CN1180884C - Catalyst for cyclopropanizing reaction of olefine and its preparing process - Google Patents
Catalyst for cyclopropanizing reaction of olefine and its preparing process Download PDFInfo
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- CN1180884C CN1180884C CNB011200944A CN01120094A CN1180884C CN 1180884 C CN1180884 C CN 1180884C CN B011200944 A CNB011200944 A CN B011200944A CN 01120094 A CN01120094 A CN 01120094A CN 1180884 C CN1180884 C CN 1180884C
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Abstract
The present invention relates to a supported catalyst which is used for cyclopropanizing reaction of 2, 5-dimethyl-2, 4-hexadiene. The present invention comprise active constituents which comprise one of elements of Fe, Co, Ni, Cu, Zn, Cr, Mn, or Ti, etc. or a mixture of the elements, and an auxiliary agent which comprises one of the alkali metal elements of Li, Na, K, etc. or a mixture of the elements, wherein the adding quantity of the active constituents is 20-90%(calculated by oxide) of the total amount of the catalyst, and the adding quantity of the auxiliary agent is 0.1-5.0%(calculated by oxide) of the total amount of the catalyst. Aluminum oxide, silica gel, activated carbon, etc. serve as carriers. The preparation of the catalyst adopts a dipping method which is added with active constituents, and carriers adopt acid or alkali liquid with pH = 4-13 for modification preprocessing. In a dipping process of the active constituents, one or a plurality of oxygen containing organic compounds containing a hydroxy group or a carboxyl are added. When the catalyst is used for cyclopropanizing reaction of olefin and diazo acetic ester, the catalyst has the characteristics of less dosage, high yield, less coking quantity, etc. The catalyst is easily separated with a reaction system.
Description
Technical field
The present invention relates to a kind of loaded catalyst, provide a kind of especially and be used for 2,5-dimethyl-2, the preparation method of 4-hexadiene cyclopropanization reaction loaded catalyst.In the presence of this catalyst, the cyclopropanization reaction with alkene and diazonium acetate carry out prepares the first chrysanthemumic acid methyl esters, the first chrysanthemumic acid ethyl ester etc.Characteristics such as this process has the reaction yield height, coking is few, catalyst amount is few, catalyst and reaction system are easily separated.
Technical background
Olefin catalytic is Cyclopropanated to be the synthetic important method of a class organic intermediate, is widely used in processes such as medicine and pesticide industry synthesize, as the synthetic pesticide intermediate first chrysanthemumic acid methyl esters, the first chrysanthemumic acid ethyl ester, dichlor chrysanthemic acid methyl esters, dichlor chrysanthemic acid ethyl ester etc.The synthetic method that adopts is to adopt the homogeneous catalysis method synthetic mostly at present, is catalyst etc. as adopting schiff bases copper class complex compound; The coking of course of reaction is more when adopting these class methods, not only causes wastage of material, and the intractability of the not clear tarry discarded object that generates is very big, seriously polluted; Also cause industrial pipeline to stop up easily, influence the trouble-free operation of commercial plant; In addition, because the separation difficulty of homogeneous catalyst and product makes catalyst enter product, can't reclaim and reuse, synthetic cost is higher, and waste is serious.Therefore, developing a kind of Cyclopropanated catalyst of heterogeneous alkene easily separated, that coking is few, yield is high, consumption is few is the development goal of industrial quarters and research department.
BP GB 1,533, and 381 reported method are that employing copper sulphate is catalyst, with 1, and 1-two chloro-4-methyl isophthalic acids, 3-pentadiene and ethyl diazoacetate reaction, the yield of synthetic dichlor chrysanthemic acid ethyl ester is 40-50%.This method has used the inorganic salts of copper to be catalyst, but the reactivity of catalyst is not high, and the yield of target product is also lower.
The Japan Patent spy opens clear 51-19747 reported method, has used the solid inorganic oxide cupric oxide to be catalyst, in the presence of this catalyst, makes 1,1-two chloro-4-methyl isophthalic acids, 3-pentadiene and the synthetic dichlor chrysanthemic acid ethyl ester of ethyl diazoacetate reaction; Though catalyst separates easily with reaction system, the product yield that obtains only 35%, industrial application value is little.
Chinese patent 97119481.5 has reported that a kind of carrier-free multicomponent inorganic oxide powder is a catalyst, pulverous inorganic oxide comprises one or more in cupric oxide, manganese oxide, cobalt oxide, the iron oxide etc., with 1,1-two chloro-4-methyl isophthalic acids, 3-pentadiene and ethyl diazoacetate reaction, synthetic dichlor chrysanthemic acid ethyl ester; Yield is 52-67.6%.Adopt this method, catalyst separates easily with product, and yield is higher, has industrial application value; But because catalyst is to make by simple and mechanical mixed method, the surface area of catalyst is less, and the grain size of active component is bigger, and the skewness of active component all has considerable influence to activity of such catalysts and product yield.
Summary of the invention
The objective of the invention is: develop and a kind ofly be used for 2,5-dimethyl-2, cyclopropanization reaction loaded catalyst that 4-hexadiene and diazoacetic acid methyl esters carry out and preparation method thereof.This catalyst has improved surface area, and active component is evenly distributed; For reaction, have high yield, low coking rate, catalyst amount few and with characteristics such as reaction system is easily separated.
For achieving the above object, the invention provides a kind of loaded catalyst, the activity of such catalysts component comprises: one or more of elements such as Fe, Co, Ni, Cu, Zn, Cr, Mn or Ti, addition is the 20-90% (in oxide) of total catalyst weight, and one or more of alkali metals such as auxiliary agent Li, Na, K, addition is the 0.1-5.0% (in oxide) of total catalyst weight, and other is a carrier.The preferable content of active component and adjuvant component is the 60-90% of catalyst gross mass among the present invention, and optimum content is 65-75% (in an oxide).These elements exist with reducing condition, oxidation state or other ionic condition in catalyst.
In above-mentioned catalyst, need to add appropriate carriers; Heterogeneous catalytic reaction carries out in solid catalyst surface, and suitable carriers can increase the effective surface area and the proper pore structure of catalyst effectively, improves the heat endurance of catalyst, can also increase the relative number in activated centre.Catalyst carrier can be silica gel, aluminium oxide, active carbon etc.
In addition, the invention provides a kind of above-mentioned Preparation of catalysts method, be to adopt dipping method to add active component and adjuvant component and the loaded catalyst that forms, its step is 1) the modification preliminary treatment carried out in the carrier acid of pH=4-13 before use or the aqueous slkali; 2) be taken up in order of priority dipping active component and adjuvant component; 3) behind each dipping, carry out drying, under 200-500 ℃, carry out roasting then.In addition, when being carrier with active carbon, roasting is carried out under inert gas or reducibility gas.
In above-mentioned preparation method, catalyst carrier needed to carry out the finishing preliminary treatment of acid or alkali before the dipping active component.Because the surface area of different carriers is different with the pH value of surperficial point of zero electric charge correspondence, during the active component of direct impregnation, active component has bigger difference in the distribution and the grain size size of catalyst surface.As SiO
2Surface charge when being zero, about the pH=2 of corresponding aqueous medium, and Al
2O
3PH value when surperficial zero charge is about 9.The method of the modification by acid or alkali changes the surface acid alkalescence of carrier, the distribution of adjustable activity component.PH value according to the surperficial point of zero electric charge correspondence of different carriers, can modify the surface by methods such as acid or alkaline aqueous solution dipping, filtration and oven dry, be beneficial to effective dispersion of active component, avoid in the dipping process diffusion difficulty, or make active component stop up the duct because of the alkalescence on surface in the aperture deposition.The acid of adopting can be inorganic or organic acids such as rare nitric acid, hydrochloric acid, oxalic acid, malonic acid; The alkali that adopts when base-modified can be inorganic or organic bases such as ammoniacal liquor, KOH, NaOH, pyridine derivate.
In addition, in above-mentioned preparation method, the dipping active component adopts nitrate, chloride or the acetate solution that contains Fe, Co, Ni, Cu, Zn, Cr, Mn or Ti, and the dipping auxiliary agent adopts nitrate, chloride, acetate or the hydroxide solution that contains Li, Na or K.
In addition, in above-mentioned preparation method, compounding agent solution preferably adopts the hydroxide of Li, Na or K.
In addition, in above-mentioned preparation method, in the dipping process of catalyst activity component, add the oxygen-containing organic compound that one or more contain hydroxyl or carboxyl.
In above-mentioned preparation method, in the dipping active component, need to add organic compound; This organic compound can be the template agent of catalyst, also the complexing agent of active component.After the dipping active component, by oven dry and roasting, organic compound decomposes or volatilization is left away.This organic compound can be polyvinyl alcohol, polyethylene glycol, glucose, citric acid or malonic acid etc. one or more contain the oxygen-containing organic compound of hydroxyl or carboxyl.
The catalyst of the invention described above can be used for cyclopropane reaction of olefin, and particularly 2,5-dimethyl-2,4-hexadiene cyclopropanization reaction adds the quality of catalyst in the reaction and the better quality ratio of diazoacetic acid methyl esters is 1: 1000, and optimal proportion is 1: 300; The preferred proportion of catalyst and alkene quality is 1: 10-3000, optimal proportion are 1: 50-1000.
The specific embodiment
Below by embodiment in detail the present invention is described in detail:
Embodiment 1: the preparation of catalyst A and activity
Take by weighing the dry active oxidation aluminium powder (20-40 order) of 12.6 grams, contain 0.35 aqueous solution dipping that restrains KOH after 24 hours, record the pH=9 that modifies solution with 50ml; The solid that filters is 120 ℃ of oven dry; After 350 ℃ of roastings and cooling, with the mixed aqueous solution dipping that contains polyvinyl alcohol, cobalt, copper, iron isoreactivity component 20 hours, 110 ℃ of oven dry down, 450 ℃ of roastings 2 hours; The gained solid contains the aqueous solution dipping 20 hours of 0.75 gram potassium hydroxide with 40 grams, 110 ℃ of oven dry down, and 400 ℃ of roastings 2 hours.The active component addition is 70% (in an oxide) of catalyst gross mass in the catalyst A that obtains.The composition and the specific area of catalyst A are listed in table 1.
In the there-necked flask of 250ml; add 0.10 gram catalyst A; add 20 grams 2 again; 5-dimethyl-2, the 4-hexadiene heats up 130 ℃ under nitrogen protection; drip the dichloroethane solution of 6.9 grams (folding hundred amounts) diazoacetic acid methyl esters; dropwised in 1 hour, and continued to stir after 1 hour and reduce to room temperature, filter to isolate catalyst and be equipped with repeated use.After weighing, filtrate uses gas chromatograph internal mark method determination content, calculated yield (in the diazoacetic acid methyl esters).Product yield (%) is listed in table 1.
Embodiment 2: the preparation of catalyst B, C, D and activity
Take by weighing the dry active oxidation aluminium powder of 37.8 grams, contain 1.05 aqueous solution dippings that restrain KOH after 24 hours, record the pH=9 that modifies solution with 150ml; The solid that filters is 120 ℃ of oven dry; 350 ℃ of following roastings 2 hours.Carrier after gained modified is equally divided into 3 parts, respectively with citric acid content is identical, the inorganic salts active component content is different mixture aqueous solution dipping 20 hours, and 110 ℃ of oven dry down, 450 ℃ of roastings 2 hours; The gained solid contains 0.75 gram potassium hydroxide with 40 grams and got aqueous solution dipping 20 hours, 110 ℃ of oven dry down, and 400 ℃ of roastings 2 hours.The catalyst that obtains is respectively B, C and D.Character such as catalyst composition and specific area are listed in table 1.
Cyclopropanization reaction is except that the catalyst difference, and all the other operations and condition and embodiment 1 are identical, and product yield (%) is listed in table 1.
The composition of table 1: catalyst A-D and activity
| Catalyst | Modify the pH value | Amount of active ingredients (w% is in oxide) | Specific area | Yield | ||||
| Cu | Fe | Co | K | Add up to | (m 2/g) | (％) | ||
| A | 9 | 21.3 | 25.7 | 21.5 | 1.5 | 70.0 | 73.0 | 80.0 |
| B | 9 | 22.9 | 27.5 | 23.1 | 1.5 | 75.0 | 89.0 | 74.7 |
| C | 9 | 24.3 | 29.3 | 24.5 | 1.9 | 80.0 | 102.2 | 75.2 |
| D | 9 | 26.1 | 31.4 | 26.3 | 1.8 | 85.6 | 103.6 | 74.6 |
Embodiment 3: catalyst E
1-E
5Preparation with active
Take by weighing the dry active oxidation aluminium powder of 12.6 grams at every turn, contain 0.35 aqueous solution dipping that restrains KOH after 24 hours, record the pH=9 that modifies solution with 50ml; Except that active component was different with the alkali metal kind, all the other Preparation of Catalyst were identical with embodiment 1 with the operating procedure that reactivity is estimated.Catalyst is formed and product yield (%) is listed in table 2.
Table 2: catalyst E
1-E
5Composition and activity
| Catalyst | Amount of active ingredients (w% is in oxide) | Yield | ||||||
| Cu | Fe | Co | Zn | Cr | K | Li | (％) | |
| E 1 | 21.3 | 0 | 0 | 0 | 0 | 1.5 | 0 | 70.4 |
| E 2 | 21.3 | 25.7 | 0 | 0 | 0 | 0 | 1.5 | 73.6 |
| E 3 | 0 | 25.7 | 21.5 | 0 | 0 | 1.9 | 0 | 68.3 |
| E 4 | 0 | 0 | 21.5 | 16.2 | 0 | 0 | 1.8 | 45.9 |
| E 5 | 0 | 0 | 0 | 16.2 | 25.7 | 0 | 1.5 | 47.8 |
Embodiment 4: catalyst F
1-F
7Preparation and activity
Take by weighing the dry active oxidation aluminium powder of 12.6 grams, the aqueous solution dipping that contains different content KOH or nitric acid with 50ml was measured the pH value of modifying solution after 24 hours respectively at every turn.Except that the pH value difference of carrier modification solution, all the other Preparation of Catalyst are identical with embodiment 1 with the raw material consumption with the operating procedure that reactivity is estimated.Catalyst composition, specific area and product yield (%) are listed in table 3.
Table 3: catalyst F
1-F
7Composition and activity
| Catalyst | Modify the pH value | Activity component load quantity (w%, oxide meter) | Specific area | Yield | |||
| Cu | Fe | Co | K | (m 2/g) | (％) | ||
| F 1 | 4 | 21.3 | 25.7 | 21.5 | 1.5 | 129.2 | 70.3 |
| F 2 | 5 | 21.3 | 25.7 | 21.5 | 1.5 | 101.0 | 73.2 |
| F 3 | 6 | 21.3 | 25.7 | 21.5 | 1.5 | 89.9 | 78.4 |
| F 4 | 7 | 21.3 | 25.7 | 21.5 | 1.5 | 85.8 | 77.3 |
| F 5 | 10 | 21.3 | 25.7 | 21.5 | 1.5 | 103.5 | 76.6 |
| F 6 | 11 | 21.3 | 25.7 | 21.5 | 1.5 | 117.2 | 74.9 |
| F 7 | 13 | 21.3 | 25.7 | 21.5 | 1.5 | 126.4 | 75.4 |
Embodiment 5: reaction temperature and catalyst activity
Except that reaction temperature, the reactive moieties among catalyst composition, operation condition and inventory and the embodiment 1 is identical, and reactivity the results are shown in table 4.
Table 4: reaction temperature is to the activity influence of catalyst A
| Catalyst | Reaction temperature | Yield |
| (℃) | (％) | |
| A | 80 | 51.8 |
| A | 90 | 73.0 |
| A | 110 | 75.6 |
| A | 130 | 80.0 |
Embodiment 6: catalyst inventory and reactivity
Except that the catalyst inventory, the reactive moieties among reaction temperature, catalyst composition, operation condition and inventory and the embodiment 1 is identical, and reactivity the results are shown in table 5.
Table 5: the consumption of catalyst A is to the influence of activity
| Catalyst | The ingredient proportion of cyclopropanization reaction (w/w) | Product yield | ||
| Catalyst | 2,5-dimethyl-2,4-hexadiene | The diazoacetic acid methyl esters | (％) | |
| A | 1 | 50 | 17.5 | 78.3 |
| A | 1 | 100 | 35.1 | 79.6 |
| A | 1 | 200 | 70.2 | 80.0 |
| A | 1 | 400 | 140.4 | 83.5 |
| A | 1 | 800 | 280.7 | 84.6 |
| A | 1 | 1200 | 421.0 | 66.0 |
| A | 1 | 2800 | 982.5 | 49.2 |
Comparative example 1: the preparation of catalyst G and performance
After commercially available cupric oxide, iron oxide, cobalt oxide, potassium hydroxide isoreactivity component carried out mechanical mixture according to the ratio of active component among the embodiment 1, be ground to below 100 orders.Except that the catalyst difference, all the other operations of cyclopropane reaction of olefin are identical with embodiment 1 with inventory; The yield that records product is 62.8%.
Comparative example 2: catalyst H
1-H
5Preparation and performance
Copper nitrate, the dissolving of ferric nitrate mixture water add basic cobaltous carbonate and glucose and react, and this mixture aqueous solution evaporation is near dried.200 ℃ of dryings 2 hours, 450 ℃ of roastings 2 hours; Flooded 24 hours with the KOH aqueous solution again.After the oven dry, 400 ℃ of roastings 2 hours.Except that the catalyst difference, all the other operations of cyclopropane reaction of olefin are identical with embodiment 1 with inventory; Gained catalyst H
1-H
5Composition (in oxide) and product yield list in table 6.
Table 6: the H of catalyst
1-H
5Composition and activity
| Catalyst | Active component addition (w%, oxide meter) | Yield | |||
| Cu | Fe | Co | K | (％) | |
| G 1 | 40.4 | 48.6 | 8.1 | 2.9 | 54.7 |
| G 2 | 37.3 | 45.0 | 15.0 | 2.7 | 67.6 |
| G 3 | 34.7 | 41.8 | 21.0 | 2.5 | 70.1 |
| G 4 | 32.5 | 39.1 | 26.1 | 2.3 | 60.5 |
| G 5 | 30.5 | 36.7 | 30.7 | 2.2 | 64.7 |
Result according to above-described embodiment and comparative example can obtain, and the loaded catalyst of the present invention's preparation has following characteristics: (1) has high activity for cyclopropane reaction of olefin, and product yield reaches 84.6%. (2) catalyst amount is few, and the optimum quality ratio of catalyst and alkene is about 1: 800, with the mass ratio of diazoacetic acid methyl esters be about 1: 300. (3) the course of reaction coking is few, finds no obvious polymer and generates. (4) easily separated with reaction system. Therefore, the catalyst of the present invention's preparation has industrial application value.
Claims (6)
1. one kind is used for 2,5-dimethyl-2, the preparation method of 4-hexadiene catalyst for cyclopropane reaction, it is characterized in that: the activity of such catalysts component is one or more of Fe, Co, Ni, Cu, Zn, Cr, Mn or Ti element, and addition is counted the 20-90% of total catalyst weight with oxide; Auxiliary agent is one or more among alkali metal Li, Na or the K, in the oxide addition is 0.1-5.0%, all the other are aluminium oxide, silica gel or absorbent charcoal carrier, adopt dipping method to add active component and adjuvant component and the loaded catalyst that forms, the steps include:
1) carrier is modified preliminary treatment before use in the acid of pH=4-13 or aqueous slkali; 2) be taken up in order of priority dipping active component and adjuvant component; 3) behind each dipping, carry out drying, under 200-500 ℃, carry out roasting then.
2. preparation method according to claim 1 is characterized in that roasting is carried out when being carrier with active carbon under inert gas or reducibility gas.
3. preparation method according to claim 1, it is characterized in that flooding active component and adopt nitrate, chloride or the acetate solution that contains Fe, Co, Ni, Cu, Zn, Cr, Mn or Ti, auxiliary agent adopts nitrate, chloride, acetate or the hydroxide solution that contains Li, Na or K.
4. preparation method according to claim 3 is characterized in that compounding agent solution adopts the hydroxide of Li, Na or K.
5. preparation method according to claim 2 is characterized in that: in the dipping process of catalyst activity component, add the oxygen-containing organic compound that one or more contain hydroxyl or carboxyl.
6. preparation method according to claim 5 is characterized in that: oxygen-containing organic compound is polyvinyl alcohol, polyethylene glycol, glucose, citric acid or malonic acid.
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| CNB011200944A CN1180884C (en) | 2001-07-13 | 2001-07-13 | Catalyst for cyclopropanizing reaction of olefine and its preparing process |
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|---|---|---|---|
| CNB011200944A CN1180884C (en) | 2001-07-13 | 2001-07-13 | Catalyst for cyclopropanizing reaction of olefine and its preparing process |
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| CN101816941B (en) * | 2009-02-27 | 2011-11-30 | 中国石油化工股份有限公司 | Catalyst for isopropylamine and application thereof |
| CN101597347B (en) * | 2009-06-19 | 2011-03-09 | 上海化工研究院 | Main catalyst component for polymerizing ethylene and ethylene polymerizing catalyst containing the component |
| CN102441408B (en) * | 2010-10-13 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method for hydrogenation catalyst |
| CN104177548B (en) * | 2014-08-19 | 2016-08-24 | 武汉大学 | A kind of fluorescence pyrazoline grafting polyvinyl alcohol and preparation method thereof |
| CN104941646B (en) * | 2015-05-25 | 2017-07-14 | 安徽海德石油化工有限公司 | A kind of heavy naphtha catalytic reforming prepares high-knock rating gasoline catalyst |
| CN105056924B (en) * | 2015-08-18 | 2017-08-15 | 南京大学 | A kind of Ti3+Adulterate non-precious metal catalyst preparation and its in the application of selective hydrogenation |
| CN110026212B (en) * | 2019-05-23 | 2022-03-04 | 临海市利民化工有限公司 | Cracking catalyst and method for preparing sitafloxacin intermediate by using same |
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