CN103372462B - A kind of decomposing cycloalkyl hydrogen peroxide water-soluble catalytic agent system and application - Google Patents

Abstract

The invention relates to a water-soluble catalyst system for decomposing cycloalkyl hydroperoxide. The system is mainly composed of metal ions and acid radical ions. The catalyst system can make cyclohexyl hydroperoxide Efficiently decomposes into cyclohexanol and cyclohexanone.

Description

A water-soluble catalyst system for decomposing cycloalkyl hydroperoxide and its application

technical field

The present invention relates to the development and application of catalyst systems in the field of petrochemical industry; specifically, it relates to the development of a water-soluble catalyst system, and the catalyst system decomposes cycloalkyl hydroperoxide under non-alkaline water-oil two-phase conditions , The application method of preparing corresponding cycloalkyl ketones and cycloalkyl alcohols.

technical background

Cycloalkyl hydroperoxide is an intermediate product of cycloalkane free radical oxidation, and this intermediate can be decomposed to obtain final products cycloalkyl alcohol and cycloalkyl ketone. Take the industrial production process of cyclohexane oxidation to produce cyclohexanol and cyclohexanone as an example. Cyclohexane is first oxidized by air to obtain an oxidized solution containing cyclohexyl hydroperoxide. This oxidized solution must be further decomposed to make it The cyclohexyl hydroperoxide decomposes to the final cyclohexanol and cyclohexanone. Therefore, the decomposition reaction of cyclohexyl hydroperoxide is one of the key steps in the oxidation of cyclohexane to produce cyclohexanol and cyclohexanone.

At present, the industrial decomposition method of cyclohexyl hydroperoxide mainly adopts alkali decomposition method, which uses an alkaline aqueous solution of sodium hydroxide containing cobalt ions to decompose cyclohexane hydroperoxide. Although this decomposition method has the advantages of fast decomposition reaction speed and long-term stable operation of the reaction equipment; it has the disadvantages of requiring a large amount of NaOH consumption and producing a large amount of environmentally harmful alkali slag.

In order to overcome the deficiencies of the existing industrial decomposition methods, since the industrial production of cyclohexane oxidation has been realized, a large number of researches on the non-alkali catalytic decomposition of cyclohexyl hydroperoxide have been carried out. Using water as the existing phase of the catalyst to carry out two-phase alkali-free catalytic decomposition of cycloalkyl hydroperoxide has the advantage of being easy to separate from the alkane oxidation liquid after the decomposition reaction is completed, thereby facilitating the reuse of the catalyst. Xiao Zaosheng disclosed in the patent CN1184097A that he used an aqueous solution containing chromium salt and cobalt salt to decompose cyclohexyl hydroperoxide in cyclohexane oxidation solution under acidic conditions. The applicant of this patent discloses the research on catalytic decomposition of cyclohexyl hydroperoxide using various catalysts of water-oil two-phase system in patents CN200410054609.3, CN200410068873.2, and CN200710159027.5.

The aqueous phase non-alkali catalyzed decomposition of cycloalkyl hydroperoxide is a complicated process. In addition to the main reaction of catalytic decomposition, the catalyst may also promote the further oxidation and polymerization of the products cyclohexanone and cyclohexanol, etc. reaction, in order to reduce side reactions and improve selectivity, the present invention is based on the patent CN200710159027.5 water-oil two-phase alkali-free catalytic decomposition of cycloalkyl hydroperoxide, and further improves the non-alkali catalytic decomposition cycle by increasing the solute composition of the catalyst solution. Catalytic activity and selectivity of alkyl hydroperoxide reactions.

Contents of the invention

According to the present invention, the catalyst used is an aqueous solution containing transition metal ions, non-transition metal ions and acid radical anions, and this kind of catalyst system can make cyclohexyl hydroperoxide efficiently Decomposed into cyclohexanol and cyclohexanone. In the decomposition reaction of cycloalkyl hydroperoxide catalyzed by transition metal ions in aqueous phase, the properties such as the activity and degree of hydration of transition metal ions will affect its catalytic activity and selectivity. By introducing non-transition metal ions and acid radical anions into the transition metal ion catalyst aqueous solution system, due to various Interaction, so that the ion activity, ion hydration degree, water activity, etc. will change, and the activity and selectivity of the catalyst solution system will be improved.

According to the present invention, the aqueous catalyst solution used must contain at least one transition metal ion with activity for decomposing cycloalkyl hydroperoxide, and one or more non-transition metal ions. The transition metal ions that can be used can be from Cu ⁺ , Cu ²⁺ , Cr ³⁺ , Cr ⁶⁺ , Co ²⁺ , Fe ³⁺ , V ⁴⁺ , V ⁵⁺ , V ³⁺ , Mo ⁶⁺ , Ru ³⁺ However, in consideration of cost, activity and safety, it is preferably selected from Cu ⁺ , Cu ²⁺ , V ⁴⁺ , V ⁵⁺ , V ³⁺ , Mo ⁶⁺ , and Ru ³⁺ . The non-transition metal ions that can be used can be selected from Li ⁺ , Na ⁺ , K ⁺ , Ca ²⁺ , Mg ²⁺ , etc., and considering cost and solubility in water, Li ⁺ , Na ⁺ , K ⁺ are preferred. The content of transition metal ions in the aqueous phase can be optional between 0.1ppm and 20wt%, but considering the possible impact of cost and too many transition metal ions on side reactions, it is preferably between 1ppm and 10wt%, preferably Between 10ppm and 5Wt%. Similarly, non-transition metal ions, as auxiliary components affecting the activity and selectivity of transition metals, can be contained in the aqueous phase in the range of 0.1-50 wt%, preferably 1-20 wt%.

According to the invention, the transition metal ions used can be present in any form which is active in catalytically decomposing cycloalkyl hydroperoxides. Such as N-butylimidazolium complex copper ion, vanadyl tartrate complex ion, chromate ion, metavanadate ion, molybdate ion, phosphorus molybdenum vanadium heteropolyacid ion, etc.

According to the invention, the anion of the system is one or more acid ions. The acid radical ion can be added together with the metal ion used in the system in the form of metal salt; it can also be formed by adding alkali metal or alkaline earth metal hydroxide to the reaction system to neutralize the organic acid in the reaction system. Including monobasic organic acid radicals or dibasic organic acid radicals containing 1-6 carbon atoms; such as formate, acetate, butyrate, valerate, oxalate, succinate, glutarate, adipate, etc.

According to the present invention, the reaction substrate is cyclohexane oxidation solution, in which cyclohexyl hydroperoxide undergoes decomposition reaction to generate cyclohexanol and cyclohexanone. The weight percentage of hydroperoxide containing cyclohexane in this solution is generally between 0.1%-10%, but usually between 0.5%-4%.

According to the present invention, the volume ratio of the aqueous catalyst solution to the organic phase of the decomposition raw material liquid is 1:100, preferably 1:10. If the catalyst solution is too small, the reaction speed will be slow, and if too much, it will not only increase the amount and cost of the catalyst, but also reduce the effective volume of the decomposition equipment. The decomposition reaction can be carried out in a batch tank reactor, or under the condition of continuous flow of feed and discharge.

According to the present invention, the catalyst system decomposes cycloalkyl hydroperoxide under stirring and heating conditions, and the reaction temperature is 20-160°C, preferably 60-110°C. If the temperature is lower than 60°C, the reaction rate will be too slow; if the temperature is higher than 110°C, the side reaction will be intensified.

The cycloalkyl group is a cycloalkyl group with 3-18 carbon atoms in the ring, such as cyclohexyl, cyclopentyl, and cyclooctadecyl.

detailed description

According to the present invention, the content of cyclohexyl hydroperoxide is analyzed by iodometric method; cyclohexanol and cyclohexanone are quantified by gas chromatography internal standard method.

The following examples are used to illustrate the use effect of the present invention, but the given embodiments are not intended to limit all applications of the present invention.

The acquisition process of the cyclohexane solution containing cyclohexyl hydroperoxide: Cyclohexane was bubbling and oxidized with air for 1 hour under stirring conditions of 160°C and 1.2Mpa to obtain cyclohexane hydroperoxide containing 2.1mol% cyclohexane hexane solution.

Example 1:

Add 0.05 g of ammonium molybdate, 0.1 g of oxalic acid, 0.1 g of sodium adipate and 1 g of water into a 50 ml stainless steel reaction kettle, and stir at room temperature to form a blue-black solution. 10 g of a cyclohexane solution containing 2.1 mol% cyclohexane hydroperoxide was added thereto. Replace the reactor with nitrogen, then close the gas inlet and outlet valves, heat up to 85°C while stirring, continue the constant temperature reaction for 20 minutes, then cool down, take out the upper organic phase for analysis, the test results are shown in Table 1.

Example 2:

Add 0.01 gram of ammonium molybdate, 0.05 gram of tartaric acid, 0.2 gram of sodium acetate and 1 gram of water into a 50 ml stainless steel reaction kettle, and stir at room temperature to form a blue-black solution. 10 g of a cyclohexane solution containing 2.1 mol% cyclohexane hydroperoxide was added thereto. The reaction kettle was first replaced with nitrogen, and then the gas inlet and outlet valves were tightly closed, and the temperature was raised to 105°C while stirring, and the constant temperature reaction was continued for 10 minutes, then the temperature was lowered, and the upper organic phase was taken out for analysis.

Example 3:

Add 0.05 gram of cupric chloride, 0.1 gram of N-butyl imidazole, 0.2 gram of mixed acid sodium (this mixed acid sodium is neutralized with NaOH in cyclohexane oxidation liquid, the mixed by-product organic that separates obtains in a 50 milliliters of stainless steel reactors) Acid sodium salt) and 2 grams of water, stirred at room temperature to generate a blue solution. 10 g of a cyclohexane solution containing 2.1 mol% cyclohexane hydroperoxide was added thereto. Replace the reactor with nitrogen, then close the gas inlet and outlet valves, heat up to 95°C while stirring, continue the constant temperature reaction for 30 minutes, then cool down, take out the upper organic phase for analysis, the test results are shown in Table 1.

Example 4:

Add 0.001 g of ammonium molybdate, 0.1 g of glucose, 0.15 g of potassium isobutyrate and 2.5 g of water into a 50 ml stainless steel reactor, and stir at room temperature to generate an aqueous solution. 10 g of a cyclohexane solution containing 2.1 mol% cyclohexane hydroperoxide was added thereto. Replace the reactor with nitrogen, then close the inlet and outlet valves, heat up to 105°C while stirring, continue the constant temperature reaction for 30 minutes, then cool down, take out the upper organic phase for analysis, the test results are shown in Table 1.

Example 5:

Into a 50 ml stainless steel reaction kettle was added 0.05 g of ammonium metavanadate, 0.1 g of sodium glutarate and 1.5 g of water. 10 g of a cyclohexane solution containing 3.2 mol% cyclohexane hydroperoxide was added thereto. Replace the reactor with nitrogen, then close the gas inlet and outlet valves, heat up to 85°C while stirring, continue the constant temperature reaction for 20 minutes, then cool down, take out the upper organic phase for analysis, the test results are shown in Table 1.

Embodiment 6:

Add 0.001 gram of ammonium metavanadate, 0.01 gram of oxalic acid, 0.4 gram of lithium acetate and 3 grams of water into a 50 milliliter stainless steel reaction kettle, and stir at room temperature to generate a complex vanadium tartrate aqueous solution. 10 g of a cyclohexane solution containing 3.2 mol% cyclohexane hydroperoxide was added thereto. Replace the reactor with nitrogen, then close the gas inlet and outlet valves, heat up to 85°C while stirring, continue the constant temperature reaction for 15 minutes, then cool down, take out the upper organic phase for analysis, the test results are shown in Table 1.

Embodiment 7:

Into a 50 ml stainless steel reaction kettle was added 0.001 g of vanadium pentoxide, 0.004 g of tartaric acid, 0.1 g of sodium lactate and 0.5 g of water. 10 g of a cyclohexane solution containing 3.2 mol% cyclohexane hydroperoxide was added thereto. Replace the reactor with nitrogen, then close the gas inlet and outlet valves, heat up to 80°C while stirring, continue the constant temperature reaction for 20 minutes, then lower the temperature, take out the upper organic phase for analysis, the test results are shown in Table 1.

Embodiment 8:

After the upper organic phase of Example 10 was poured out, 10 grams of cyclohexane solution containing 3.2 mol% cyclohexane hydroperoxide was added to the reaction kettle again. Replace the reactor with nitrogen, then close the gas inlet and outlet valves, heat up to 80°C while stirring, continue the constant temperature reaction for 20 minutes, then lower the temperature, take out the upper organic phase for analysis, the test results are shown in Table 1.

Comparative Example C1

Add 0.01 gram of ammonium molybdate, 0.05 gram of tartaric acid and 1 gram of water into a 50 ml stainless steel reaction kettle, and stir at room temperature to form a blue-black solution. 10 g of a cyclohexane solution containing 2.1 mol% cyclohexane hydroperoxide was added thereto. Replace the reactor with nitrogen, then close the gas inlet and outlet valves, heat up to 105°C while stirring, continue the constant temperature reaction for 10 minutes, then lower the temperature, take out the upper organic phase for analysis, and the reaction results are listed in Table 1.

Comparative Example C2

Into a 50 ml stainless steel reaction kettle was added 0.001 g of vanadium pentoxide, 0.004 g of tartaric acid and 0.5 g of water. 10 g of a cyclohexane solution containing 3.2 mol% cyclohexane hydroperoxide was added thereto. The reactor was first replaced with nitrogen, then the gas inlet and outlet valves were closed tightly, and the temperature was raised to 80°C while stirring. The constant temperature reaction was continued for 20 minutes and then the temperature was lowered. The upper organic phase was taken out for analysis. The reaction results are listed in Table 1.

Table 1 embodiment and comparative example decompose cyclohexyl hydroperoxide result

Claims (6)

1. an application of decomposing cycloalkyl hydroperoxide water-soluble catalyst system, is characterized in that: The catalyst system can efficiently decompose cycloalkyl hydroperoxide into cycloalkanol and cycloalkanone under the condition of pH≤7; The system is an aqueous solution composed of metal ions and acid radical ions, The metal ions in the catalyst system include at least one transition metal ion and at least one non-transition metal ion; Among them, the transition metal ions are Cr ³⁺ , Cr ⁶⁺ , Mo ⁶⁺ or Ru ³⁺ ; the non-transition metal ions are Li ⁺ , Na ⁺ , Ca ²⁺ or Mg ²⁺ ; the content of transition metal ions in the water phase The range is 10ppm-5wt%; the content range of non-transition metal ions is 1-20wt%; The acid radical ion is added together with the metal ion used in the system in the form of a metal salt; or is formed by adding an alkali metal or alkaline earth metal hydroxide to the reaction system to neutralize the organic acid in the reaction raw material; The acquisition process of cycloalkyl hydroperoxide: cycloalkane is oxidized by air to form an oxidation solution containing cycloalkyl hydroperoxide, and the oxidation solution contains not only cycloalkyl hydroperoxide, but also organic acids as by-products. 2. the application of catalyst system according to claim 1, is characterized in that: The organic acid radical of the organic acid is a monobasic organic acid radical or a dibasic organic acid radical containing 1-6 carbon atoms; including formate, acetate, butyrate, valerate, oxalate, succinate, valerate diacid, or adipate. 3. the application of catalyst system according to claim 1 is characterized in that: the transition metal ion used exists in any form with catalytic decomposition cycloalkyl hydroperoxide activity; Comprise N-butylimidazolium copper ion, Vanadyl tartrate ion, chromate ion, metavanadate ion or molybdate ion. 4. catalyst system application according to claim 1, it is characterized in that: use this catalyst system to decompose in the cycloalkyl hydroperoxide process in alkane oxidation liquid, the volume ratio of catalyst aqueous solution and decomposition raw material liquid organic phase is 1: 100; The catalyst system decomposes the cycloalkyl hydroperoxide under the condition of stirring and heating, and the reaction temperature is 20-160 DEG C. 5. The application of the catalyst system according to claim 4, characterized in that: the catalytic system decomposes cycloalkyl hydroperoxide under stirring and heating conditions, and the reaction temperature is 60-110°C. 6. The application of the catalyst system according to claim 1, characterized in that: the volume ratio of the catalyst system to the organic phase of cycloalkyl hydroperoxide is 1:2-20; The cycloalkyl group is a cycloalkyl group with 3-18 carbon atoms in the ring.