～60 ℃ of temperature, pressure 0.3～2.5MPa.
The method for preparing propylene oxide provided by the invention can adopt periodical operation or operate continuously mode.When carrying out, behind propylene, solvent, catalyzer adding reactor, add oxygen, hydrogen continuously with intermittent mode; Can adopt fixed-bed reactor when carrying out in a continuous manner, behind the catalyzer of packing into solvent, propylene, oxygen, hydrogen be added continuously; Maybe can adopt slurry bed reactor, catalyzer, solvent making beating back are added propylene, oxygen, hydrogen continuously, the while is separated product constantly.Adopting under periodical operation or the successive feeding manner, reacting total gas space velocity is 10～10000h
-1, be preferably 100～5000h
-1
Method provided by the invention can also adopt closed tank reactor, is about to catalyzer, solvent, propylene and oxygen, hydrogen and adds afterreaction simultaneously.
In the method provided by the invention, the catalyst system therefor main active component is precious metal palladium and hollow HTS.Wherein, hollow HTS has increased the velocity of diffusion of reactant and product as the carrier and the epoxidation activity component of palladium metal, has reduced the generation of side reactions such as PO open loop, and selectivity is good; Because the extra-framework titanium content of hollow HTS is low, its catalytic oxidation activity, selectivity of product and activity stability obviously improve, and especially the hydrogen effective rate of utilization is brought up to more than 35% by 23% apparently higher than prior art.
Embodiment
By the following examples the present invention is further described, but does not therefore limit content of the present invention.
Used reagent is commercially available chemically pure reagent among the embodiment.
Traditional HTS (TS-1) used in the Comparative Examples is by prior art Zeolites, 1992, and (TS-1) sieve sample that the method described in the Vol.12 943-950 page or leaf is prepared.
Hollow HTS HTS used among the embodiment builds the production of long company for the Sinopec Hunan, is the Industrial products of the described HTS of Chinese patent CN1301599A.
In Comparative Examples and embodiment:
Percent value before the catalyzer is represented the quality percentage composition of palladium;
Propylene conversion (%)=(molar weight-unreacted propylene molar weight of propylene in feeding intake)/molar weight * 100% of propylene in feeding intake;
Total hydrogen molar weight * 100% of hydrogen effective rate of utilization (%)=propylene oxide and derivative molar weight/reaction consumes thereof;
Total molar weight * 100% that transforms of the molar weight/propylene of propylene oxide selectivity (%)=propylene oxide in products.
Comparative Examples 1
The explanation of this Comparative Examples is the reaction process that catalyzer is prepared propylene oxide with the 0.5%Pd/TS-1 of traditional HTS (TS-1) supported palladium preparation.
Preparation of Catalyst: get traditional titanium-silicon molecular sieve TS-1 sample 10 grams and 15ml water and join the PdCl that 5ml concentration is 0.01g/ml
2In the aqueous solution, be 40 ℃ in temperature and stirred 24 hours down, suitably sealing therebetween, natural drying at room temperature is 48 hours then, promptly obtains utilizing traditional HTS (TS-1) supported palladium to prepare load type palladium/HTS (0.5%Pd/TS-1) catalyzer.
Catalyzer need be in nitrogen hydrogen mixed gas atmosphere before the reaction that is prepared propylene oxide is reduction activation 3 hours under 300 ℃ the condition in temperature.
Is 1: 1: 1 with propylene, oxygen, hydrogen, solvent methanol and catalyzer according to the mol ratio of propylene and oxygen, hydrogen, and the mass ratio of solvent methanol and catalyzer is 50, is that 60 ℃, pressure are under the 0.5MPa in temperature, is 1000h in total gas volume air speed
-1The following reaction.
The result who reacts 2 hours is as follows: propylene conversion is 2.4%; The hydrogen effective rate of utilization is 18%; The propylene oxide selectivity is 90%.
It is as follows to react the result who carries out 8 hours: propylene conversion is 1.1%; The hydrogen effective rate of utilization is 21%; The propylene oxide selectivity is 82%.
Comparative Examples 2
The reaction process of Preparation of Catalyst propylene oxide is done in the explanation of this Comparative Examples with the 2%Pd/TS-1 of traditional HTS (TS-1) supported palladium preparation.
Preparation of Catalyst: get traditional titanium-silicon molecular sieve TS-1 sample 10 grams and join the PdCl that 20ml concentration is 0.01g/ml
2In the aqueous solution, be 40 ℃ in temperature and stirred 24 hours down, suitably sealing therebetween, natural drying at room temperature is 48 hours then, promptly obtains utilizing traditional HTS (TS-1) supported palladium to prepare load type palladium/HTS (2%Pd/TS-1) catalyzer.
Catalyzer need be in nitrogen hydrogen mixed gas atmosphere before the reaction that is prepared propylene oxide is reduction activation 3 hours under 300 ℃ the condition in temperature.
Is 1: 1: 1 with propylene, oxygen, hydrogen, solvent methanol and catalyzer according to the mol ratio of propylene and oxygen, hydrogen, and the mass ratio of solvent methanol and catalyzer is 200, is that 20 ℃ of pressure are under the 0.5MPa in temperature, is 500h in total gas volume air speed
-1The following reaction.
The result who reacts 2 hours is as follows: propylene conversion is 3.2%; The hydrogen effective rate of utilization is 23%; The propylene oxide selectivity is 91%.
It is as follows to react the result who carries out 8 hours: propylene conversion is 1.5%; The hydrogen effective rate of utilization is 22%; The propylene oxide selectivity is 75%.
Embodiment 1
Present embodiment illustrates that hollow HTS (HTS) supported palladium prepares the process of load type palladium/HTS (0.5%Pd/HTS) catalyzer.
Get hollow HTS HTS sample 10 grams and join the PdCl that 20ml concentration is 0.01g/ml
2In the aqueous solution, being 40 ℃ in temperature stirred 24 hours down, suitably sealing therebetween, natural drying at room temperature is 48 hours then, promptly obtain utilizing hollow HTS (HTS) supported palladium to prepare load type palladium/HTS (0.5%Pd/HTS) catalyzer, be numbered A (need be in nitrogen hydrogen mixed gas atmosphere before the reaction that is prepared propylene oxide be reduction activation 3 hours under 300 ℃ the condition, down with) in temperature.
Embodiment 2
The present embodiment explanation utilizes hollow HTS (HTS) supported palladium to prepare the process of load type palladium/HTS (2%Pd/HTS) catalyzer.
Get hollow HTS HTS sample 10 grams and 15ml water and join the PdCl that 5ml concentration is 0.01g/ml
2In the aqueous solution, be 40 ℃ in temperature and stirred 24 hours down, suitably sealing therebetween, natural drying at room temperature 48 hours promptly obtains utilizing hollow HTS (HTS) supported palladium to prepare load type palladium/HTS (2%Pd/HTS) catalyzer, is numbered B.
Embodiment 3
Is 1: 1: 1 with the HTS A of propylene, oxygen, hydrogen, solvent and supported palladium according to the mol ratio of propylene and oxygen, hydrogen, the mass ratio of solvent methanol and catalyzer is 50, in temperature is that 60 ℃ of pressure are under the 0.5MPa, is 1000h in total gas volume air speed
-1The following reaction.
The result who reacts 2 hours is as follows: propylene conversion is 6.8%; The hydrogen effective rate of utilization is 40%; The propylene oxide selectivity is 96%.
It is as follows to react the result who carries out 8 hours: propylene conversion is 6.5%; The hydrogen effective rate of utilization is 38%; The propylene oxide selectivity is 94%.
The result who reacts 120 hours is as follows: propylene conversion is 6.3%; The hydrogen effective rate of utilization is 36%; The propylene oxide selectivity is 95%.
Embodiment 4
Is 1: 2: 5 with the HTS B of propylene, oxygen, hydrogen, solvent and supported palladium according to the mol ratio of propylene and oxygen, hydrogen, the mass ratio of solvent methanol and catalyzer is 200, in temperature is that 40 ℃ of pressure are under the 0.2MPa, is 2000h in total gas volume air speed
-1The following reaction.
The result who reacts 2 hours is as follows: propylene conversion is 5.6%; The hydrogen effective rate of utilization is 38%; The propylene oxide selectivity is 95%.
It is as follows to react the result who carries out 8 hours: propylene conversion is 5.5%; The hydrogen effective rate of utilization is 36%; The propylene oxide selectivity is 94%.
The result who reacts 120 hours is as follows: propylene conversion is 5.2%; The hydrogen effective rate of utilization is 35%; The propylene oxide selectivity is 92%.
Embodiment 5
Is 1: 5: 2 with the HTS A of propylene, oxygen, hydrogen, solvent and supported palladium according to the mol ratio of propylene and oxygen, hydrogen, the mass ratio of solvent methanol and catalyzer is 25, in temperature is that 30 ℃ of pressure are under the 1.5MPa, is 500h in total gas volume air speed
-1The following reaction.
The result who reacts 2 hours is as follows: propylene conversion is 6.5%; The hydrogen effective rate of utilization is 45%; The propylene oxide selectivity is 93%.
It is as follows to react the result who carries out 8 hours: propylene conversion is 6.4%; The hydrogen effective rate of utilization is 39%; The propylene oxide selectivity is 92%.
The result who reacts 120 hours is as follows: propylene conversion is 6.1%; The hydrogen effective rate of utilization is 38%; The propylene oxide selectivity is 93%.
Embodiment 6
Is 1: 0.5: 3 with the HTS B of propylene, oxygen, hydrogen, solvent and supported palladium according to the mol ratio of propylene and oxygen, hydrogen, the mass ratio of solvent methanol and catalyzer is 80, in temperature is that 20 ℃ of pressure are under the 0.5MPa, is 2000h in total gas volume air speed
-1The following reaction.
The result who reacts 2 hours is as follows: propylene conversion is 7.2%; The hydrogen effective rate of utilization is 36%; The propylene oxide selectivity is 94%.
It is as follows to react the result who carries out 8 hours: propylene conversion is 6.5%; The hydrogen effective rate of utilization is 35%; The propylene oxide selectivity is 94%.
The result who reacts 120 hours is as follows: propylene conversion is 6.3%; The hydrogen effective rate of utilization is 36%; The propylene oxide selectivity is 92%.
Embodiment 7
Is 1: 2: 0.5 with the HTS A of propylene, oxygen, hydrogen, solvent and supported palladium according to the mol ratio of propylene and oxygen, hydrogen, the mass ratio of solvent methanol and catalyzer is 400, in temperature is that 30 ℃ of pressure are under the 2.5MPa, is 1500h in total gas volume air speed
-1The following reaction.
The result who reacts 2 hours is as follows: propylene conversion is 6.5%; The hydrogen effective rate of utilization is 45%; The propylene oxide selectivity is 95%.
It is as follows to react the result who carries out 8 hours: propylene conversion is 6.2%; The hydrogen effective rate of utilization is 39%; The propylene oxide selectivity is 95%.
The result who reacts 120 hours is as follows: propylene conversion is 6.1%; The hydrogen effective rate of utilization is 38%; The propylene oxide selectivity is 93%.
Embodiment 8
Is 1: 0.8: 0.6 with the HTS B of propylene, oxygen, hydrogen, solvent and supported palladium according to the mol ratio of propylene and oxygen, hydrogen, the mass ratio of solvent methanol and catalyzer is 80, in temperature is that 40 ℃ of pressure are under the 0.8MPa, is 200h in total gas volume air speed
-1The following reaction.
The result who reacts 2 hours is as follows: propylene conversion is 6.2%; The hydrogen effective rate of utilization is 36%; The propylene oxide selectivity is 95%.
It is as follows to react the result who carries out 8 hours: propylene conversion is 5.5%; The hydrogen effective rate of utilization is 35%; The propylene oxide selectivity is 95%.
The result who reacts 120 hours is as follows: propylene conversion is 5.3%; The hydrogen effective rate of utilization is 36%; The propylene oxide selectivity is 92%.
Embodiment 9
Is 1: 0.4: 1.2 with the HTS A of propylene, oxygen, hydrogen, solvent and supported palladium according to the mol ratio of propylene and oxygen, hydrogen, the mass ratio of solvent methanol and catalyzer is 120, in temperature is that 50 ℃ of pressure are under the 1.5MPa, is 800h in total gas volume air speed
-1The following reaction.
The result who reacts 2 hours is as follows: propylene conversion is 5.8%; The hydrogen effective rate of utilization is 45%; The propylene oxide selectivity is 96%.
It is as follows to react the result who carries out 8 hours: propylene conversion is 5.7%; The hydrogen effective rate of utilization is 39%; The propylene oxide selectivity is 94%.
The result who reacts 120 hours is as follows: propylene conversion is 8.1%; The hydrogen effective rate of utilization is 38%; The propylene oxide selectivity is 93%.
Embodiment 10
Is 1: 2: 0.3 with the HTS B of propylene, oxygen, hydrogen, solvent and supported palladium according to the mol ratio of propylene and oxygen, hydrogen, the mass ratio of solvent methanol and catalyzer is 250, in temperature is that 25 ℃ of pressure are under the 1.8MPa, is 4000h in total gas volume air speed
-1The following reaction.
The result who reacts 2 hours is as follows: propylene conversion is 6.0%; The hydrogen effective rate of utilization is 36%; The propylene oxide selectivity is 95%.
It is as follows to react the result who carries out 8 hours: propylene conversion is 5.5%; The hydrogen effective rate of utilization is 35%; The propylene oxide selectivity is 93%.
The result who reacts 120 hours is as follows: propylene conversion is 5.3%; The hydrogen effective rate of utilization is 36%; The propylene oxide selectivity is 92%.
Embodiment 11
The HTS A of present embodiment explanation supported palladium does catalyzer carries out propylene ring oxidation reaction in tank reactor process.
Is 1: 2: 1 with propylene, oxygen, hydrogen, solvent methanol and A according to the mol ratio of propylene and methyl alcohol, oxygen, hydrogen: 1, and the mass ratio of methyl alcohol and catalyzer is 40, is that 60 ℃ of pressure are to react under the 0.8MPa in temperature.The result who reacts 2 hours is as follows: propylene conversion is 6.2%; The hydrogen effective rate of utilization is that 38% propylene oxide selectivity is 95%.It is as follows to react the result who carries out 12 hours: propylene conversion is 16.5%; The hydrogen effective rate of utilization is 35%; The propylene oxide selectivity is 84%.
Embodiment 12
The HTS B of present embodiment explanation supported palladium does catalyzer carries out propylene ring oxidation reaction in tank reactor process.
Is 1: 25: 2 with propylene, oxygen, hydrogen, solvent methanol and B according to the mol ratio of propylene and methyl alcohol, oxygen, hydrogen: 2, and the mass ratio of methyl alcohol and catalyzer is 150, is that 30 ℃ of pressure are to react under the 1.6MPa in temperature.The result who reacts 2 hours is as follows: propylene conversion is 6.7%; The hydrogen effective rate of utilization is 37%; The propylene oxide selectivity is 94%.It is as follows to react the result who carries out 12 hours: propylene conversion is 17.2%; The hydrogen effective rate of utilization is 35%; The propylene oxide selectivity is 86%.
From the result of Comparative Examples 1,2 and embodiment 3-12 as can be seen: the method for preparing propylene oxide provided by the invention, have high propylene conversion and propylene oxide selectivity, especially the hydrogen effective rate of utilization is higher, and activity stability is better.
Claims (10)
1. method for preparing propylene oxide, it is characterized in that being 0～80 ℃ in temperature is under the condition of 0.1～3.0MPa with pressure, with propylene, oxygen, hydrogen, solvent and catalyst mix contact reacts, propylene and oxygen, the mol ratio of hydrogen is 1: (0.1～10): (0.1～10), the mass ratio of propylene and catalyzer is (0.1～50): 1, the mass ratio of solvent and catalyzer is (10～1000): 1, catalyzer be supported palladium have a MFI structure of hollow HTS, the cavity part radical length of this zeolite crystal is 5～300 nanometers, this molecular sieve is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is at least 70 milligrams/gram, has hysteresis loop between the adsorption isothermal line of cryogenic nitrogen absorption and the desorption isotherm.
2. according to the method for claim 1, the quality percentage composition that it is characterized in that palladium in the catalyzer is 0.05-10%.
3. according to the method for claim 1, said palladium is carried on the hollow HTS with pickling process.
4. according to the method for claim 1, the mol ratio of propylene and oxygen is 1: (0.2～5.0), the mol ratio of propylene and hydrogen are 1: (0.2～5.0), the mass ratio of solvent and catalyzer are (20～500): 1.
5. according to the method for claim 1, it is characterized in that temperature of reaction is 20～60 ℃, reaction pressure is 0.3～2.5MPa.
6. according to the method for claim 1 or 4, it is characterized in that said solvent is selected from alcohol, ketone or nitrile.
7. according to the method for claim 6, said alcohol is selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol or isopropylcarbinol, and said ketone is acetone or butanone, and said nitrile is an acetonitrile.
8. according to the method for claim 1, said solvent is methyl alcohol and/or water.
9. according to the method for claim 1, it is characterized in that adopting periodical operation or operate continuously mode, reacting total gas space velocity is 10～10000h
-1
10. according to the method for claim 9, the total gas space velocity of said reaction is 100～5000h
-1
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| KR20120139675A (en) * | 2010-02-03 | 2012-12-27 | 스미또모 가가꾸 가부시끼가이샤 | Method for producing propylene oxide |
| WO2011116157A1 (en) * | 2010-03-17 | 2011-09-22 | Dow Technology Investments Llc | Catalytic fixed bed reactor for producing ethylene oxide by partial oxidation of ethylene |
| CN102441430B (en) * | 2010-10-11 | 2013-06-12 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and alkene epoxidation method |
| CN103012064B (en) * | 2011-09-28 | 2015-03-18 | 中国石油化工股份有限公司 | Method for preparing propylene glycol from propylene |
| CN103121980B (en) * | 2011-11-18 | 2015-09-09 | 中国石油化工股份有限公司 | The method of epoxidation of propylene |
| MY188483A (en) * | 2014-09-29 | 2021-12-14 | China Petroleum & Chem Corp | Olefin oxidation process, reaction apparatus and system |
| CN106146430B (en) * | 2015-03-24 | 2019-07-23 | 中国石油化工股份有限公司 | Method that is a kind of while producing propylene oxide and acetone |
| CN111724863B (en) * | 2019-03-22 | 2023-01-31 | 中国石油化工股份有限公司 | Method for predicting and controlling hydrogen peroxide conversion rate in preparation of epoxypropane by TS-1 method |
| CN115745919B (en) * | 2022-10-20 | 2024-03-19 | 中国科学院大连化学物理研究所 | Synthetic method of epoxypropane |
| CN115872842A (en) * | 2022-11-30 | 2023-03-31 | 浙江工业大学 | Method for catalytically synthesizing 1-phenyl-1,2-dimethoxyethane by palladium-containing titanium-silicon molecular sieve |
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| CN1376151A (en) * | 1999-09-27 | 2002-10-23 | 阿科化学技术公司 | Catalyst preparation and epoxidation process |
| US6867312B1 (en) * | 2004-03-17 | 2005-03-15 | Arco Chemical Technology, L.P. | Propylene oxide process |
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| CN1376151A (en) * | 1999-09-27 | 2002-10-23 | 阿科化学技术公司 | Catalyst preparation and epoxidation process |
| CN1301599A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
| US6867312B1 (en) * | 2004-03-17 | 2005-03-15 | Arco Chemical Technology, L.P. | Propylene oxide process |
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| CN101397282A (en) | 2009-04-01 |
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