KR100720834B1 - Methods to prepare oxygenated hydrocarbons using nickel containing porous materials - Google Patents

Abstract

The present invention relates to a method for producing an oxide of a hydrocarbon using a porous material containing nickel, and more particularly, in performing oxidative functionalization reactions such as epoxidation and hydroxylation of unsaturated hydrocarbons using hydrogen peroxide as an oxidizing agent. The present invention relates to a method for preparing oxides of various hydrocarbon compounds by using nickel-containing porous materials such as phosphate catalysts as catalysts, and the method for preparing oxides of hydrocarbon compounds according to the present invention has higher productivity, yield and selectivity than conventional catalysts. Excellent and easy reuse of catalysts makes it possible to produce oxides of hydrocarbons in an economical way.

Porous material, nickel phosphate, nickel aluminophosphate, catalyst, oxidation functionalization, epoxidation, hydroxylation, oxidation reaction

Description

Method for prepare oxygenated hydrocarbons using nickel containing porous materials

The present invention is characterized by using a porous material containing nickel when oxidizing various hydrocarbon compounds using hydrogen peroxide as an oxidant, and excellent in productivity, activity and selectivity by using the catalyst of the present invention. The organic oxide can be prepared, and when the oxidation functionalization is performed using the catalyst of the present invention, there is almost no leaching of the active ingredient from the catalyst during the catalytic reaction, so that the catalyst can be easily reused. .

From an environmentally friendly point of view, the selective oxidizing agent used for the liquid phase oxidation functionalization of organic compounds requires the use of hydrogen peroxide, which is harmless to the environment, instead of molecular oxygen or organic peroxides. The use of oxygen as an oxidant has disadvantages due to low selectivity due to various side reactions, and when organic peroxides and peroxides are used as oxidants, organic matters can be by-produced after decomposition and cause environmental pollution. However, when hydrogen peroxide is used as an oxidizing agent, active oxygen species and water are produced after decomposition, and thus are not only highly selective for oxidative functionalization but also have no environmental problems. Therefore, the use of hydrogen peroxide rather than molecular oxygen or organic peroxide is preferred as an oxidizing agent of organic compounds, and for this reason, many studies have recently been conducted to utilize hydrogen peroxide in liquid oxidative functionalization. Various kinds of catalysts are used to oxidize the oxides. It is known that heterogeneous catalysts including transition metals such as molybdenum, titanium, vanadium, tungsten, copper, and lead are suitable as components of the catalyst (Advanced Synthesis and Catalysis, 345 (2003), 457). The catalyst containing the transition metal is of interest because it shows good properties. For example, Korean Patent Laid-Open No. 2002-0084500 discloses a technique related to a catalyst for oxidation reaction, which comprises a porous molecular sieve catalyst containing lead.

Recently, molecular sieves in which titanium, such as titanium silicate (TS-1 series zeolite), are substituted at skeletal positions have emerged as very useful catalysts for the oxidation functionalization of hydrocarbons in the presence of hydrogen peroxide and under mild conditions. TS-1 zeolite is a ZSM-5-structured zeolite with a very high silicon content and is coordinated with tetrahedrons in the low Ti (IV) paper structure, which highly disperses the active site of the catalyst, thus greatly increasing the selectivity of oxidation functionalization. And oxidative functionalization can be carried out by an aqueous hydrogen peroxide solution under very mild conditions. As an example of this, Adv. Catal. 41 (1996) 2, Micropor. Mesopor. Mater. 73 (2004) 137, Acc. Chem. Res. 31 (1998) 485 et al., A study on the use of a titanium catalyst comprising a molecular sieve such as titanium silicate-1 (TS-1) or Ti-MWW for the oxidation functionalization can be found.

In the oxidation functionalization of the hydrocarbon, porous materials containing various kinds of transition metals have been used, but there is still a need for a lot of room for improvement in productivity, conversion rate, selectivity, and suppression of side reactions. Development is required.

In general, in the reaction of oxidizing hydrocarbons using a porous material containing a transition metal, the leaching of the active ingredient of the catalyst does not occur because the leaching of the active ingredient is considered a serious problem during the recovery of the catalyst during or after the reaction. The development of catalysts has a great advantage in industrial use.

Accordingly, the present inventors have studied nickel catalysts that are excellent in conversion and selectivity and easy to reuse in oxidative functionalization of hydrocarbons using hydrogen peroxide as an oxidizing agent in order to solve the above technical problems. The present invention has been completed by knowing that an oxide of a hydrocarbon compound can be effectively produced by using the prepared porous catalyst together with hydrogen peroxide.

Accordingly, the present invention is excellent in productivity, conversion and selectivity by using a nickel-containing porous material, preferably nickel phosphate and nickel aluminophosphate catalysts, in carrying out the oxidation functionalization of hydrocarbons using hydrogen peroxide as the oxidant. It is an object to provide a method for producing oxides of various hydrocarbons.

The present invention relates to a method for producing an oxide of a hydrocarbon using a porous material containing nickel, and more particularly, epoxidation and hygithiation of unsaturated hydrocarbons using hydrogen peroxide as an oxidant together with a nickel phosphate catalyst and a nickel aluminophosphate catalyst. The method for producing oxides of various hydrocarbons is characterized by carrying out oxidation functionalization such as these.

Referring to the present invention in more detail as follows.

The catalyst for oxidation functionalization according to the present invention is a porous material containing nickel capable of effectively oxidizing hydrocarbons by hydrogen peroxide, preferably nickel aluminophosphate including nickel phosphate and Ni-AlPO- n , more preferably. Preferably selected from VSB-1, VSB-5 and Ni-AlPO-5.

The nickel phosphate and nickel aluminophosphate can be easily prepared by reaction at high temperature in the presence of phosphoric acid, nickel and aluminum salt by a known method. The obtained nickel phosphate and nickel aluminophosphate are X-ray powder rotating method and scanning electron The structure and surface image can be confirmed by a microscope (SEM).

In the present invention, the nickel phosphate and nickel alumino phosphate can be used directly in the oxidative functionalization, and the surface of the nickel phosphate may be treated to reduce hydrophilicity and increase hydrophobicity to improve reactivity and selectivity.

As an example of the surface treatment method, a silylation reaction, a dehydroxylation reaction, a dehydration reaction, and the like may be selected. Mesopor. Mater. 28 (1999) 217. and J. Colloid Interface Sci. 121 (1988) 63 describes silylation reactions. Typical reaction conditions for the silylation reaction are made by reacting the silylated reactants in a hydrocarbon solvent at 0-120 ° C. for 30 minutes to 12 hours. The yield or selectivity can be obtained when a porous material containing silylated surface-treated nickel is used for oxidative functionalization. This can be improved.

In another aspect of the present invention, the catalyst can be dehydrated prior to oxidation functionalization. Dehydration of the catalyst is carried out by heating at 50-600 ° C. for 30 minutes to 12 hours before the catalyst is introduced into the reactor, and the dehydrated catalyst can be improved in yield or selectivity like the silylated surface treated catalyst.

In the present invention, one or more metal components among transition metals other than nickel or lanthanide metals may be added to the porous material containing nickel as a catalyst. The added metal component may be selected from titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, molybdenum, zirconium, hafnium, cerium, and in Korea Patent No. 10-0525209, components such as transition metals may be selected. The nickel-containing porous material included is described. Likewise, when the porous material containing nickel to which the transition metal is added is used for oxidative functionalization, the yield or selectivity of specific oxidative functionalization may be improved. The hydrocarbon compound used as a raw material for the oxidation functionalization of the present invention is an unsaturated hydrocarbon compound, preferably an olefin and a cycloolefin compound, and more preferably an alkylated derivative of benzene, phenol and phenol as an olefin and cycloolefin. Propylene, butene, pentene, octene, hexene, styrene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclododecene, norbornene, dodecene, heptene, limonene, limonenebutadiene, cinnamil alcohol, nerol And other hydrocarbons such as various alcohols and ketones can be used.

The catalyst for oxidation functionalization of the present invention can be used for the oxidation functionalization reaction of almost all unsaturated hydrocarbons, and preferably for the oxidation functionalization reaction selected from epoxidation, hydroxylation, ammoxidation and oxidation. have.

Oxidation functionalization of the present invention is carried out at a temperature of 0-300 ℃, preferably 40-150 ℃ which is a condition of the general oxidation reaction and the reaction time is 1 minutes-3 days, preferably 30 minutes to 10 hours It is characterized in that performed by.

The content of the nickel phosphate catalyst and the nickel aluminophosphate catalyst is preferably used in a weight ratio of 0.0001-1.0 of the unsaturated hydrocarbon reactants, more preferably 0.001-0.5. In this case, if the content of the catalyst is low, the yield may be lowered. If the content of the catalyst is too high, side reactions may occur, which is not preferable. The molar ratio of hydrogen peroxide / substrate for oxidative functionalization is 0.1-10 and 0.2-5 is more suitable. Too low a low conversion rate, too high a hydrogen peroxide efficiency and various side reactions occur.

The present invention is also characterized in that the catalyst used in the oxidation functionalization of hydrocarbons can be reused.

Nickel-containing porous material described in the present invention has the advantage that can be reused immediately after recovery because there is no deterioration of activity during reuse because the catalyst does not occur in the reaction. In general, in the reaction of oxidizing hydrocarbons using a porous material containing a transition metal, the leaching of the active ingredient is considered a serious problem, but the nickel-containing porous material described in the present invention does not cause the catalyst to leach during the reaction. As a result, there is no deterioration of activity during reuse and the advantage of heterogeneous catalysts can be utilized, which is a great advantage in industrial use. In addition, no special regeneration method of the catalyst is required and the recovery method can be reused by simply recovering, washing and drying the used catalyst.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to the following Examples.

EXAMPLE

<Catalyst preparation>

As the porous material containing nickel of the present invention, VSB-1, VSB-5 and Ni-AlPO-5 were used, and each was synthesized by a known method.

1) Manufacturing Method of VSB-1

VSB-1 is described in Chem. Mater. It was synthesized as described in 17 (2005) 4455. Explaining the typical reaction conditions, the ratio of phosphoric acid: nickel chloride: ammonium fluoride: water as the composition of the reactant is 1: 1: 2.5: 100, and after 1 hour reaction at 180 ° C. under mild acid condition of pH 3-5. VSB-1 was prepared by drying through centrifugation and washing, and the structure and surface image were confirmed by X-ray powder rotation and scanning electron microscopy (SEM).

2) Manufacturing Method of VSB-5

VSB-5 is described in J. Phys. Chem. B 109 (2005) 845 and Chem. Mater. It was synthesized as described in 17 (2005) 4455. To explain the typical reaction conditions, the ratio of phosphoric acid: nickel chloride: ammonia: water is 0.63: 1: 3: 100 as the composition of the reactant, and the reaction is centrifuged after reaction at 180 ° C. for 2 hours under weak base conditions of pH 7-8. The VSB-5 was prepared by drying through a washing and washing process, and the structure and surface image were confirmed by X-ray powder rotation and scanning electron microscopy (SEM).

3) Ni-AlPO-5 and AlPO-5

AlPO-5, Ni-AlPO-5 is described in J. Mater. Chem. 14 (2004) 280. The typical reaction conditions are described in terms of the composition of the reactants: the ratio of phosphoric acid: aluminum: nickel: triethylamine: water in a ratio of 1: 1: (0-0.5): 0.6: 25, under a weak acid condition of pH 3-6. After 30 minutes of reaction at 180 ℃ by drying through centrifugation and washing Ni-AlPO-5 and AlPO-5 could be prepared and the structure and surface images could be confirmed by X-ray powder diffraction and scanning electron microscopy (SEM).

4) Porous materials containing nickel with reduced hydrophilicity and increased hydrophobicity

Synthesized nickel-containing porous materials are described in Micropor. Mesopor. Mater. 28 (1999) 217. and J. Colloid Interface Sci. 121 (1988) The material was converted to a substance having increased hydrophobicity and reduced hydrophilicity as described in 63. The typical reaction conditions were prepared by reacting the silylated reactant (trimethylmethoxysilane) at 55 ° C. for 15 hours in a toluene solvent. The degree of silylation was evaluated by quantitatively analyzing the content of methyl groups present in the catalyst using Fourier transform infrared spectroscopy (FTIR).

5) Nickel-containing porous material to which at least one metal component of transition metal or lanthanide metal is added

Metal-VSB-5 is described in J. Phys. Chem. B 109 (2005) 845, Metal-VSB-1 is Chem. Mater. 16 (2004) 5552. The typical reaction conditions are very similar to VSB-1 and VSB-5 and synthesized by the addition of metal precursors. The transition metal or lanthanide metal had a composition of 0.001-0.5 molar ratio to nickel.

Oxidation Functionalization of Hydrocarbons

The olefin epoxidation reaction was carried out to test the prepared catalyst. The results are shown in the following examples.

Example 1

Cyclohexene epoxidation was carried out to evaluate the catalytic activity. This was carried out in a commercial super reactor equipped with a stirrer and a reflux condenser, and a conventional method is described, in which a ratio of 0.35 g of VSB-5 catalyst, 5 ml of cyclohexene, 18 ml of acetonitrile and hydrogen peroxide: cyclohexene is 3: 1. In order to control the amount of hydrogen peroxide was added to the reactor. The catalyst used was used after the dehydration reaction by heating at 300 ℃ for 4 hours before the input to the super reactor, and the epoxidation reaction was carried out by stirring the reaction in the reactor for 8 hours at 60 ℃. The product obtained was cyclohexene oxide, 1,2-cyclohexane diol (each compound obtained hereinafter referred to as epoxide, diol) and other by-products, the product content was analyzed using gas chromatography and the conversion and Selectivity (epoxide and diol) was determined and shown in Table 1.

Example 2

The same procedure as in Example 1 was carried out, but the catalyst recovered after the reaction was separated and dried, and then dried and dehydrated at 300 ° C. for 4 hours, and used for catalytic reaction. Selectivity (epoxide and diol) was determined and shown in Table 1.

Example 3

The same procedure as in Example 2 was carried out, but the catalyst recovered after two uses was dehydrated at 300 ° C. for 4 hours, and then the oxidation functionalization proceeded. The content of the product was analyzed using gas chromatography, and the conversion and selectivity ( Epoxide and diol) were determined and shown in Table 1.

Example 4

In the same manner as in Example 3, using the catalyst recovered after three times, the dehydration reaction followed by the oxidation functionalization reaction, the product content was analyzed using gas chromatography and the conversion and selectivity (epoxide and Diol) was determined and shown in Table 1.

Example 5

The reaction was carried out in the same manner as in Example 1, but the reaction proceeded using cyclooctene instead of cyclohexene, and the reaction time was 7 hours. The content of the product was analyzed using gas chromatography and the conversion and selectivity (epoxide and diol) were determined and shown in Table 1. Epoxide selectivity was high.

Example 6

The reaction was carried out in the same manner as in Example 1, but using silylated VBS-5 (hereinafter referred to as Si / VSB-5) as a catalyst, and the content of the product was analyzed using gas chromatography. Selectivity (epoxide and diol) was determined and shown in Table 1. Epoxide selectivity was high.

Example 7

The catalyst was used in the same manner as in Example 1, but the catalyst used was dehydrated (heated at 300 ° C. for 4 hours), and the conversion and selectivity (epoxide and diol) were determined and shown in Table 1. Epoxide selectivity was high.

Example 8

The reaction was carried out in the same manner as in Example 1, using the dehydrated VBS-1 as a catalyst, the product content was analyzed using gas chromatography and the conversion and selectivity (epoxide and diol) were determined. 1 is shown. Epoxide selectivity was high.

Example 9

The reaction was carried out in the same manner as in Example 1, but the reaction was carried out using Ni-AlPO-5 as a catalyst, the content of the product was analyzed by gas chromatography, and the conversion and selectivity (epoxide and diol) were determined. 1 is shown. Epoxide selectivity was high.

Example 10

The reaction was carried out in the same manner as in Example 1, except that VSB-5 (hereinafter, Fe-VSB-5) containing iron (Fe) as a transition metal was used as a catalyst, and the product was subjected to gas chromatography. Was analyzed and the conversion and selectivity (epoxide and diol) were determined and shown in Table 1.

Example 11

The reaction was carried out in the same manner as in Example 1, except that VSB-5 (hereinafter referred to as Ti-VSB-5) containing titanium (Ti) as a transition metal was used as a catalyst, and the product was subjected to gas chromatography. Was analyzed and the conversion and selectivity (epoxide and diol) were determined and shown in Table 1.

Example 12

The reaction was carried out in the same manner as in Example 1, except that VSB-1 (hereinafter referred to as Co-VSB-1) containing cobalt (Co) as a transition metal was used as a catalyst, and the product was subjected to gas chromatography. Was analyzed and the conversion and selectivity (epoxide and diol) were determined and shown in Table 1.

Example 13

The reaction was carried out in the same manner as in Example 1, but the reaction proceeded using 0.02 g instead of 0.35 g, the product content was analyzed using gas chromatography, and the conversion and selectivity (epoxide and diol) were determined. Shown in

Comparative Example 1

The reaction was carried out in the same manner as in Example 1, but the reaction was carried out using 0.35 g of nickel oxide (NiO) as a catalyst, and the content of the product was analyzed using gas chromatography, and the yield and selectivity (epoxide and diol) were measured. The crystals are shown in Table 1.

Comparative Example 2

The reaction was carried out in the same manner as in Comparative Example 1, the reaction was carried out using 1 g of nickel chloride (NiCl 2 · 6H 2 O) as a catalyst and the product content was analyzed using gas chromatography, yield and selectivity (epoxide and diol) It was determined and shown in Table 1.

Comparative Example 3

The reaction was carried out in the same manner as in Comparative Example 1, but the reaction was carried out using 1 g of nickel acetate (Ni (OAc) 2 · 4H 2 O) as a catalyst and the product content was analyzed using gas chromatography, yield and selectivity (epoxy) Side and diol) are determined and shown in Table 1.

[Comparative Example 4]

The reaction was carried out in the same manner as in Comparative Example 1, but the reaction proceeded without using a catalyst, and the content of the product was analyzed using gas chromatography, and the yield and selectivity (epoxide and diol) were determined and shown in Table 1.

[Comparative Example 5]

The reaction was carried out in the same manner as in Example 1, but the reaction was carried out using AlPO-5 as a catalyst, the content of the product was analyzed using gas chromatography, and the yield and selectivity (epoxide and diol) were determined. Indicated.

Table 1 shows the results of Examples 1 to 13 and Comparative Examples 1 to 5.

TABLE 1

As shown in Table 1, cyclohexene oxide and 1,2, which are industrially useful as main products when the epoxidation reaction of cyclohexene is carried out using a nickel-containing porous material of the present invention using a catalyst and hydrogen peroxide as an oxidizing agent. At least 80% of cyclohexane diol is produced, in particular, the selectivity of epoxide is at least 45%, and in the present invention, when the catalyst recovered after the reaction is firstly reused, only a slight decrease in activity occurs, thereby decreasing the activity of the catalyst thereafter. It also turned out not to be large. In addition, in the analysis by inductively coupled plasma (ICP), it was found that Ni was not detected in the solution when the catalyst was applied to this reaction. Therefore, leaching of the active ingredient did not occur, and thus it could be reused. There is great advantage in industrial use. In addition, even with 0.5% of catalyst, the conversion rate was 68%, so the productivity per catalyst weight is extremely high.

In addition, Comparative Examples 1 to 5 of the above table show the superiority of the catalyst of the present invention by showing the yield and selectivity when using the catalyst of the present invention and a nickel compound other than the porous material as a catalyst, and also shows the present invention. By using cyclohexene and cyclooctene as reactants for the catalyst, it is shown that the catalyst of the present invention can be applied to the oxidation functionalization of various olefins.

In the above table, the nickel-containing porous catalyst of the present invention may select nickel phosphate and nickel aluminophosphate according to the catalyst, and dehydration and silylation reaction may be selected according to the surface treatment method of the catalyst. By showing that various kinds of catalysts can be prepared by selecting a method of adding transition metals for the change of constituents, there is a possibility that they can be applied under optimum conditions for the industrialization of specific oxidative functionalization. The oxide production method is expected to have a great applicability and ripple effect.

As described above, the present invention is characterized by using a porous material containing nickel when oxidizing various hydrocarbon compounds using hydrogen peroxide as the oxidizing agent, and by using the catalyst of the present invention, productivity, activity and selection Excellent organic oxide can be prepared in the drawing. In addition, when the oxidation functionalization is carried out using the catalyst of the present invention, there is almost no riching that the active ingredient escapes from the catalyst during the catalytic reaction, so that the catalyst can be easily reused immediately after separation and washing and drying. The possibility of practical use is very high, and it is expected that the applicability and the ripple effect of oxidative functionalization will be very large.

Claims (15)

In the method for producing an oxide of a hydrocarbon by an oxidative functionalization reaction using hydrogen peroxide, the oxidative functionalization reaction is an epoxidation reaction or a hydroxylation reaction, and the porous nickel phosphate as the oxidation functionalization catalyst Or a porous nickel aluminophosphate. The method of claim 1, wherein olefin or cycloolefin is selected as the hydrocarbon. The method of claim 1, wherein the oxidation functionalization reaction is carried out by a reaction time of 1 minute to 3 days at a temperature of 0-300 ℃. The process of claim 1 wherein the catalyst used is reused. delete delete The method of claim 1, wherein the porous nickel phosphate is selected from those having a structure of VSB-1, VSB-5. The method of claim 1, wherein the porous nickel aluminophosphate has a structure of Ni-AIPO-5. delete delete The method of claim 1, wherein the oxidative functionalization reaction is an epoxidation reaction. delete The method for producing an oxide of a hydrocarbon according to claim 11, wherein olefin or cycloolefin is selected as a raw material for the epoxidation reaction. The oxide of a hydrocarbon according to claim 13, wherein the catalyst further contains a metal component selected from titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, molybdenum, zirconium, hafnium, and cerium. How to prepare. The method of claim 1, wherein silylation, dehydroxylation, or dehydration is used to reduce the hydrophilicity and increase hydrophobicity of the porous nickel phosphate or the porous nickel aluminophosphate to increase the selectivity of the oxidative functionalization reaction. Method for producing an oxide of a hydrocarbon, characterized in that.