CN1347760A - Ag-CuCl catalyst for the direct oxidation of propylene with air to prepare epoxypropane - Google Patents
Ag-CuCl catalyst for the direct oxidation of propylene with air to prepare epoxypropane Download PDFInfo
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- CN1347760A CN1347760A CN 01136129 CN01136129A CN1347760A CN 1347760 A CN1347760 A CN 1347760A CN 01136129 CN01136129 CN 01136129 CN 01136129 A CN01136129 A CN 01136129A CN 1347760 A CN1347760 A CN 1347760A
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Abstract
The catalyst has precursor comprising Ag and CuCl and features that powdered Ag and powdered CuCl after being mixed mechanically are roasted in air atmosphere at 300-650 deg.c; that the Ag-CuCl catalyst prepared through the simple process has composition dependent on the CuCl content; that the catalyst with CuCl content of 15-30 wt% and composition of AgCl, CuO and Ag has optimal catalyst performance including propylene conversion rate of 3-5 % and epoxypropane selectivity of 30-40 %; and that during reaction, the activity of the catalyst exhibits raising trend while the selectivity maintaining unchanged.
Description
Technical field
The present invention relates to a kind of Ag-CuCl Catalysts and its preparation method with catalytic air direct oxidation propylene system propylene oxide reaction ability.
Background technology
Expoxy propane (PO) is one of important basic Organic Chemicals.Be important organic chemicals, as the raw material of polyurethane, propane diols, non-ionic surface active agent, oil field demulsifier etc.Since 1860 first behind the synthesizing epoxypropane, so far, down 20 kinds of its production technologies.Present industrial main employing chlorohydrination and Halcon method.Because the serious environmental problem and the high production cost of existing production technology.Exploitation cleaning, cheap production of propylene oxide technology are one of current problems of paying close attention to the most in the world always.Be optimal technology path wherein with air direct oxidation propylene system expoxy propane.ICI company has applied for the patent (U.S.4168247 (1979) of a series of relevant producing propylene oxide by direct oxidation of propylene since 1976; 4390738 (1983)).The selectivity of using copper base or argentum-based catalyzer to obtain expoxy propane is 70%, and propylene conversion is 2%.Olin company had once announced a pilot-plant driving situation with the direct vapour phase oxidation process production of propylene expoxy propane in nineteen ninety, and had applied for a series of patents (U.S.4785123 (1988); 4882443 (1989); 4883889 (1989); 4885374 (1989)).In most of the cases the selectivity of expoxy propane has only 15～30%, and when best choice 46%, propylene conversion has only 12.5%.Because selectivity and productive rate are lower, also be in early stage developing stage.Although there has been the patent of many catalyst in this field, Ag-CuCl is not appeared in the newspapers as yet as the research of the direct air oxidation system expoxy propane of propylene.
Summary of the invention
The invention provides a kind of Ag-CuCl catalyst with the direct air oxidation system expoxy propane of propylene.Be made up of Ag and CuCl, the CuCl content of auxiliary agent is 5～30% of catalyst weight, and the best is 15～30%.Earlier powders A g and the CuCl for preparing mixed by a certain percentage, roasting in air atmosphere in muffle furnace, can obtain practical thing phase composition is the catalyst of AgCl, CuO and Ag.
The above-mentioned Preparation of catalysts method of the present invention is at first to pass through AgNO
3Reduction, pyrolytic or Ag
2O reduction makes powders A g, and again with powder CuCl mechanical mixture, through 300～650 ℃ of roastings 1～6 hour in air atmosphere, and optimum calcination temperature is 350-400 ℃.
Characteristics of the present invention are: (1) Ag and CuCl are after high-temperature roasting, and the Ag of formation, CuO and Ag mixture make catalyst have higher expoxy propane selectivity.The content of CuCl is very big to the reactivity worth influence.When CuCl performance the best during in 25% left and right sides, conversion ratio can reach about 3%, and selectivity can reach 30～40%.(2) catalytic performance is relevant with content and the sintering temperature of CuCl.And conversion ratio improves along with the increase in reaction time, and selectivity is stablized constant.
Ag-CuCl catalysis material provided by the invention can be used for the direct air oxidation system expoxy propane of propylene.
Description of drawings
Fig. 1 is the curve map of expression reaction time to the propylene conversion influence of Ag-CuCl (350A) catalyst.
Fig. 2 selects sex curve map for the expression reaction time to the expoxy propane of Ag-CuCl (350A) catalyst.
Fig. 3 is the TPR collection of illustrative plates of catalyst.
The specific embodiment
Below by embodiment in detail the present invention is described in detail
Embodiment 1
The detailed preparation process of powders A g (A): equimolar silver nitrate and glucose mixed aqueous solution add potassium hydroxide solution under 30 ℃ of stirring conditions, at 75 ℃ of aging 1h, filter then, wash again, at last at 120 ℃ of baking 12h.
The detailed preparation process of powders A g (B): in a certain amount of liquor argenti nitratis ophthalmicus, add hydrazine hydrate reduction, sedimentation and filtration, washing were dried by the fire 10 hours down at 120 ℃ at last.
Embodiment 3
The detailed preparation process of powders A g (C): silver nitrate directly decomposed 4 hours through 500 ℃.
Embodiment 4
The detailed preparation process of powders A g (D): in a certain amount of liquor argenti nitratis ophthalmicus, add NaOH or potassium hydroxide solution, to precipitating fully, filters, wash, back 120 ℃ are descended to dry by the fire 10 hours, at last 300 ℃ of following hydrogen reducings 2 hours.。
Embodiment 5
Ag-CuCl (300A) Preparation of catalysts: claim a certain proportion of powders A g (A) and CuCl, mechanical mixture is even, and the speed with 20 ℃/min in muffle furnace heats up, and rises to 300 ℃ of insulations 3～6 hours.
Embodiment 6
Ag-CuCl (350A) Preparation of catalysts: claim a certain proportion of powders A g (A) and CuCl, mechanical mixture is even, and the speed with 20 ℃/min in muffle furnace heats up, and rises to 350 ℃ of insulations 3～6 hours.
Embodiment 7
Ag-CuCl (400A) Preparation of catalysts: claim a certain proportion of powders A g (A) and CuCl, mechanical mixture is even, and the speed with 20 ℃/min in muffle furnace heats up, and rises to 400 ℃ of insulations 3～6 hours.
Embodiment 8
Ag-CuCl (500A) Preparation of catalysts: claim a certain proportion of powders A g (A) and CuCl, mechanical mixture is even, and the speed with 20 ℃/min in muffle furnace heats up, and rises to 500 ℃ of insulations 3～6 hours.
Embodiment 9
Ag-CuCl (650A) Preparation of catalysts: claim a certain proportion of powders A g (A) and CuCl, mechanical mixture is even, and the speed with 20 ℃/min in muffle furnace heats up, and rises to 650 ℃ of insulations 3～6 hours.
Ag-CuCl (350B) Preparation of catalysts: claim a certain proportion of powders A g (B) and CuCl, mechanical mixture is even, and the speed with 20 ℃/min in muffle furnace heats up, and rises to 350 ℃ of insulations 3～6 hours.
Embodiment 11
Ag-CuCl (350C) Preparation of catalysts: claim a certain proportion of powders A g (C) and CuCl, mechanical mixture is even, and the speed with 20～50 ℃/min in muffle furnace heats up, and rises to 350 ℃ of insulations 3～6 hours.
Embodiment 12
Ag-CuCl (350D) Preparation of catalysts: claim a certain proportion of powders A g (D) and CuCl, mechanical mixture is even, and the speed with 20 ℃/min in muffle furnace heats up, and rises to 350 ℃ of insulations 3～6 hours.
Embodiment 13
The propylene ring oxidation reaction condition is: catalyst 0.2ml is diluted to 1ml with quartz sand, C
3 =: O
2=1: 2, air speed 18000h
-1, 350 ℃ of reaction temperatures.
Embodiment 14
CuCl content is to the influence of the propylene oxidation reactivity worth of Ag-CuCl (350A) catalyst.The results are shown in Table 1.By table as seen, the adding of CuCl has obviously suppressed the oxidation activity of Ag, but the selection of expoxy propane obviously improves.When CuCl content was between 15～30%, conversion ratio and selectivity changed little, and expoxy propane is unique organic product.Further improve CuCl content, conversion ratio and selectivity and descend, and in the organic product except expoxy propane, water and carbon dioxide etc., also have acetaldehyde, acetone and methacrylaldehyde.
Table 1 CuCl content is to the influence of the propylene oxidation reactivity worth of Ag-CuCl (350A) catalyst
| Catalyst | Reaction time (min) | Conversion ratio (%) | Selectivity (%) |
| Expoxy propane acetaldehyde acetone methacrylaldehyde | |||
| ????Ag ?Ag-CuCl(5％) Ag-CuCl(15％) Ag-CuCl(20％) Ag-CuCl(25％) Ag-CuCl(30％) Ag-CuCl(35％) Ag-CuCl(40％) Ag-CuCl(50％) | ????57 ????220 ????100 ????302 ????109 ????329 ????90 ????150 ????110 ????185 ????121 ????304 ????90 ????91 ????285 ????68 ????169 | ????33.2 ????31.6 ????1.85 ????2.51 ????1.64 ????2.40 ????1.63 ????2.33 ????1.84 ????1.90 ????1.60 ????2.31 ????1.49 ????1.52 ????2.04 ????1.43 ????1.47 | ????0.86??????-???????-??????- ????0.42??????-???????-??????- ????15.7??????-???????-??????- ????13.8??????-???????-??????- ????30.6??????-???????-??????- ????29.7??????-???????-??????- ????30.5??????-???????-??????- ????33.6??????-???????-??????- ????29.9??????-???????-??????- ????30.5??????-???????-??????- ????29.6??????-???????-??????- ????30.0??????-???????-??????- ????27.7????6.84????6.52????6.02 ????26.7????15.14???7.41????9.00 ????27.9??????-???????-??????- ????14.4????1.92????3.86????8.49 ????13.3????1.62????4.93????5.20 |
Embodiment 15
CuCl content is to the influence of Ag-CuCl (350A) catalyst thing phase composition.The results are shown in Table 2.By table as seen, CuCl content is very big to the influence of catalyst thing phase composition.When CuCl content≤30%, catalyst is made up of AgCl, CuO and Ag, and at this moment, catalytic performance is higher.Its catalytic performance is apparently higher than independent AgCl, CuO or Ag catalyst.When CuCl content＞30%, catalyst is by AgCl, CuO, Ag, Cu
2O and CuCl form, and at this moment, catalyst conversion ratio and selectivity descend.This shows, when three kinds of things of AgCl, CuO and Ag coexist mutually, help the epoxidation reaction of propylene.
Table 2 CuCl content is to the influence of Ag-CuCl (350A) catalyst thing phase composition
The phase composition of catalyst thing
Ag?????????????????????Ag
Ag-CuCl(5％)?????????Ag，AgCl，CuO
Ag-CuCl(15％)????????AgCl，Ag，CuO
Ag-CuCl(20％)????????AgCl，CuO，Ag
Ag-CuCl(25％)????????AgCl，CuO，Ag
Ag-CuCl(30％)????????AgCl，CuO，Ag
Ag-CuCl(35％)????AgCl，CuCl，Cu
2O，CuO，Ag
Ag-CuCl(40％)????AgCl，CuCl，Cu
2O，CuO，Ag
Ag-CuCl(50％)????AgCl，CuCl，Cu
2O，CuO，Ag
Embodiment 16
Reaction time optionally influences the propylene conversion of Ag-CuCl (350A) catalyst and expoxy propane sees Fig. 1 and 2 respectively.By Fig. 1,2 as seen, along with the increase Ag-CuCl (15%) in reaction time and the conversion ratio of Ag-CuCl (30%) catalyst increase, and the expoxy propane selectivity changes not quite.Ag and Ag-CuCl (5%) selection of catalysts is on a declining curve.
Embodiment 17
Sintering temperature to Ag-CuCl (25%) (A) influence of catalyst see Table 3.By table as seen, sintering temperature is that good, too high sintering temperature is unfavorable to catalyst with 350～400 ℃.
Table 3 sintering temperature is to (A) influence of catalyst of Ag-CuCl (25%) [reaction temperature: 350 ℃]
| Sintering temperature (℃) | Reaction time (min) | Conversion ratio (%) | Selectivity (%) |
| Expoxy propane acetaldehyde acetone methacrylaldehyde | |||
| ????350 ????400 ????500 ????650 | ????110 ????185 ????130 ????180 ????110 ????195 ????100 | ????1.84 ????1.90 ????1.40 ????1.50 ????1.40 ????1.53 ????0.51 | ??29.9??????-?????-??????- ??30.5??????-?????-??????- ??29.1??????-?????-??????- ??29.3??????-?????-??????- ??12.9??????-?????-??????- ??13.7??????-?????-??????- ??16.1??????-?????-????13.8 |
Embodiment 18
Reaction temperature to Ag-CuCl (25%) (350A) influence of catalyst see Table 4.By table as seen, reaction temperature is spent low and the too high generation that all is unfavorable for expoxy propane, is advisable with 350 ℃.
Table 4 reaction temperature is to (350A) influence of catalyst of Ag-CuCl (25%) [reaction time: 500min]
| Reaction temperature (℃) | Conversion ratio (%) | Selectivity (%) |
| Expoxy propane acetaldehyde acetone methacrylaldehyde | ||
| ????330 ????350 ????380 | ????2.56 ????3.05 ????5.08 | ????25.6?????-?????-???????- ????31.7?????-?????-???????- ????22.9?????-????2.03????2.60 |
Embodiment 19
C
3 =: O
2Comparison Ag-CuCl (25%) (350A) influence of catalyst sees Table 5.By table as seen, C
3 =: O
2Raise, conversion ratio increases and selectivity decline, wherein C
3 =: O
2Be good at=1: 2.
Table 5 C
3 =: O
2Comparison (350A) influence of catalyst of Ag-CuCl (25%) (reaction temperature: 350 ℃) C
3 =: O
2Than (mol) reaction time (min) conversion ratio (%) expoxy propane selectivity (%)
4∶1??????????????145??????????????1.30??????????28.7
1∶1??????????????165??????????????1.91??????????28.0
1∶2??????????????185??????????????1.90??????????30.5
1∶4??????????????150??????????????4.03??????????17.0
Containing 10%H
2H
2-N
2Under the condition of gaseous mixture, the reducing property of Ag-CuCl (350A) catalyst that utilized the TPR technical research the results are shown in Figure 3.TPR result shows that Ag-CuCl (350A) has two reduction peak, and the peak temperature about 430 and 700 ℃, compares reaction result respectively, and we think that the α peak may be the active oxygen species that generates expoxy propane.
Claims (5)
1. catalyst that is used for air direct oxidation propylene system propylene oxide reaction, it is characterized in that: the CuCl mixed-powder roasting in air by Ag and content 5-30 weight % forms, and the thing phase composition of catalyst is AgCl, CuO and Ag.
2. according to the described catalyst of claim 1, it is characterized in that: CuCl content is 15-30 weight %.。
3. the described Preparation of catalysts method of claim 1 is characterized in that: at first pass through AgNO
3Reduction, pyrolytic or Ag
2O reduction makes powders A g, again with powder CuCl mechanical mixture, through 300～650 ℃ of roastings 1～6 hour in air atmosphere.
4. according to the described Preparation of catalysts method of claim 3, it is characterized in that: sintering temperature is 350～400 ℃.
5. according to the described catalyst of claim 1, be used for by air as oxygen source direct oxidation propylene system propylene oxide reaction.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01136129 CN1128014C (en) | 2001-10-16 | 2001-10-16 | Ag-CuCl catalyst for the direct oxidation of propylene with air to prepare epoxypropane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01136129 CN1128014C (en) | 2001-10-16 | 2001-10-16 | Ag-CuCl catalyst for the direct oxidation of propylene with air to prepare epoxypropane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1347760A true CN1347760A (en) | 2002-05-08 |
| CN1128014C CN1128014C (en) | 2003-11-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01136129 Expired - Fee Related CN1128014C (en) | 2001-10-16 | 2001-10-16 | Ag-CuCl catalyst for the direct oxidation of propylene with air to prepare epoxypropane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350366A (en) * | 2011-08-25 | 2012-02-15 | 武汉理工大学 | Preparation method of Ag-AgCl-TiO2/rectorite composite photochemical catalyst |
| CN110711592A (en) * | 2019-09-05 | 2020-01-21 | 宁夏大学 | Preparation method, pretreatment method and application of propylene epoxidation catalyst |
-
2001
- 2001-10-16 CN CN 01136129 patent/CN1128014C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350366A (en) * | 2011-08-25 | 2012-02-15 | 武汉理工大学 | Preparation method of Ag-AgCl-TiO2/rectorite composite photochemical catalyst |
| CN102350366B (en) * | 2011-08-25 | 2013-07-17 | 武汉理工大学 | Preparation method of Ag-AgCl-TiO2/rectorite composite photochemical catalyst |
| CN110711592A (en) * | 2019-09-05 | 2020-01-21 | 宁夏大学 | Preparation method, pretreatment method and application of propylene epoxidation catalyst |
| CN110711592B (en) * | 2019-09-05 | 2022-07-08 | 宁夏大学 | Preparation method, pretreatment method and application of propylene epoxidation catalyst |
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| Publication number | Publication date |
|---|---|
| CN1128014C (en) | 2003-11-19 |
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