SU1097368A1 - Catalyst of epoxidation of propylene with cumene hydroperoxide - Google Patents

Abstract

CATALYST FOR EPOXIDATION OF PROPYLENE BY HYDROPERMANIUM KUMOL containing the molybdenum compound and activating additive, characterized in that, in order to increase the activity and selectivity of the catalyst, it contains as an activating additive a compound of the general formula: RRVx, where R, R is phenyl; R is phenyl, - (CIS.) -, where X is a mouse, phosphorus, antimony or their oxide, at a molar ratio, the compound molybdenum: activator additive 1:

Description

The invention relates to the field of catalysts for the oxidation of olefins, in particular molybdenum-containing catalysts for the epoxidation of propylene by cumene hydroperoxide.

A known catalyst for the epoxidation of olefins by organic hydroperoxides, comprising oxides of the elements of the V and VI groups of the periodic system and nitrogen-containing compounds that form chelate compounds with the oxide metal, for example hydroxy-8-quinoline, or compounds of the formula

R.-C-N-R, f I

About him

where R, is an alkyl or aryl radical;

P- - H, alkyl or aryl radical.

In the absence of this catalyst, the process of epoxidation of olefins is carried out at a molar ratio of catalyst to hydroperoxide (HP) of 0.005 to 0.1, the reaction temperature is 40-120 ° C, the reaction time is 9-35 minutes. The catalyst is pre-activated for 35240 minutes.

During epoxidation of propylene by cumene hydroperoxide (experimental testing under similar conditions), selectivity of 65–70 wt.% Was achieved with a HP conversion of 97%.

The main disadvantage of this catalyst is low activity, leading to the need to use high concentrations of catalyst, as well as low selectivity with the use of alkylaromatic hydroperoxides as an epoxy agent. The catalyst requires an activation stage for a long time, which leads to two stages of the process, i.e. its complexity. In addition, the duration of the process is long (up to 4.5 hours). The immediate solution of the problem is a catalyst for the epoxidation of olefins with organic hydroperoxides, which contain a molybdenum compound and a nitrogen-containing compound of the general formula: R.NHRgNHRj, where K, Hz is alkyl, aryl, cycloalkyl, naphthenyl diphenylamine; R is alkyl, aryl, or morpholine, or urotropine, or piperidins, or aminophenols of the general formula 5rN-R3 Ro where R. is hydroxyphenyl, hydroxy naphthyl, hydroxy alkylphenyl; R- is alkyl, aryl, 1uchloalkyl, naphthyl, hydroxyphenyl, hydroxyaphthyl, hydroxy alkylphenyl; R is H, alkyl, aryl, cycloalkyl, naphthyl, or stable nitroxyl radicals, for example, 2,2,6,6-tetramethylpiperi DIN-1-OXIL, in an amount of 1-100 mol per 1 mol of molybdenum compound. The process of epoxidation of olefins with organic hydroperoxides is carried out at 80-120, the molar ratio olefin: hydroperoxide (2-10): 1, the concentration of molybdenum compounds 1 10 4-10 mol / mol hydroperoxide, the reaction time is 20-60 minutes. The compounds of molybdenum and nitrogen containing compounds are introduced into the reaction mixture simultaneously with hydroperoxide and olefin without prior activation. The yield of propylene oxide during epoxidation of propylene with cumene hydroperoxide (HPC) is 70-80% by weight, with a conversion of hydroperoxide of 90%. A disadvantage of the known catalyst is its insufficiently high activity and selectivity. The purpose of the invention is to increase the reactivity and selectivity of the catalyst. The above objective is achieved by the described catalyst for epoxidation of propylene by cumene hydroperoxide containing a molybdenum compound and an activating additive, as which it contains a compound of the general formula: RRVV / a RRRX, where R, R - (lil; // R - phenyl. -Q: c- (CH) „-, where X is a mouse, phosphorus, antimony or their oxide, with a molar ratio of molybdenum compound: activating the additive 1: (1-4). A distinctive feature of this catalyst is the content as ac The specified additive is used in this quantity. The catalyst of the invention has a high activity and selectivity — the yield of propylene oxide increases to 94% by weight when the hydroperoxide is converted to 98%. The process of epoxidation of propylene with isopropyl benzene peroxide is carried out at 80-120, molar ratio olefin: hydroperoxide (4710): 1, the concentration of molybdenum compounds 110 tons 110 mol / mol hydroperoxide, the reaction time 30-60 minutes. An activating compound in the amount of 174 mol per mole of Mo is introduced into the reaction mixture simultaneously with other reagents, including the molybdenum-containing component of the catalyst. The epoxidation reaction starts without pre-activation and ends after 30-60 minutes. The yield of propylene oxide is 8094% by weight with hydroperoxide conversion of 90-98%. As the molybdenum-containing compound is used; molybdenum acetylacetonate, molybdenum alkylene glycol, molybdenum carboxylates, molybdenum hexacarbonyl, and other compounds. Example 1. In the autoclave load 45.6 g (0.3 mol) of cumene hydroperoxide (CCP), 62.9 g (1.49 mol) of propylene, 135 g of isopropyl benzene, 1.8-10 mol of carbonyl Ho and 3.6 f (CgH5) .- P (CgH) 2. The reaction is carried out with stirring at 120 ° for 60 M1Y. Hydroperoxide conversions are 96.43%, propyl oxide yield} 1a per 88.7% by weight of converted hydroperoxide, 99% by weight of converted propylene. Example2. The autoclave was charged with 45.6 g (0.3 mol) of HPA, 62.9 g (1.49 mol) of propylene, 135 g of isopropyl benzene, 1, molybdenum carbonyl. Various phosphorus compounds are introduced as an adjuvant. The reaction temperature is 120 ° C, the reaction time is 60 minutes. The data presented in Table. 1. The catalyst activity in the epoxidation reaction is characterized by the initial epoxidation reaction rate (WQJ), calculated from the curve of the accumulation of propylene oxide. The selectivity of the catalyst is characterized by the ratio of the initial epoxidation reaction rate (W to the initial consumption rate of hydroperoxide () in all directions (target and side reactions). Example 3. The autoclave is loaded with 45.6 g (0.3 mol) HPA, 62, 9 g (1.49 mol) of propylene, 135 g of isopropyl benzene 1, compounds M and an organophosphorus additive. The temperature is 120 ° C, the reaction time is 60 minutes, the data are presented in Table 2. Example 4. The autoclave is loaded with 45.6 g (0 , 3 mol) HPA, propylene, isopropyl benzene, proplenlenglycol t Mo triphenylphosphine oxide 4 mol / mol prop Elenglycol and Mo, analogously to Example 3,

Table 1 The concentration of the CCP in the initial mixture of 15 wt.%. The molar ratio of propylene:: CCP varies from (): 1, the concentration (L of propylene glycol Mo varies from (1.10 -7l S) mol / mol of CCP, temperature range 80-120 C, reaction time 30-60 minutes. Data are presented in Table 3. Example 5. In an autoclave, 45.6 g (0.3 mol.) hack, 62.9 g (1.49 mol.) propylene, 135 g isopropyl benzene, 1, molybdenum hexacarbonyl are loaded in. The triphenol derivatives are the activating additive. Antimony and mouse. The reaction mixture is kept under stirring for 60 minutes with stirring, the data are given in Table 4. For example, 45.6 g (0.3 mol.) of barcode are charged into an autoclave, 62.9 g (1.49 g). ol) propylene, 135 g of isopropyl benzene, 1.8 x 10 mol of molybdenum carbonyl. Triphenylaryne oxide in an amount of 1 is introduced as an activating additive (molar ratio activating additive: catalyst 1: 1). Reaction temperature 120 ° C, stirring time 1 h. Conversion hydroperoxide is 94.3%, the yield of propylene oxide in terms of converted hydroperoxide is 82.05%. Thus, as can be seen from the presented data, the catalyst according to the invention has an increased activity and selectivity — the oxide yield of the past is increased to 94% by weight with conversion ns to about 98%, the additive suppresses administered heterolytic decay reaction of propylene oxide.

Table 2

PPh-j 2: 1

Ph-P- (CH) 2-PPh2 2: 1

PPho 4: 1

PPh,

Ph-NH-Ph-NH-C H 2: 1

95.6

85.5 98.2 89.6 96.2 82.2

94.3

83.1

97.0

78.5

2: 1 4: 1 2: 1 1: 1

Table4

94.1 90.66 84.5

Claims (1)

CATALYST FOR EPOXIDATION OF PROPYLENE KUMO HYDRO PEROXIDE An aircraft containing a molybdenum compound and an activating additive, characterized in that, in order to increase the activity and selectivity of the catalyst, as an activating additive, it contains a compound where, where the general formula: Η R'RR ^W x, R, R is phenyl; R is phenyl, - (CH2.) _H -, n = 1-4; -c c- x - arsenic, phosphorus, antimony or their oxide, with a molar ratio of molybdenum compound: activating additive 1: (1-4). with "o