JPH0246584B2 - OREFUINRUINOEHOKISHIKAHOHO - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a process for the molybdenum-catalyzed epoxidation of C--C olefins with t-butyl hydroperoxide or t-amyl hydroperoxide in the liquid phase in a polar reaction medium. The epoxidation of olefins to produce various oxidized compounds has long been the subject of research by those skilled in the art. Furthermore, it is well known that the reactivity of various olefins varies depending on the number of substituents on the carbon atoms forming the double bond. Ethylene itself has the lowest relative rate of epoxidation, followed by propylene and other alpha olefins. Formula R ₂ C=CR ₂
Compounds of the formula (wherein R simply represents an alkyl or other substituent) can be epoxidized at the fastest rate. Of course, it has long been known that the production of ethylene oxide from ethylene is accomplished by reaction with molecular oxygen over a silver catalyst. Many patents have been issued for various silver catalyzed processes for producing ethylene oxide. Unfortunately, however, the silver catalyst method does not work well for olefins other than ethylene. For a long time, commercial production of propylene oxide was possible only by the complicated chlorohydrin process. Another commercial method for producing substituted oxides from alpha olefins such as propylene is based on organic oxide compounds such as molybdenum, tungsten, titanium, niobium, tantalum, rhenium, selenium, chromium, zirconium, tellurium, etc. Alternatively, US Pat. No. 3,351,635 shows that it can be produced by reacting an olefinic unsaturated compound with an organic hydroperoxide in the presence of a uranium catalyst.
It was not discovered until it was taught in No. US Pat. No. 3,350,422 teaches a similar process using a soluble vanadium catalyst. Molybdenum is the preferred catalyst. A corresponding excess of olefin over hydroperoxide is taught as conventional for the reaction. Also, U.S. Pat.
See also No. 3526645. Although this research is recognized as being extremely important for the development of a commercial process for producing propylene oxide that does not involve the chlorohydrin process, it is also recognized that molybdenum has a number of problems. . For example, large amounts of alcohol were produced corresponding to the peroxides used, and if t-butyl hydroperoxide was used as a co-reactant, a use and market for t-butyl alcohol had to be found. When propylene is the olefin to be epoxidized, various propylene dimers, often referred to as hexenes, are formed. In addition to the undesirable fact that propylene is not utilized optimally, various problems arise in separating the desired propylene oxide from the product mixture. Furthermore, molybdenum catalyst is unstable and the recovery rate for its reuse is low. Many other methods have been proposed for producing alkylene oxides by epoxidizing olefins (particularly propylene). U.S. Patent No. 3,666,777 awarded to Sargenti
No. 1, No. 1, No. 2003-100002, a molybdenum-containing epoxidation catalyst prepared by heating molybdenum powder with a stream containing unreacted t-butyl hydroperoxide and a polyhydroxy compound used as an oxidizing agent in the epoxidation process. A method has been found to epoxidize propylene using a solution. This polyhydroxy compound has a molecular weight of 200-300 and is formed as a by-product during the epoxidation process. British patent no.
Described in No. 1338015. An improvement in this process is the inclusion of a free radical inhibitor in the reaction mixture to prevent the formation of _C5 - _C7 hydrocarbons as by-products which must be removed by extractive distillation. Proposed free radical inhibitors include t-butylcatechol and 2,
6-di-t-butyl-4-methylphenol. In U.S. Pat. No. 3,849,451, Stein et al. disclosed in U.S. Pat. This is an improvement on the Kollar method. Schutstein et al. also suggest the use of some reaction vessels with a somewhat higher temperature in the last region in order to carry out the reaction more completely. The primary advantage of this appears to be improved yields and suppressed side reactions. Prescher et al., in U.S. Reissue Patent No. 31381, disclose a method for producing propylene oxide from propylene and hydrogen peroxide, which involves a stirred vessel, a reaction tube, and a loop reactor. Multiple reactors such as can be used.
They can, for example, use a series of multiple stirred vessels, such as 3 to 6 reaction vessels connected in stages, or 1 to 3 stirred vessels arranged in series and We recommend using the following reaction tubes. According to US Pat. No. 3,418,430 to Lussell et al., in the presence of a metal epoxidation catalyst such as a molybdenum compound in a solvent solution, the molar ratio of propylene to hydroperoxide is from 0.5:1 to 100:1 (preferably 2:1 to 10:1),
A method for producing propylene oxide by reacting propylene with an organic hydroperoxide at a temperature of -20 to 200 °C (preferably 50 to 120 °C) is disclosed, according to which olefin The conversion rate of is low (e.g. 10-30%) and unreacted oxygen is removed from unreacted propylene. U.S. Pat. No. 3,434,975 to Sheng et al. discloses a method for producing molybdenum compounds useful as catalysts for reactions of olefins and organic hydroperoxides, in which molybdenum metal is saturated with carbon dioxide. In the presence of ₁ - _C4 alcohol,
It is reacted with an organic hydroperoxide such as t-butyl hydroperoxide, a peracid or hydrogen peroxide. U.S. Pat. No. _3,862,961 to Shien et al. describes a molybdenum _- catalyzed epoxidation reaction of alpha-olefins and alpha-substituted olefins using relatively unstable hydroperoxides. This is accomplished by using a certain amount of a stabilizer consisting of a sec- or t-monohydric alcohol. The preferred alcohol appears to be t-butyl alcohol. Citric acid is manufactured by Herzog in U.S. Patent No.
It is used to minimize iron-catalyzed decomposition of organic hydroperoxides without adversely affecting the reaction between hydroperoxides and olefins in a similar oxirane production process taught in No. 3,928,393. According to the inventors of U.S. Pat. No. 4,217,287, when barium oxide is present in the reaction mixture, catalytic epoxidation reactions of olefins with organic hydroperoxides use relatively low molar ratios of olefin to hydroperoxide. This can be carried out successfully with good selectivity to epoxides based on the converted hydroperoxides. The alpha olefinically unsaturated compound must be added in small portions to the organic hydroperoxide to ensure that an effective excess of hydroperoxide is present. Selective Olefin Epoxidation at High Hydroperoxide to Olefin Ratio
Hydroperoxide to Olefin Rations, Journal of Catalysis
Selective epoxidation of olefins using cumene hydroperoxide (CHP), as reported by Wu and Swift in vol. 43, pp. 380-383 (1976), When barium oxide is present with a molybdenum catalyst, this is achieved when the ratio of CHP to olefin is high. Catalysts other than molybdenum have also been tried. Copper polyphthalocyanines activated by contact with aromatic heterocyclic amines as discovered by Brownstein et al. and described in U.S. Pat. and is an effective catalyst for the oxidation of alicyclic compounds (eg propylene). Various methods for making molybdenum catalysts useful in these olefin epoxidation processes are described in the following patents: US Pat. No. 3,362,972 to Kollar;
U.S. Pat. No. 3,480,563 to Bonetti et al.; U.S. Pat. No. 3,578,690 to Becker; U.S. Pat.
It is number 4009122. It has also been proposed to use t-butyl alcohol produced when propylene is reacted with t-butyl hydroperoxide as an intermediate in the synthesis of other organic compounds. And Schneider proposed a method for producing isoprene in U.S. Pat.
3418340 to give t-butyl alcohol. Connor et al. in US Pat. No. 3,836,603 propose the use of t-butyl alcohol as an intermediate in a multi-step process for the production of p-xylene. Also related to the present discovery are these patents relating to methods for separating propylene oxide from other by-products formed. These patents show great interest in separating useful propylene oxide from hexene oligomers with very similar boiling points. It would be a significant advance in this technology if no oligomeric by-products were produced, or if they were produced, their separation steps were so small that they were unnecessary, as was the case in these patents. U.S. Pat. No. 3,464,897 describes the separation of propylene oxide from other hydrocarbons having boiling points close to that of propylene oxide by distilling the mixture in the presence of open-chain or cyclic paraffins containing 8 to 12 carbon atoms. is listed. Similarly, propylene oxide was
The same absorbent disclosed in No. 3,607,669 can be used to separate it from water. Propylene oxide is produced from the by-products by fractional distillation in the presence of hydrocarbons having 8 to 20 carbon atoms according to US Pat. No. 3,843,488. Furthermore, according to U.S. Pat. No. 3,909,366, propylene oxide is extracted from paraffinic and olefinic carbonized impurities by extractive distillation in the presence of aromatic hydrocarbons having 6 to 12 carbon atoms. It is taught that hydrogens are produced. The present invention utilizes a charged hydroperoxide (t-butyl hydroperoxide or t-amyl hydroperoxide) as a catalyst in the presence of an effective amount of a soluble molybdenum catalyst in a liquid phase in a reaction zone to react with a charged C ₃ -C ₂₀ . The present invention relates to a method for reacting with an olefin to produce an olefin epoxide, a product corresponding to the charged olefin, and an alcohol, a product corresponding to the charged hydroperoxide. Charge a solution of about 30% by weight of the charged hydroperoxide in the product alcohol to the reaction zone and add enough of the charged olefin to the reaction zone to provide a ratio of about 0.5 to about 2 moles of charged olefin to 1 mole of charged peroxide. By charging the reaction medium in an appropriate amount relative to the amount of the charging solution in the alcohol produced, the amount of polar components (hydroperoxide charged, alcohol produced and epoxide produced) is increased to 60% by weight or more in the reaction zone. improved by the method of the present invention by maintaining the The preferred olefin charged is propylene and the preferred hydroperoxide is t-butyl hydroperoxide. The corresponding epoxide in this case is propylene oxide and the alcohol produced is t-butyl alcohol. Under atmospheric conditions, t-butyl hydroperoxide and t-amyl hydroperoxide are relatively stable materials. However, as temperatures rise, these hydroperoxides tend to become unstable, resulting in the onset of thermal and/or catalytic decomposition and the production of undesirable byproducts such as ketones, low molecular weight alcohols, tertiary alcohols, and oxygen. Product formation occurs. Reacting such a hydroperoxide with an olefin using a catalyst,
This is a particularly troublesome problem at temperatures of 50-180°C (e.g. 100-130°C) commonly used when producing olefin epoxides. This problem can be overcome, at least in part, by conducting the epoxidation reaction in the presence of an excess of olefin reactant. However, unreacted olefin must be separated from the epoxide reaction product for reuse, and separation becomes increasingly difficult as the molecular weight of the olefin reactant increases. The problem is that it can also occur when using smaller molecular weight olefins, and the utility costs associated with recovering and reusing large quantities of olefins anyway are greater than the costs of producing the corresponding olefin epoxide and alcohol reaction products. This puts considerable pressure on the In addition, it increases the reaction rate, thereby increasing the TBHP
Alternatively, if excess propylene is used to suppress the side reactions of TAHP, a serious problem arises in the form of propylene dimers. Dimer formation is a secondary reaction and is accelerated as the concentration of propylene increases. Also, the use of excess propylene provides a non-polar medium, which in turn tends to make the molybdenum catalyst less solubilized during the reaction. According to the present invention, a C ₃ -C ₂₀ olefin is converted into t-butyl hydroperoxide or t-butyl hydroperoxide in the liquid phase in the presence of a catalytically effective amount of a soluble molybdenum catalyst.
In a process for preparing olefin epoxides by reaction with amyl hydroperoxide, the hydroperoxide is charged to the reaction zone with a solution of at least 30% by weight of the corresponding product alcohol, and the olefin is added to the reaction zone per mole of hydroperoxide. It has been discovered that charging the reaction zone in amounts such that 0.5 to 2 moles of olefin, relative to the hydroperoxide charged, results in unexpectedly high selectivities to olefin epoxide based on hydroperoxide converted. Reactants and Catalysts The process of the present invention is used to epoxidize _C3 - _C20 olefinically unsaturated compounds, such as substituted or unsubstituted aliphatic and cycloaliphatic olefins. This method is particularly useful for epoxidizing compounds having at least one double bond located in the alpha position or internally of the carbon chain. Typical compounds include propylene, n
-Butylene, isobutylene, pentenes, methylpentenes, hexenes, octenes, dodecenes, cyclohexene, substituted cyclohexenes, butadiene, styrene, substituted styrenes, vinyltoluene, vinylcyclohexene, phenylcyclohexene, and the like. The invention is very useful for the epoxidation of primary or alpha olefins, and propylene is particularly advantageously epoxidized according to the process of the invention. Surprisingly, it has been found that the process of the invention does not work equally well for all hydroperoxides. For example, when cumene hydroperoxide is used and propylene is used in a very excessive amount, the selectivity to propylene oxide based on the added cumene hydroperoxide is poor. t-Butyl hydroperoxide (TBHP) and t-amyl hydroperoxide (TAHP)
is the hydroperoxide used in the method of the invention. Among them, t-butyl hydroperoxide is preferred. The TBHP must be provided as a solution of at least 30% by weight, preferably about 40-75% by weight, in t-butyl alcohol. Suitable catalysts for the epoxidation process of the invention are molybdenum catalysts that are soluble in the reaction medium. Examples of suitable soluble catalysts are molybdenum compounds such as molybdenum octonate, molybdenum naphthenate, molybdenum acetylacetonate, molybdenum/alcohol complexes, molybdenum/glycol complexes, and the like. Other catalysts known to be useful are 1984
Molybdenum complexes of alkylene glycols and molybdenum compounds as described in U.S. Pat. be. Briefly, these complexes are prepared by reacting ammonium-containing molybdenum compounds with alkylene glycols in the presence of water at elevated temperatures (eg, 80-130°C). Among molybdenum compounds containing ammonium, preferred are ammonium heptamolybdate tetrahydrate or ammonium dimolybdate hydrate. Preferred alkylene glycols are ethylene glycol and/or propylene glycol, although others have been found to be useful. Still other catalysts which have been found useful in the practice of the present invention are U.S. patent application Ser. It is a molybdenum complex of monohydric alcohols as described in Simply put, 2-
It is obtained by reacting an alkanol such as ethylhexanol with molybdenum oxide in the presence of ammonium hydroxide or by reacting an alkanol with ammonium heptamolybdate in the presence of a controlled amount of water. Reaction conditions Epoxidation reaction is 50~180℃, preferably 90~
It is carried out in a temperature range of 140°C. A particularly preferred range is 100-130°C, with about 110-120°C being the most preferred one-step operating temperature. It has been found that using a slight molar excess of olefin increases the oxide concentration, improves oxide selectivity and increases the amount of molybdenum that can be recovered. These advantages are due to the more polar reaction medium (lower propylene concentration, higher TBHP/TBA concentration), which stabilizes the TBHP and makes the molybdenum catalyst more active and soluble over the entire reaction time.
The lower temperature of our invention stabilizes the catalyst and prevents the decomposition of TBHP through undesirable pathways. The catalyst concentration in the process of the invention should be in the range of 50 to 100 ppm (0.01 to 0.10% by weight) based on the total amount of reactants charged. The concentration of catalyst is calculated as molybdenum metal. The preferred range is 200~
It is 600ppm. Generally about 250-500 ppm is the most preferred concentration. These catalyst concentrations are similar to those currently used in prior art methods (they range from 50 to
200ppm). Furthermore, it has been found that the process of the present invention provides a process in which the molybdenum catalyst is in solution in the medium during the reaction period. The epoxidation reaction of the present invention is carried out in the presence of a polar solvent. The polar solvent should be compatible with the hydroperoxide reactant (ie, should have the same carbon skeleton as the hydroperoxide). T-butyl hydroperoxide and TBA are commercially produced simultaneously by oxidation of isobutane, with TBA being the polar solvent if TBHP is used as the hydroperoxide.
TBA produced simultaneously with TBHP will normally provide all the polar solvent required for the present invention. Preferably, the solution of TBHP in TBA contains very little water (0-1% by weight). Preferably, the concentration of water is less than 0.5% by weight. The reaction can be carried out such that hydroperoxide conversion (usually 96-99%) is achieved while maintaining high epoxide selectivity (usually also 96-99%) based on the hydroperoxides reacted. . It is very unusual for these two values to be so high at the same time. This is because the profitability of commercial olefin epoxidation plants increases significantly as the yield of olefin epoxide increases. Reaction times can vary widely from the order of minutes to hours. Generally speaking, reaction times range from 30 minutes to 3 or 4 hours;
1.5 to 2.0 hours is about the average time. The preferred one-step reaction time/temperature is 2 hours at 110-120°C. Preferably, the reaction is carried out in two or more temperature steps. The reaction operation generally begins by charging the olefin to a reaction vessel. The hydroperoxide, polar solvent and catalyst are then added and the contents heated to the desired temperature. Another method is to heat the olefin reactant to or near the desired reaction temperature and then add the hydroperoxide, polar solvent, and catalyst. Additional heat is provided by the exotherm of the reaction. The reaction is allowed to proceed for the desired time at the reaction temperature, generally 110-120°C, or is carried out for 1 hour at 50-120°C, followed by 1 hour at 120-120°C.
It is carried out for 1 hour at 150°C. The mixture is cooled and the oxide is recovered. Generally speaking, the oxide concentration is at a propylene/TBHP molar ratio of 1.6.
~1.9:1 (TBHP content is 68-80% by weight) and about 24-28% when propylene/TBHP molar ratio is 1.1:1-1.2:1 (TBHP content is 68-80% by weight) ), it is about 31-32%. Using a series of reactors helps achieve the goals of high reaction medium polarity and low olefin concentration. The use of a multistage reactor allows for the stepwise addition of olefins, thereby increasing the polarity of the reaction medium and, in the case of propylene, further reducing the formation of propylene dimers. . This idea is called a continuous stirred tank reaction (CSTR) or a series of CSTR reactions.
This can be further improved by using . This is because CSTRs inherently provide lower concentrations of reactants compared to plug flow reactors (PFRs). A more effective method is CSTR or a series of
using a CSTR followed by one or more plug flow reactors.
The reason is that in a plug flow reactor the conversion can be more effectively forced to completion. It is possible, and also desirable, to operate each step at progressively higher temperatures. For example, the CSTR can be carried out at a reaction temperature of about 70-115°C, preferably 90-115°C, most preferably 100-110°C. PFR is higher temperature i.e. 115~150℃, most preferably 120~
It should be operated in a temperature range of 140°C. The plug reactor may be of any design familiar to those skilled in the art, such as jacketed reactors, heat transfer reactors, adiabatic reactors, and combinations thereof. The effluent from the CSTR can be referred to as an intermediate reaction mixture since the reaction is not complete. The residence time of the reactants in each reactor is up to the operator, but is preferably adjusted so that about 30% to about 50% by weight TBHP is converted in the CSTR. CSTR and PFR
The average residence time in the reaction mixture is adjusted based on other reaction conditions such as catalyst concentration, reaction temperature, etc., in a manner well known to those skilled in the art. Under the reaction conditions of the present invention, propylene oxide is produced in high concentrations (24-32%) and has a high selectivity (96-99%) based on the converted t-butyl hydroperoxide and a It was discovered that the yield of propylene oxide produced on the basis of One particularly preferred set of operating conditions (particularly for continuous processes) is to use the propylene and hydroperoxide reactants at low molar ratios of propylene to hydroperoxide (e.g., a charge of propylene to about 1 mole of hydroperoxide charge). 0.5 to about 2 moles). Another preferred method of operation is to carry out the first 0.5 to 1.5 hour reaction at low temperature (50 to 120°C), usually 0.5 to about 1.5 hours.
A temperature step is used so that the second step, which is a time reaction, is carried out at a higher temperature (usually 120-150°C). The low molar ratio of propylene to TBHP is facilitated by the optional stepwise addition of propylene to the staged reactors. According to this technique, the amount of olefin accumulated at any point in the stepwise series of reaction vessels is very small relative to the hydroperoxide. Usually, the charging ratio of propylene to hydroperoxide is about 2:1 to 20:1 expressed in molar ratio.
It is thought that it will change within the range of . Initial molar ratios of olefin to hydroperoxide of less than 2:1 were considered undesirable due to decreased selectivity. In the present invention, the initial charge molar ratio of olefin to hydroperoxide should not exceed 2.0:1. Propylene and TBHP to continuously stirred talc reactor
The wide range expressed by the preparation speed is 0.5:1 ~
The ratio is 2.0:1, preferably 0.9:1 to 1.8:1. Most preferably the molar ratio of olefin to hydroperoxide in the charge is from 1.05:1 to
The ratio is 1.35:1. If excess propylene is charged, the ratio of propylene to TBHP in the CSTR will be different from the initial charge ratio because both propylene and TBHP are consumed in the reactions that occur. In this case, as the conversion rate of TBHP increases, the ratio of propylene to TBHP also increases. For example, charged propylene and
If the initial molar ratio of TBHP is 1 mole of TBHP to 1.15 moles of propylene, and the rate of withdrawal of the reaction medium from the CSTR is such that the conversion of TBHP is maintained at 50% in the CSTR, The average molar ratio of unreacted propylene to reacted TBHP will be about 1.3:1. If the withdrawal rate of the reaction medium is such that the conversion of TBHP in the CSTR is maintained at about 90%, the average molar ratio of unreacted propylene to unreacted TBHP is about 2.5:1. It will be. In this same case, if we assume that TBHP was charged as a 70% by weight solution in t-butyl alcohol (TBA), the feed to the CSTR would be approximately 72.7% by weight of polar material (propylene, TBHP and It will consist of the charge TBHP divided by the sum of the weight of TBA (the sum of the weights of TBHP and TBA).As the reaction progresses, propylene (a non-polar substance) is converted to propylene oxide (a polar substance), resulting in the above-mentioned TBHP At 50% conversion, the reaction medium contains approximately 84.6% by weight of polar materials (unreacted
TBHP, charged TBHP, TBA formed as reaction products, and the total weight of propylene oxide divided by the sum of these four materials and unreacted propylene). mentioned above
At 90% conversion of TBHP, the reaction medium will consist of about 94% by weight polar material based on this same criterion. The method and apparatus of the present invention will be illustrated by the following examples, but the present invention is not limited thereto. Polarity of the Reaction Medium Example 1 To demonstrate the importance of the polarity of the reaction medium when practicing the present invention, three experiments were conducted using propylene, propane, t-butyl hydroperoxide, and t-butyl alcohol as feed materials. A series of batch experiments were conducted. In all experiments, the catalyst used was a molybdenum/ethylene glycol complex prepared as follows: Catalyst Preparation Mechanical stirrer, nitrogen inlet, thermometer, DeanStark trap, One round bottom Morton flask equipped with a condenser and nitrogen bubbler was charged with 100 g of ammonium heptamolybdate tetrahydrate and 300 g of ethylene glycol. While slowly bubbling nitrogen through the flask, heat the reaction mixture to 85-110°C for about 1 hour.
heated for an hour. At the end of the heating period, the reaction was almost complete and almost all of the ammonium heptamolybdate had dissolved. This reaction mixture is approximately 85
Aspirator vacuum was applied at a temperature of ~95°C for approximately 1.5 hours, followed by reheating at 90-100°C for an additional hour.
When cooled, it contains 16.1% molybdenum (determined by atomic absorption spectroscopy), 1.17% nitrogen (determined by Kjeldahl method) and 1.67% water (determined by Karl Fisher method).
A transparent liquid catalyst composition was obtained containing: Epoxidation Experiments Epoxidation experiments conducted in a 300 ml stainless steel autoclave are summarized in Tables 1 and 2. The above autoclave was charged with the propylene feed components at ambient temperature and then t-
The butyl hydroperoxide (TBHP) feed component was premixed with 0.38 g of catalyst before being charged. A catalyst concentration of approximately 350 ppm in the reaction medium was thus obtained.
In the pure propylene experiments, the TBHP feed component consisted of about 72.36 weight percent TBHP dissolved in t-butyl alcohol containing about 0.2 weight percent water. experiments with propylene/propane mixtures with propane added to the propylene feed;
and propylene/TBA mixtures in which t-butyl alcohol was further added to the TBHP feed, the TBHP feed was approximately 73 wt% TBHP dissolved in t-butyl alcohol containing about 0.2 wt% water. It was something that would become possible. The amounts of feed components were adjusted in each experiment to achieve the desired molar ratio of propylene to TBHP as shown in Tables 1 and 2. Thus, for example, in Run 1 of Table 1, the propylene feed component consisted of about 49.4 grams of propylene, and the TBHP feed component consisted of about 93.36 grams of TBHP, about 35.4 grams of t-butyl alcohol, about 0.26 grams of water, and about 100 grams of catalyst.
It consisted of 0.38g. In Experiment 2 of Table 1, the propylene feed components were approximately 34.65 grams of propylene and approximately 35.45 grams of propane.
It consisted of g. TBHP supply ingredients are:
TBHP71.72g, t-butyl alcohol 26.33g,
It consisted of about 0.2 g water and about 0.38 g catalyst. In Experiment 3 of Table 1, the propylene feed component consisted of approximately 36.4 g of propylene, TBHP
The feed components consisted of about 74.36 g of TBHP, about 64.27 g of t-butyl alcohol, about 0.2 g of water, and about 0.38 g of catalyst. All experiments shown in Table 1 were performed at reaction temperature
The reaction was carried out at 120°C for about 2.0 hours. All experiments shown in Table 2 were conducted at a reaction temperature of 110°C and a reaction time of 1.0 h, followed by a reaction temperature of 130°C and a reaction time of 1.0 h.
It took 1.0 hours. The reactants used and the results obtained are shown in Tables 1 and 2.

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【table】

[Table] First, looking at Table 1, you can see that the experiments are arranged in "triplicates" based on the molar ratio of propylene to TBHP. It can be seen that in each "triad" the molar ratio of propylene to TBHP gradually increases. Looking at the fourth column showing the selectivity results for propylene oxide based on TBHP, we see that the addition of 1 mol of propane in experiment 1 decreased the polarity of the feed and increased the polarity in the feed (TBHP and TBA). When the components accounted for only about 58.2% by weight of the feed, the selectivity decreased significantly compared to Experiment 2 of the present invention, where the polar components accounted for about 74.6% by weight of the feed. I know that there is. The same amount of TBA as the amount of propane used in Experiment 1 was added to increase the polarity of the feed, and the polar component in the feed was approximately 80.6% by weight.
Run 3 shows that the lower selectivity of Run 1 is not due to "dilution" of the reactants, but is due to a decrease in the polarity of the feed. In Experiment 3, the exact same "dilution" was applied to Experiment 2 as in Experiment 1. A similar effect on propylene oxide selectivity based on reacted TBHP was observed in the second, third and fourth
It is observed in the "triads" of the group (Experiments 4 to 12). Looking at the fifth set of triplets (Experiments 13 to 15), we find that experiments
In 13, polar components accounted for only 40.9% by weight of the ingredients.
(calculated value), and in Experiment 14, the polar component was only 58.3% by weight (calculated value) of the ingredients;
Substantially similar results are obtained. As shown in experiment 15, the proportion of polar components in the feed is 1
% to 72.8 wt%, the selectivity of TBHP to propylene oxide improved only slightly. As the initial propylene to TBHP ratio increases (1.9 to 2.1:1), the polar media stabilizing effect of TBHP and the catalyst increases the reaction rate (as the reaction rate of TBHP increases as a result of the increased propylene concentration). is “lost” by becoming smaller). The disadvantage of increasing the propylene concentration is that the formation of propylene dimers increases, as is evident from the results shown in column 8. Looking at the next set of data (Experiments 16-19), experiments
16 to 18, the polar component is about 32.2% by weight, about
52.2% by weight and approximately 47.1% by weight, and substantially similar results were obtained. In experiment 119, where the polar components accounted for approximately 67.1% by weight of the feed,
The selectivity of TBHP to propylene oxide has not improved. However, as shown in column 8, experiments 16-
Note the even more significant increase in the amount of propylene dimer in 21 due to the higher molar ratio of propylene to TBHP. In experiments 16-21, the selectivity of TBHP to propylene oxide was increased by a rapid increase in reaction rate (propylene
As the molar ratio to TBHP increased, TBHP
was "lost" due to a reduction in the decomposition reaction of Next, looking at Table 2, in experiments 22, 25, and 28, in which the polar components accounted for 58.4% by weight, 54.7% by weight, and 52.2% by weight of the ingredients, respectively, the polar components accounted for 74.5% by weight of the ingredients, respectively. 71.6% by weight,
Experiments 23, 26 and 69.6% by weight of the present invention
It can be seen that the trend of clearly inferior selectivity of TBHP to propylene oxide (column 4) compared to 27 is repeated. Experiment 22,
The selectivities of 25 and 28 are clearly inferior when compared with the selectivities obtained in experiments 24, 27 and 30, where the polar components accounted for 79.3%, 78.2% and 76.0% by weight of the feed, respectively. It's on. Example 2 In Examples 2-4, a relatively high concentration of catalyst is important from a yield, selectivity, and conversion standpoint when the epoxidation reaction is carried out at low reaction temperatures. It shows that there is. A 316 stainless steel autoclave (purged with nitrogen) with a capacity of 300 ml was charged with 43.9 g (1.0452 moles) of propylene at room temperature. Also, pre-mixed TBHP solution (TBHA60.75
%, TBA 38.91% and water 0.34%)
88.2 g and molybdenum/2-ethyl-1-hexanol catalyst (molybdenum content 5.96%) were charged at room temperature. The molybdenum/2-ethyl-1-hexanol catalyst is prepared by heating 29.0 g of molybdenum trioxide with 299.5 g of 2-ethyl-1-hexanol, 20 ml of concentrated ammonium hydroxide, and 250 ml of toluene from room temperature to 140°C for 15 to 45 minutes. and about 9ml of water
and about 165 ml of toluene were removed. Heating was continued at 140<0>C to 153<0>C for an additional 4.25 hours, at which point about 16 ml of water and about 234 ml of toluene were collected. The reaction mixture was filtered, and since the liquid contained water, it was dried with a molecular sieve. When the dried material was filtered again and analyzed for molybdenum, it was found that it contained 5.96% molybdenum. Propylene was charged into the autoclave, and then 0.9 g of the above catalyst premixed with TBHP was charged at room temperature. In this experiment, the propylene/TBHP molar ratio was 1.75:1, TBHP/TBA
The molar ratio of was 1.28:1 and the amount of catalyst was 0.0403% by weight molybdenum based on the total reaction charge. The autoclave was heated to 110°C for 30 minutes while stirring, and maintained at 110°C for 90 minutes. The reaction mixture was cooled to room temperature and sampled under pressure. The total weight of the recovered product was 133.0g;
Also, total weight of liquid product (after propylene removal)
The weight was 93.0g. Analysis of the liquid product revealed 1.18% TBHP
It was found that it included. Number of grams of residual TBHP = 1.0974 g Number of moles of residual TBHP = 0.0122 moles Number of moles of TBHP reacted = number of moles supplied - number of moles remaining = 0.5954 - 0.0122 = 0.5832 mole Conversion rate of TBHP = number of moles reacted / number of moles supplied = 0.5332 /0.5954 = 97.94% The total product was analyzed under pressure and found to contain 24.729% by weight propylene oxide and 0.152% by weight propylene glycol. It should be noted that the total product contains only 13.922% unreacted propylene. Propylene oxide (PO) grams = 32.8896g PO moles = 0.5671 mole Selectivity to PO = PO moles/reacted TBHP moles = 0.5671/0.5832 = 97.23% PO yield = PO moles/supplied TBHP Number of moles = 0.5671/0.5954 = 95.24% Furthermore, when the above liquid product was analyzed by atomic absorption spectroscopy, it was found that it contained 526 ppm of molybdenum, and the recovery rate of molybdenum was 91.5%. Example 3 45.3 g of propylene was placed in a 316 stainless steel autoclave (purged with nitrogen) with a capacity of 300 ml.
(1.07857 mol) was added. Similarly at room temperature, pre-mixed TBHP solution (TBHP60.75%,
88.15 g (consisting of 38.91% TBA and 0.34% water) and 0.45 g of molybdenum/2-ethyl-1-hexanol catalyst (5.96% molybdenum content) prepared as described in Example 2 were charged. In this epoxidation reaction, the molar ratio of propylene to TBHP was 1.81:1, the molar ratio of TBHP/TBA was 1.28:1, and the amount of molybdenum catalyst was 0.0200% by weight based on the total reaction charge. The amount of catalyst used in this example is about half that of Example 2. Again, the low ratio of propylene to TBHP results in a significant increase in molybdenum recovery. The autoclave was heated to 110°C for 30 minutes while stirring and held at 110°C for 90 minutes. The reaction mixture was cooled to room temperature and sampled under pressure. The total weight of the recovered product was 133.9g;
Also, the total weight of the liquid product (after removing propylene) is
It weighed 94.2g. Analysis of the liquid product revealed that
It contained 264 ppm of molybdenum, and the recovery rate of molybdenum was 93.0%. The liquid product was analyzed and found to still contain 3.92% TBHP. Number of grams of residual TBHP = 94.2 x 3.92% = 3.69264 g Number of moles of TBHP remaining = 0.0410 moles Number of moles of TBHP reacted = number of moles supplied - number of moles remaining = 0.5950 - 0.0410 = 0.5540 mole Conversion rate of TBHP = number of moles reacted/supplied Number of moles converted = 0.5540/0.5950 = 93.11% Analysis of the total product under pressure revealed 22.928% by weight of propylene oxide and unreacted propylene.
It was found that it contains 16.14%. Propylene oxide (PO) grams = 133.9 x 22.928% = 30.70 g PO moles = 0.5293 moles Selectivity to PO = PO moles / supplied TBHP moles = 0.5293/0.5540 = 95.54% PO yield = PO moles number/number of moles of TBHP supplied = 0.5293/0.5950 = 88.96% In Example 3, the experiment was substantially the same as Example 2 except that the catalyst concentration was lowered, but Example 2 with a higher catalyst concentration and In comparison, the yield of propylene oxide was about 6% lower. However, it should be noted that in Example 3, the molybdenum recovery (soluble molybdenum) in the reaction effluent was very high (93.0%), even higher than in Example 2 (91.5%). . Example 4 Propylene was added at room temperature to a 316 stainless steel autoclave with a capacity of 300 ml and purged with nitrogen.
48.3g (1.1500 mol) was added. To the propylene was added a premixed TBHP solution (124.2 g) and molybdenum catalyst (1.2 g). The 124.2 g TBHP component in the premixed TBHP/molybdenum catalyst solution had the following composition:
TBHP60.50%, TBA39.30% and water 0.2%. The molybdenum catalyst component in the premixed TBHP/molybdenum catalyst solution is molybdenum/2-ethyl-1-hexanol (6.50% molybdenum content).
It consisted of 1.2 g of catalyst. Concentrated molybdenum catalyst converts 299.5 g of 2-ethyl-1-hexanol into molybdenum trioxide (MoO ₃ ).
29.0 g and adding 20 ml of concentrated ammonium hydroxide to this mixture. The catalyst formation reaction mixture was heated to 180°C and held at that temperature for 5 hours, removing approximately 21 ml of water. The reaction mixture was cooled and filtered. According to atomic absorption spectrometry, the molybdenum content of the liquid was 6.50% (molybdenum content in the soluble catalyst: 97.7%). In this reaction, the molar ratio of propylene to TBHP is only 1.38:1, TBHP/
The molar ratio of TBA was 1.27:1. The amount of molybdenum catalyst used had a molybdenum content of 0.0449% by weight based on the total reaction charge.
110 while stirring the autoclave and contents.
℃ for 120 minutes (2 hours). The reaction mixture was cooled, depressurized and collected into two sample containers. Total product weight was 173.5g. The total weight of the liquid product was 142.2 g. Analysis of the liquid product revealed that it contained 1.70% TBHP. Number of grams of residual TBHP = 2.4174 g Number of moles of residual TBHP = 0.026 moles Number of moles of reacted TBHP = number of moles supplied - number of moles remaining = 0.8349 - 0.0269 = 0.8080 moles Conversion rate = 0.8080/0.8349 = 96.78% Atomic absorption spectroscopy of the liquid product When analyzed using a method, it was found that it contained 527 ppm of molybdenum, and the molybdenum recovery rate was essentially 96.1%. Examples 5 and 6 Examples 5 and 6 are similar to Example 2 except that different molybdenum/2-ethylhexanol catalysts were used.
It was carried out in the same manner as in 4. However, the results are essentially the same; at the end of the reaction,
Soluble molybdenum was recovered in very high yields (96% in both experiments). These results are summarized below in the form of a simple table. Note that the experiment was conducted at 110°C for 1.5 hours.

[Table] At the beginning of our research in this area, we found that experimental results were dramatically improved when dry TBHP (less than 0.4% by weight H ₂ O) was used in place of commercially available TBHP. Therefore, TBHP/
Preferably, the TBA solution contains very little water, ie less than 0.5% by weight of water. Conventionally, in patents and literature, it has been said that when the propylene/TBHP molar ratio is low, the selectivity is low, so a high olefin/hydroperoxide molar ratio was selected at the beginning of the propylene epoxidation experiment. More than 130 epoxidation experiments were conducted with propylene/TBHP molar ratios ranging from 6:1 to 10:1. Regarding these propylene/TBHP molar ratios,
Various changes in catalyst and reaction conditions did not appear to significantly affect the experimental results of the epoxidation. Furthermore, the molar ratio of propylene/TBHP is 6 to 10:
1, the molybdenum recovery was in the range of 60-80%. However, by lowering the initial propylene/TBHP molar ratio in an attempt to find a method that would help distinguish between the large number of molybdenum catalysts synthesized, the reaction temperature, residence time, and molybdenum catalyst concentration were adjusted appropriately. Then, surprisingly,
It has been found that the selectivity of propylene oxide is improved. Furthermore, it has been found that good results are obtained when the epoxidation reaction is carried out at a relatively low temperature using a relatively high concentration of molybdenum catalyst. Furthermore, it was also a surprising discovery that most of the charged molybdenum became soluble molybdenum, and that the proportion of soluble molybdenum increased as the propylene/TBHP charge ratio decreased. Furthermore, it has been found that when the propylene/TBHP charging ratio is small, the amount of by-product propylene dimer produced is also small. Table 4 provides data on the concentration of propylene dimer in the reactor effluent. Propylene dimer in the reactor effluent was determined using GC mass spectrometry. The specifically mentioned propylene dimer is an undesirable by-product. This is because propylene dimer is azeotropic with propylene oxide and must be best separated from propylene oxide by costly extractive distillation. The cost of extractive distillation columns and the utility costs for operating such purification units are very high. The examples in Table 5 using conventional propylene oxide process conditions are as follows:
The table shows that the levels of propylene dimer are surprisingly low. There are examples in Table 5 where the propylene/TBHP molar ratio is low, the reaction is stepwise, and the experimental results are improved not only at low catalyst levels but also at high TBHP concentrations. These examples show that the propylene/TBHP molar ratio is between 1.1 and 1.2:
1 shows preferred reaction conditions. The examples in Table 6 show that molybdenum catalysts can be recycled with good results. Examples 21 to 25 in Table 7 use 1000 ml of this process.
The experimental results obtained when the reactor was scaled up 3.3 times are shown. The operational difference in these examples is that after charging the propylene to the reactor,
Prior to adding the TBHP/TBA/catalyst solution, it was heated to a temperature at or near the reaction temperature. The reaction can be carried out exothermically at the desired temperature. Good results can be maintained even at these scaled-up quantities. Table 5 shows the preparation of a typical catalyst consisting of 2-ethyl-1-hexanol and ammonium heptamolybdate (ammonium heptamolybdate). In Table 8 there are examples showing that the reaction can proceed continuously in a two-part reactor scheme.
CSTR is followed by PFR at a slightly higher temperature. Also shown are examples with low propylene/TBHP ratios. In some cases, the catalyst recovery rate is listed as slightly higher than 100%. This excess is due to experimental error; catalyst recovery is quantitative in nature. The method of the present invention produces high concentrations of propylene oxide (24-32%) due to the low propylene/TBHP molar ratio and the use of polar reaction solvents;
Much less propylene is used. In this method, 4-16% of propylene is unreacted. The selectivity (moles of propylene oxide produced/moles of TBHP consumed) does not decrease even when the propylene/TBHP molar ratio is lowered.
Surprisingly, it can be seen that the selectivity of propylene oxide based on TBHP increases. This is due to the high polarity of the reaction solvent. Surprisingly, using the process of the present invention, the selectivity to alkylene oxide is at least 96%, the concentration of alkylene oxide in the product stream can be at least 24%, and the selectivity to alkylene oxide is at least 96%. the yield is at least 94%, and
The conversion of hydroperoxide can be at least 96%. Furthermore, surprisingly, propylene oxide/
The recovery rate of molybdenum when the ratio of TBHP is low is:
Generally >90%.

【table】

[Table] Atsuta.
3: The catalyst is MoO ₃ /2〓ethylhexanol/NH ₄ OH/
It was heated with toluene complex (5.96% molybdenum).

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【table】

【table】

[Table] Note: See Table 5 for descriptions of each catalyst used in each of the above experiments and its manufacturing method.

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【table】

[Table] Selection of Hydroperoxides The experiments shown show that t-
This was done to show that amyl hydroperoxide can also be used. Example 32 Production of catalyst Mechanical stirrer, nitrogen inlet, thermometer,
Ammonium heptamolybdate (catalyst A) was added to one round-bottom malt flask equipped with a Dean Stark trap, condenser, and nitrogen bubbler.
or ammonium dimolybdate (catalyst B)
100g and 300g of ethylene glycol were charged. The reaction mixture was heated to 85-110° C. for about 1 hour while passing nitrogen slowly through the flask. At the end of the heating period, the reaction was substantially complete and substantially all of the ammonium molybdate was dissolved. The reaction mixture was subjected to aspirator vacuum at about 85-95°C for about 1.5 hours and then
Reheated to 90-100°C for an additional hour. When cooled,
16.1% molybdenum (determined by atomic absorption spectroscopy), 1.17% nitrogen (determined by Kjeldahl method) and 1.67% water (determined by Karl-Fitscher method)
A transparent liquid catalyst composition (catalyst A) was obtained. Acid value of this catalyst (KOHmg per 1g of sample)
number) was determined by duplicate analysis.
It turned out to be 80.94 and 167.85. Catalyst B is
It was determined by atomic absorption spectroscopy to contain 13.2% molybdenum. Epoxidation Experiments Epoxidation experiments conducted in a 300 ml stainless steel autoclave are summarized in Table 9. Charge the propylene feed components at room temperature, then t-amyl hydroperoxide (TAHP)
The feed components were premixed with 0.38 g of catalyst before charging. A catalyst concentration of approximately 350 ppm in the reaction medium was thus obtained. The TAHP feed component is 70% by weight in t-amyl alcohol containing approximately 0.2% water.
It consisted of a TAHP solution. The reaction conditions used and the results obtained are summarized in Table 9.

【table】

[Table] From Table 9, in all examples, the selectivity for propylene oxide was good, and t-
It can be seen that the conversion of amyl hydroperoxide was good. In order to expand the technical idea of the present invention, TBHP or
Various experiments were performed using hydroperoxides other than TAHP, such as cumene hydroperoxide (CHP). As a result, surprisingly, although TBHP and CHP behave similarly at high propylene/hydroperoxide molar ratios,
It has been found that at the low molar ratios of the present invention, ie, below about 2:1, their behavior is different. When the catalyst concentration used is high, the yield of propylene oxide using CHP is lower than that when the molar ratio of propylene/cumene hydroperoxide is low.
The yield of propylene oxide was lower than that obtained using TBHP. When CHP is used in the low molar ratio example, the propylene oxide selectivity relative to reacted CHP increases as the catalyst concentration increases, but not as much as when TBHP is used in the same example. I can't reach it. It has therefore also been found that the choice of hydroperoxide is also critical in order to obtain good results, especially with respect to the process of the invention. Such discoveries are discussed in detail in the Examples below. These examples were performed according to the operating procedures described above and using the parameters noted in the table. Tables 10 and 11 show the superimposed effect of the propylene/CHP molar ratio. When using CHP, the selectivity to propylene oxide based on reacted CHP decreases as the propylene/CHP charge ratio decreases. Examples 32-36 show that the propylene oxide selectivity decreases as the propylene/CHP charge ratio decreases, and the dimer content (on a "pure PO" basis, i.e. propylene distilled off) decreases as the propylene/CHP charge ratio decreases.
shows a general increase at low catalyst levels (69-78 ppm). Examples 37 and 38 show similar trends for moderate catalyst levels (approximately 250 ppm), and Examples 39-45 show that these undesirable results are more pronounced at high catalyst concentrations (400-400 ppm).
449ppm) is also shown to be true. When using CHP, the production of propylene dimers does not decrease as the propylene/CHP feed ratio decreases, unlike when the propylene/TBHP feed ratio decreases. In fact, dimer formation tends to increase as the initial propylene/CHP ratio decreases. Furthermore, Table 10 shows these trends for two different CHP concentrations, 30% and 59%, of CHP in cumyl alcohol;
It should be noted that good results have been shown to be obtained for PO selectivity. Table 12 holds the propylene/CHP molar charge ratio constant (about 3:1 for Examples 34, 37 and 39 and about 1.3: for Examples 35 and 41).
1) Propylene oxide selectivity, CHP conversion, and propylene oxide yield based on reacted CHP all increase when increasing the catalyst level from the 60-80 ppm molybdenum catalyst region to the 250-450 ppm catalyst region. The foregoing embodiments have been rearranged in such a manner as to be evident. Propylene dimer production is also reduced. However, it should be noted that for Examples 35 and 41, at low propylene/CHP ratios, the selectivity of propylene oxide based on reacted CHP is still low.
Therefore, when using TBHP, the selectivity of propylene oxide to the reacted TBHP standard is better at a low propylene/TBHP molar ratio, whereas when using CHP, the ratio of reactants is kept high. It seems necessary. Table 13 lists the specified catalyst level (250 ppm or
400-450ppm), CHP concentration is from 30%
Four previous examples and two new examples to demonstrate that propylene oxide selectivity relative to reacted CHP decreases and propylene dimer production increases when increasing to 59%. (50 and 51) exist. The yield of propylene oxide is also reduced. Table 14 shows the propylene/CHP charging ratio.
The ratio is 1.3:1 to 1.4:1, and the CHP concentration (30.0→43
→50%) or catalyst concentration (total input amount basis 60→250→
The previous example has been rearranged in yet another way to demonstrate that changing the 450%) does not improve PO selectivity or yield. In fact, for reactant molar ratios of 1.3:1 to 1.4:1, optimal catalyst levels appear to be in the range of 200 to 350 ppm. It must be noted that the production of propylene dimers increases with decreasing PO selectivity and decreases with increasing PO selectivity. This latter relationship is not observed in the case of TBHP. The CHP experimental results presented here are consistent with Kollar's U.S. patent, in which CHP conversion and epoxide selectivity decrease with decreasing molar ratio.
It is confirmed to some extent in No. 3351635 (see Table 10). However, the use of a high concentration of catalyst as in the present invention was not found in the above-mentioned US Pat. No. 3,351,635,
It has not been found that even a certain degree of improvement is possible when using CHP, nor that a dramatic improvement is possible when using TBHP. In conclusion, Example 55 is similar to Example 39, except that the stepwise reaction (90°C for 1 hour followed by 110°C for 1 hour) is carried out in one step at 90°C for 1 hour.
I did essentially the same thing. Other minor differences are that the charging ratio is 7.18:1 instead of 7.03:1, and the catalyst concentration is 79ppm instead of 78ppm.
As with TBHP, the CHP conversion is
much lower (66 compared to 97.7% in Example 39)
%).

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TABLE Olefin Selection Although, for convenience, propylene has been used in the foregoing examples of the invention, the invention can also be practiced with other _C3 - _C20 olefins to provide comparative data. This is illustrated by the following specific examples. When epoxidizing higher _C4 to _C20 olefins, it is important to convert the olefins substantially quantitatively to epoxides. The reason is that the feedstock and the epoxide reaction product have similar physical properties and separation of the feedstock and the epoxide reaction product is extremely difficult. Example 33 A 1 volume round bottom Molton flask equipped with a mechanical stirrer, Dean Stark trap, thermometer, nitrogen inlet and nitrogen bubbler was charged with Climax Molybdenum.
_{2 - ethyl - 1} - 182.32 g of hexanol (99% purity, manufactured by Alpha, molecular weight = 130.2, number of moles = 1.4) and 14.4 ml of water were charged. The ratio of moles of alcohol (2-ethyl-1-hexanol)/gram atoms of molybdenum is 7.0/1, and the ratio of moles of added H ₂ O/gram atoms of molybdenum is 4.0/1. It should be noted that The reaction mixture was gently heated to 178 °C;
It was held at 178-180°C for 5 hours. During this time _H2O29
ml was removed with a Dean Stark trap. The cooled reaction mixture was filtered through a glass furnace paper (grass filter).
paper) to remove solids. The weight of the liquid was 176.3g. % of molybdenum in the liquid by AA (atomic absorption spectroscopy) = 10.1% % of nitrogen in the liquid by Kjeldahl method = 0.34
% Number of grams of molybdenum supplied = 19.187 Number of grams of molybdenum solubilized in the liquid = 17.81 % of molybdenum mixed in the catalyst = 92.80% Example 34 Magnetic stirrer bar, thermometer, condenser, nitrogen introduction 42.0 g of octene-1 (molecular weight 112, 0.375 mol) was charged into a 250 ml round-bottom Molton flask equipped with a spout and a nitrogen bubbler.
Subsequently, 35.5 g of 72.0% TBHP solution was charged together with 0.39 g of molybdenum catalyst 5810-60 (10.1% molybdenum) premixed with TBHP/TBA. The reaction mixture was slowly heated to 95°C (exotherm to 99°C) and then held at that temperature (93-96°C) for 2.0 hours.
After cooling, the reaction mixture was free of solids and weighed 74.1 g. TBHP weight % = 1.70% Octene oxide weight % = 46.182 Octene weight % = 12.677% Octen oxide g = 34.221 Number of epoxide moles = 0.26735 Selectivity of C ⁸ epoxide = 0.26785/1.2703 = 98.91% Yield of C ₈ epoxide = 0.26735/ The table also shows some other examples It is shown.
In these Examples, the operating procedures and equipment were exactly the same as those in Example 34.

【table】

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Claims (1)

[Claims] 1. A hydroperoxide selected from t-butyl hydroperoxide and t-amyl hydroperoxide is heated to 50% by weight in the presence of a soluble molybdenum catalyst.
A method for epoxidizing olefins by reacting in liquid phase at a temperature of ~180°C to produce olefin epoxide, which is a product corresponding to olefin, and t-butyl alcohol and t-amyl alcohol, which are products corresponding to hydroperoxide. wherein the molar ratio of olefin to hydroperoxide is from 0.5:1 to 2:1, the hydroperoxide is fed to the reaction medium as a solution in the corresponding product alcohol with a concentration of at least 30% by weight, and the reaction medium is A process characterized in that the content of polar components therein is maintained at least 60% by weight, said polar components consisting of said hydroperoxide, said corresponding alcohol and said corresponding product olefin epoxide. 2. The process of claim 1, wherein the product solution of hydroperoxide in alcohol contains 0 to 1% water by weight. 3. Claims 1 or 3 in which the reaction is carried out stepwise, first in a continuous stirred tank reactor or series of such reactors and then in one or more plug flow reactors. The method described in Section 2. 4. The method according to any one of claims 1 to 3, wherein the catalyst is a complex consisting of molybdenum and 2-ethylhexanol or alkylene glycol.