CN1446626A - Catalyst uitlized for preparing propylene oxide in one-step oxidation of propylene gas phase and its preparation method - Google Patents

Catalyst uitlized for preparing propylene oxide in one-step oxidation of propylene gas phase and its preparation method Download PDF

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CN1446626A
CN1446626A CN 03116195 CN03116195A CN1446626A CN 1446626 A CN1446626 A CN 1446626A CN 03116195 CN03116195 CN 03116195 CN 03116195 A CN03116195 A CN 03116195A CN 1446626 A CN1446626 A CN 1446626A
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catalyzer
hour
silver
aqueous solution
roasting
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CN1181915C (en
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卢冠忠
金国杰
郭杨龙
王筠松
郭耘
刘晓晖
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East China University of Science and Technology
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Abstract

A catalyst Ag-MoO3/ZrO2 for preparing epoxy propane by gas-phase one-step oxidization of propene contains Ag as active component, MoO3 as cocatalyst and ZrO2 as carrier. Its advantages are high selectivity and stability and less by-product.

Description

A kind of preparing propylene oxide from propylene by gas-phase one-step oxidation Catalysts and its preparation method
Technical field
The present invention relates to a kind of novel propylene gas-phase one-step oxidation catalyst for producing epoxypropane, this catalyzer is used for the preparing propylene oxide from propylene by gas-phase one-step oxidation with molecular oxygen as oxidant.
Background technology
Propylene oxide is a kind of important Organic Chemicals, is mainly used in to produce urethane polyether glycol and propylene glycol.Chlorohydrination and peroxidation method are the main method of present industrial production propylene oxide, but the generation of the discharging of mass production refuse and joint product is deadly defects of these two kinds of production technologies.Under the liquid phase mild conditions, use hydrogen peroxide as oxidant, the TS-1 molecular sieve can become the propylene catalysis epoxidation propylene oxide and have higher yields, but because the production cost of TS-1 and hydrogen peroxide is higher, this technology also is difficult to realize commercialization in the long term from now on.In order to solve problem of environmental pollution and reducing production costs simultaneously, use molecular oxygen as oxidant, be that people thirst for solution and are considered to the challenging problem of tool to the direct gas phase catalysis of propylene epoxidation system propylene oxide always.The main method that the silver-colored catalysis epoxidation ethylene production oxyethane that adopts molecular oxygen as oxidant is ethylene oxide production, people such as Lu Guanzhong preparation has also been studied the unsupported silver catalyst (Lu that contains NaCl, G.Z., and Zuo, X.B., Catal.Lett.1999,58:67), on this catalyzer, can obtain 15.0% propylene oxide yield with air oxidant.The ARCO company of the U.S. is active constituent with Ag, make carrier with some lime carbonate, in unstripped gas, add the propylene conversion (Cooker, B., the Gaffney that obtain 60～64% propylene oxide selectivity and 1.5～2.5% under the situation of inhibitor such as vinylchlorid, oxynitride and carbonic acid gas, A.M., Jewson, J.D., andOnimus, W.H., U.S.Patent 5 780 657).Although above-mentioned work has all obtained result preferably, need add reasons such as multiple inhibitor owing to silver content height or unstripped gas in the catalyzer and cause catalyzer cost height, the operational path complexity is brought difficulty to industrial applications.Therefore in unstripped gas, do not add under the prerequisite of any inhibitor, prepare loading type, low-silver-loaded amount and have high propylene oxide optionally catalyzer just seem of crucial importance.
Summary of the invention
The technical issues that need to address of the present invention provide a kind of preparing propylene oxide from propylene by gas-phase one-step oxidation Catalysts and its preparation method, the present invention is with molecular oxygen as oxidant, and need not to add in unstripped gas under the situation of inhibitor and can obtain the loaded catalyst of the preparing propylene oxide from propylene by gas-phase one-step oxidation of high propylene oxide selectivity and higher conversion with low-silver-loaded amount.
The said catalyzer of the present invention is a kind of composition, comprises Ag, the promotor MoO of catalytically effective amount 3With carrier ZrO 2
Specifically, catalyzer by weight percentage, the content of each component is:
Ag???????????10～50％
MoO 3????????0.1～8％
ZrO 2????????49.9～89.9％
Preferably:
Ag???????????14～40％
MoO 3????????1～6％
ZrO 2????????59～85％
Preparation of catalysts method of the present invention comprises the steps:
Method (1):
Press proportioning with silver suboxide (Ag 2O) generate silver-colored ammonium complex solution with oxalic acid, reacting ethylenediamine, then with ammonium molybdate ((NH 4) 6Mo 7O 24.4H 2O) be dissolved in this solution and form mixing solutions, then zirconium dioxide is slowly added and stirs fast and vibrate, carry out drying and roasting subsequently to form uniform slurries, to be preferably in the ultrasonic wave.Again behind absolute ethanol washing, through compressing tablet, fragmentation, be sized to 20～40 orders, promptly make catalyzer.
Drying temperature is 80～120 ℃, and the time is 1～8 hour;
Maturing temperature is 250～500 ℃, and the time is 1～8 hour.
Method (2):
By proportioning zirconium dioxide is joined the silver nitrate aqueous solution for preparing in advance and form slurries and stirring fast, preferably carry out ultra-sonic oscillation, carry out drying and roasting then, drying temperature is 80～120 ℃, time is 1～8 hour, maturing temperature is 250～500 ℃, time is 1～8 hour, get 20～40 purpose particles through compressing tablet, fragmentation, screening, behind the stoichiometric ammonium molybdate aqueous solution of incipient impregnation, in 80～120 ℃ of dryings 1～8 hour, 250～500 ℃ of roastings 1～8 hour promptly got catalyst prod of the present invention.
Method (3)
With the mixed aqueous solution of Silver Nitrate and glucose and potassium hydroxide aqueous solution react silver-colored precipitation, this precipitation gets active silver after aging, washing, oven dry.
Evenly also the ammonium molybdate aqueous solution of 20～40 order particle incipient impregnation stoichiometric ratios is got in compressing tablet, fragmentation, screening with the abundant ground and mixed of zirconium dioxide with active silver, 80～120 ℃ of dryings 1～8 hour, 250～500 ℃ of roastings promptly got catalyzer in 1～8 hour then.
The catalyzer that makes as stated above little anti--carry out performance evaluation in the chromatogram machinery, evaluation procedure is summarized as follows:
The mixing raw material gas of the propylene for preparing by a certain percentage, oxygen and nitrogen is reacted by beds, and the tail gas that contains reaction product is analyzed by two on-line gas chromatographies.The appreciation condition of catalyzer is:
With 0.5 milliliter, particle diameter is that 20～40 purpose catalyzer are put in the flat-temperature zone that internal diameter is 5 millimeters stainless steel fixed-bed reactor, and temperature of reaction is 300～400 ℃, gas space velocity 7500h -1, unstripped gas is made up of 22.7% propylene, 9.0% oxygen and balance gas nitrogen.Oxygen conversion, propylene conversion and propylene oxide selectivity are calculated respectively as follows:
Figure A0311619500061
Figure A0311619500062
Figure A0311619500063
Embodiment
Embodiment 1
Measure 2.5 milliliters of quadrols, 2.0 milliliters of oxalic acid and 5.0 ml distilled waters and be put in the small beaker and fully stir, add 3.39 gram silver suboxides then and make it to dissolve fully and generate silver-colored ammonium complex solution.Then add 0.78 gram ammonium molybdate, treat ammonium molybdate dissolving after, slowly add 12.0 gram zirconium dioxides and stirred ultra-sonic oscillation 30 minutes 120 minutes fast.Stir dipping to the time at 60～80 ℃ subsequently near anhydrous state, in 110 ℃ of oven dry 4 hours, 400 ℃ of roastings 4 hours.Use the equivalent absolute ethanol washing then three times, and in 80 ℃ of dryings 2 hours, it is standby that 20～40 orders are got in compressing tablet, fragmentation, screening.Catalyzer is composed as follows:
Catalyzer is formed (weight %)
Ag????????????20.0
MoO 3?????????4.0
ZrO 276.0 catalyst performance evaluation the results are shown in Table 1.
Embodiment 2
Except the amount of silver suboxide changes 3.31 grams into, the amount of ammonium molybdate changes into outside 0.38 gram, and Preparation of Catalyst is with embodiment 1.Catalyzer is composed as follows:
Catalyzer is formed (weight %)
Ag???????????20.0
MoO 3????????2.0
ZrO 278.0 catalyst performance evaluation the results are shown in Table 1.
Embodiment 3
Except the amount of ammonium molybdate and zirconium dioxide changes into respectively 0.52 gram and 7.0 restrains, Preparation of Catalyst is with embodiment 1.Catalyzer is composed as follows:
Catalyzer is formed (weight %)
Ag???????????30.0
MoO 3??????????4.0
ZrO 266.0 catalyst performance evaluation the results are shown in Table 1.
Embodiment 4
12.0 gram zirconium dioxides are slowly joined formed slurries and quick stirring in the solution that is made into by 4.97 gram Silver Nitrates and 5 ml distilled waters 120 minutes, ultra-sonic oscillation slowly were heated near anhydrous state after 30 minutes.In 110 ℃ of oven dry 4 hours, 450 ℃ of roastings were after 4 hours, and 20～40 order particles, 7.58 grams are got in compressing tablet, fragmentation, screening, and incipient impregnation contains the aqueous solution of 0.39 gram ammonium molybdate, in 110 ℃ of dryings 4 hours, and 400 ℃ of roastings 4 hours.Catalyzer is composed as follows:
Catalyzer is formed (weight %)
Ag????????????20.0
MoO 3?????????4.0
ZrO 276.0 catalyst performance evaluation the results are shown in Table 1.
Embodiment 5
Take by weighing 10.26 gram Silver Nitrates and 2.05 gram glucose and be dissolved in 100 ml distilled waters and stir form mixing solutions, the 10 ml water solution that will contain 9.05 gram potassium hydroxide then at the uniform velocity join in this solution cotton-shaped silver precipitation.This precipitation at room temperature aging 120 minutes is washed with distilled water to neutrality, gets active silver in 4 hours in 110 ℃ of oven dry.After getting the active silver of 2.63 grams and grinding evenly with 10.0 gram zirconium dioxide thorough mixing, 20～40 order particles are got in compressing tablet, fragmentation, screening, and incipient impregnation contains the aqueous solution of 0.65 gram ammonium molybdate.In 110 ℃ of oven dry 4 hours, 400 ℃ of roastings 4 hours.Catalyzer is composed as follows:
Catalyzer is formed (weight %)
Ag???????????????20.0
MoO 3????????????4.0
ZrO 276.0 catalyst performance evaluation the results are shown in Table 1.Comparative Examples 1
Except that not adding ammonium molybdate and the amount of silver suboxide being changed into 3.22 grams, Preparation of Catalyst is with embodiment 1.Catalyzer is composed as follows:
Catalyzer is formed (weight %)
Ag????????????20.0
MoO 3???????????-
ZrO 280.0 catalyst performance evaluation the results are shown in Table 1.Comparative Examples 2
Except that zirconium dioxide is changed into the lime carbonate, Preparation of Catalyst is with embodiment 1.Catalyzer is composed as follows:
Catalyzer is formed (weight %)
Ag???????????????20.0
MoO 3????????????4.0
CaCO 376.0 catalyst performance evaluation the results are shown in Table 1.Comparative Examples 3
Except zirconium dioxide is changed into the silicon-dioxide, Preparation of catalysts is with embodiment 1.Catalyzer is composed as follows:
Catalyzer is formed (weight %)
Ag??????????????20.0
MoO 3???????????4.0
SiO 276.0 catalyst performance evaluation the results are shown in Table 1.Comparative Examples 4
Except zirconium dioxide is changed into TiO 2-ZrO 2Outward, the Preparation of catalysts method is with embodiment 1.Catalyzer is composed as follows:
Catalyzer is formed (weight %)
Ag?????????????20.0
MoO 3??????????4.0
TiO 2-ZrO 276.0 catalyst performance evaluation the results are shown in Table 1.Comparative Examples 5
Remove zirconium dioxide is changed into TiO 2-SiO 2Outward, the Preparation of catalysts method is with embodiment 1.Catalyzer is composed as follows:
Catalyzer is formed (weight %)
Ag????????????20.0
MoO 3?????????4.0
TiO 2-SiO 276.0 catalyst performance evaluation the results are shown in Table 1.The epoxidation of propylene performance of each catalyzer of table 1 (1)
Catalyzer Transformation efficiency (%) Products distribution (2)(％)
The oxygen propylene Propylene oxide propenal acetone hydrocarbons carbonic acid gas
Embodiment 1 ??4.8?????1.6 ??60.3???????0????????0???????2.4????37.3
Embodiment 2 ??5.3?????1.6 ??52.1???????0????????0???????3.5????44.4
Embodiment 3 ??6.1?????1.8 ??53.3???????0????????0???????3.2????43.5
Embodiment 4 ??9.8?????2.1 ??39.6???????0????????0???????25.0???35.4
Embodiment 5 ??14.8????3.3 ??41.3???????0????????0???????23.9???34.8
Comparative Examples 1 ??84.4????8.4 ??0.6????????0????????0???????10.5???88.9
Comparative Examples 2 ??98.9????9.1 ??0??????????0????????0???????4.4????95.6
Comparative Examples 3 ??22.5????2.4 ??10.7???????0????????0???????9.7????79.6
Comparative Examples 4 ??95.2????9.1 ??1.8????????0????????0???????6.5????91.7
Comparative Examples 5 ??99.4????9.4 ??2.0????????0????????1.7?????3.6????92.7
(1) embodiment 1～embodiment 5 and Comparative Examples 1 and Comparative Examples 3 are all 400 ℃ of evaluations; Comparative Examples 2 is 350 ℃ of evaluations; Comparative Examples 4 and Comparative Examples 5 are 300 ℃ of evaluations.
(2) hydrocarbons refers to C 1～C 6Hydro carbons.
The foregoing description explanation, Ag-MoO of the present invention 3/ ZrO 2Series catalysts is used MoO 3As electron type and structure-type promotor, use ZrO 2As carrier, propylene oxide selectivity height, by product is few, and has satisfactory stability, is a kind of good high-selectivity catalyst.

Claims (9)

1. a preparing propylene oxide from propylene by gas-phase one-step oxidation catalyzer is characterized in that, comprises catalytic active component Ag, promotor MoO 3With carrier ZrO 2
2. catalyzer according to claim 1 is characterized in that, by weight percentage, the content of each component is:
Ag???????????10～50％
MoO 3????????0.1～8％
ZrO 2????????49.9～89.9％。
3. catalyzer according to claim 2 is characterized in that, the content of each component is:
Ag???????????14～40％
MoO 3????????1～6％
ZrO 2????????59～85％。
4. according to claim 1,2 or 3 described Preparation of catalysts methods, it is characterized in that comprising the steps:
By proportioning silver suboxide and oxalic acid, reacting ethylenediamine are generated silver-colored ammonium complex solution, then ammonium molybdate is dissolved in this solution and forms mixing solutions, zirconium dioxide is added the formation slurries, and carry out drying and roasting, after after appropriate means handles, promptly make catalyzer.
5. method according to claim 4 is characterized in that, drying temperature is 80～120 ℃, and the time is 1～8 hour; Maturing temperature is 250～500 ℃, and the time is 1～8 hour.
6. according to claim 1,2 or 3 described Preparation of catalysts methods, it is characterized in that comprising the steps:
By proportioning zirconium dioxide is joined silver nitrate aqueous solution, form slurries, carry out drying and roasting then, make particle, behind the stoichiometric ammonium molybdate aqueous solution of incipient impregnation, after drying, the roasting, promptly get catalyzer of the present invention.
7. method according to claim 6 is characterized in that, by proportioning zirconium dioxide is joined silver nitrate aqueous solution, form slurries, carry out drying and roasting then, drying temperature is 80～120 ℃, and the time is 1～8 hour, maturing temperature is 250～500 ℃, time is 1～8 hour, adopts conventional method to obtain particle, behind the stoichiometric ammonium molybdate aqueous solution of incipient impregnation, in 80～120 ℃ of dryings 1～8 hour, 250～500 ℃ of roastings 1～8 hour.
8. according to claim 1,2 or 3 described Preparation of catalysts methods, it is characterized in that comprising the steps:
With the mixed aqueous solution of Silver Nitrate and glucose and potassium hydroxide aqueous solution react silver-colored precipitation, this precipitation must active silver after aging, washing, drying;
With activity silver and zirconium dioxide ground and mixed, make particle, the ammonium molybdate aqueous solution of incipient impregnation stoichiometric ratio, oven dry then, roasting promptly gets catalyzer.
9. method according to claim 8 is characterized in that in 80～120 ℃ of oven dry 1～8 hour, 250～500 ℃ of roastings 1～8 hour.
CNB031161952A 2003-04-04 2003-04-04 Catalyst uitlized for preparing propylene oxide in one-step oxidation of propylene gas phase and its preparation method Expired - Fee Related CN1181915C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109821530A (en) * 2017-11-23 2019-05-31 中国科学院大连化学物理研究所 A kind of cobalt-base catalyst and its method for propylene ring oxidation reaction
EP4180425A1 (en) * 2021-11-10 2023-05-17 Fritz-Haber-Institut Der Max-Planck-Gesellschaft Method for producing propylene oxide

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109821530A (en) * 2017-11-23 2019-05-31 中国科学院大连化学物理研究所 A kind of cobalt-base catalyst and its method for propylene ring oxidation reaction
CN109821530B (en) * 2017-11-23 2022-01-04 中国科学院大连化学物理研究所 Cobalt-based catalyst and method for applying cobalt-based catalyst to propylene epoxidation reaction
EP4180425A1 (en) * 2021-11-10 2023-05-17 Fritz-Haber-Institut Der Max-Planck-Gesellschaft Method for producing propylene oxide
WO2023083874A1 (en) * 2021-11-10 2023-05-19 Fritz-Haber-Institut Der Max-Planck- Gesellschaft Method for producing propylene oxide

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