KR930006681B1 - Catalyst for olefin oligomerization - Google Patents

Abstract

This is a new catalyst for oligomerization of C2-C4 olefin such as C4-raffinate, 1-butene, or 2-butene. The catalyst is composed of at least two transition metals selected from V, VI, VII and VIII groups in the periodic table; porous support composed of one or at least two of Al2O3, SiO2, MgO and ZrO2; and alkyl aluminum halide compound. The manufacturing method comprises; (A) impregnation and calcination of transition metal in the porous support; and (B) storing (A) product in the excess alkyl aluminum halide so as to bond some halide and supported metal catalyst.

Description

Small Polymerization Catalyst of Lower Olefin

The present invention relates to a small polymerization catalyst of lower olefins, and more particularly, to a catalyst capable of synthesizing higher olefins of C ₄ to C ₁₂ by oligomerization of lower olefins of C ₂ to C ₄ .

In general, olefins having 4 to 12 carbon atoms are used for various purposes in the petrochemical industry. Especially, C ₆ -olefin, a dimer of propylene, is useful as an octane number enhancer for gasoline used as a fuel for gasoline engines. It is also used as an intermediate for synthesizing seasonings, flavorings, medicines, dyes, resins and the like. In addition, C ₈ -olefin, which is a dimer of n-butene, is used as a basic raw material for plasticizer synthesis.

In particular, isononyl alcohol synthesized by Oxo reaction from small branched C ₈ -olefin (n-octene + methylheptene + small amount of diethylhexene mixture) forms ester compounds with phthalic anhydride or adipic acid, It is used as a plasticizer.

In addition, plasticizers DINP (diisononylphthalate), DINA (diisononyl adipate) made of isononyl alcohol, and plasticizers DOP (dioctylphthalate) made from conventional 2-ethylhexanol or methylheptanol, DOA (dione) Since there are fewer branches in three-dimensional structure than octyl adipate), it has a great effect on the quality and diversification of PVC products when used as PVC plasticizer.In the domestic PVC industry, the use of plasticizer of isononyl alcohol is increased due to the above characteristics. This is the setting you are doing.

In addition, C ₄ - C ₄ are generated in the small polymerization of olefin-terpolymer of olefins are C ₁₂ -, and is used to synthesize surfactants, lubricants, flavoring, perfumes, medicines, dyes and the like as the olefin, C ₁₂ - olefin It is also used as a high-grade lubricating oil by hydrogenation.

Currently, industrially produced C ₄ -residues react with isobutylene contained in methanol in the presence of an acid catalyst to synthesize MTBE (methyl tertiary butyl ether) to remove isobutylene and remain. ₄ - a fraction C ₄ - while bar hayeotneun named raffinate ⅱ (C ₄ -raffinate ⅱ), and these include n- butene, a situation that is currently used by the majority of these in the fuel. The ultimate object of the present invention is to produce a catalyst capable of converting these C ₄ -rapinate IIs used as fuels into chemical industrial raw materials.

On the other hand, a lot of techniques related to the production of such n-butene dimers are known, looking at these known techniques are as follows. That is, US Patent No. 4,490,571 discloses a method of reacting 2-butene at a reaction condition of 150 ° C. and 100 psig under a solid catalyst composed of BF ₃ -Al ₂ O ₃ and an amine or ether, but the conversion rate is lower than 50%. More than 90% of the dimers were produced with dimethylhexene, which was not useful for producing small branched C ₈ -olefins.

U.S. Patent No. 4,463,211 discloses a method of reacting n-butene using an ion exchange resin, Amberlyst 15, as a catalyst, but in this case also the conversion is only 80% or less and 90% or more of the dimer is dimethyl. Since it is made of hexene, it is not suitable for the production of small branched C ₈ -olefins.

In addition, US Pat. No. 4,613,580 describes a technique for preparing dimers by reacting n-butene at 350 ° C. 700 psig condition using a solid catalyst composed of a nickel salt-alumina-alkylaluminum compound. Although showing the conversion rate, there is a disadvantage that the reaction pressure must be very high, there was a problem that the stability and life of the catalyst is not maintained for a relatively long time.

Therefore, the present invention is a useful catalyst for synthesizing C ₄ to C ₁₂ olefins, which are being used in a variety of forms, from C ₂ to C ₄ lower olefins. The purpose is to provide a new small polymerization catalyst.

Hereinafter, the present invention will be described in detail.

The invention C ₄ - fraction (C ₄ -raffinate Ⅱ) or 1-butene or a catalyst used in the production of the oligomer of 2-butene, Ⅴ the Periodic Table, Ⅵ, Ⅶ and at least two transition metals selected from the group Ⅷ It is characterized by a small polymerization catalyst of a lower olefin consisting of a catalyst component, a porous carrier component composed of any one or a mixture of two or more selected from Al ₂ O ₃ , SiO ₂ , MgO and ZrO ₂ and an organoaluminum halide compound.

Referring to the present invention in more detail as follows.

The invention C ₄ - fraction (C ₄ -raffinate Ⅱ) or 1-butene or a catalyst used in the preparation of an oligomer of 2-butene, Ⅴ the Periodic Table, Ⅵ, Ⅶ, 2 or more selected from the transition group Ⅷ A catalyst formed by impregnating a metal catalyst component with a porous carrier and calcining it, and then storing it in an excess of an aluminum aluminum halide compound, whereby some of these compounds form a bond with the metal catalyst component. to be.

In this case, Al ₂ O ₃ , SiO ₂ , MgO, ZrO _2, and mixtures thereof may be used. In particular, carriers containing Al ₂ O ₃ showed excellent results in the activity of the catalyst. Transition metal compounds of Groups V, VI, V and V on the periodic table are water soluble Ni (NO ₃ ) ₂ , Ni (OH) ₂ , NiCl ₂ , Ni (CH ₃ CO ₂ ) ₂ , CrO ₃ , CrCl ₂ , Cr ( The porous carrier was impregnated with an aqueous solution of HCO ₂ ) ₃ , Cr ₂ (SO ₄ ) ₃ , CoCl ₂ , Co (NO ₃ ) 2, CoC ₂ O _4, and the like. Aluminum dihalides, aluminum halides, and the like and mixtures thereof.

According to the present invention, the porous carrier is preferably used in a molar ratio of 4 to 20 times with respect to the metal compound, wherein the organoaluminum halide compound used as the activation solution is 2 to 6 in atomic ratio with respect to the metal group of Group VIII. It is good to have enough composition.

In particular, the most preferred case in the present invention is Al ₂ O ₃ as a porous carrier, Ni as a metal catalyst component so that the molar ratio of Al ₂ O ₃ / NiO of 4 to 20, as a metal catalyst component In addition to the Ni, any one of vanadium (V), chromium (Cr) or manganese (Mn) compounds was found to be used in an amount of 5 to 20 mol% based on the NiO component. Especially in this case, the addition of vanadium greatly increases the reactivity and stability of the catalyst.

Further, an organic aluminum halogen compound used as active solution (C ₂ H ₅₎ AlCl ₂ or (C ₂ H _{5) 2} AlCl and AlCl ₃ of 1: 1 to 1: is mixed at a molar ratio of 0.4, or (C ₂ H ₅ ) ₃ Al ₂ Cl _{2 And the like} was the most preferable result.

On the other hand, in order to prepare a catalyst according to the present invention, the mixture of the metal catalyst component is dissolved in water of a molar volume corresponding to 2 to 4 times the porous carrier, and the porous carrier is mixed while stirring the aqueous solution. It was impregnated to dryness using a rotary evaporator while rotating.

The catalyst prepared as described above is allowed to flow air corresponding to 10 to 100 times the volume of the catalyst in a tubular furnace for 1 minute and calcined at 350 to 420 ° C. for 2 hours. By flowing, the catalyst in the tubular furnace was replaced with nitrogen to sinter the catalyst.

The calcined catalyst is placed in an excess of an organoaluminum halogen compound solution (molar ratio of Al / metal catalyst = 2 to 10) corresponding to 2 to 10 moles with respect to the metal catalyst component, and left to stand for about 5 hours or more. The catalyst was activated by being reduced by this organoaluminum halide.

After activating the catalyst in this way, the excess organic aluminum halide solution is discarded and the organic aluminum halide compound physically adsorbed to the catalyst is washed with a solvent such as toluene, hexane or heptane, and dried at a temperature of about 60 to 70 ° C. The catalyst was prepared by drying under reduced pressure by connecting to a vacuum pump.

On the other hand, the activity investigation of the catalyst prepared according to the present invention was carried out using a batch type reactor (batch type reactor) and a fixed bed type reactor (fixed bed type reactor).

In the catalytic activity investigation using a batch reactor, 1 g of catalyst and 30 g of n-butene prepared according to the above method were injected into a reactor equipped with a stirring device, and a reactor was installed in a constant temperature water bath of 15 to 30 ° C., followed by stirring the reactants. The reaction was carried out for 5 hours.

After the reaction was completed, the unreacted gas in the reactor was removed, the product weight was measured, and the reactivity of the catalyst was calculated by the following reaction formula to compare the activities between the catalysts.

In addition, in the catalytic activity investigation using a fixed-bed reactor, a catalyst having a metal catalyst component is pelletized to select a catalyst having a size of 6 to 8 mesh and activated after firing as in a batch reaction to activate a 1/2 inch tubular reactor. Was charged in 10 ml.

A reactor filled with a catalyst was installed in a constant temperature bath at 15 to 30 ° C., and n-butene was passed at a flow rate of LHSV = 0.5 to 2.0 hr ⁻¹ for reaction to investigate the reactivity and stability of the catalyst.

As a result of the investigation, the catalysts according to the present invention were superior in reactivity and stability compared to conventional catalysts.

When the small polymerization reaction of the lower olefin is carried out using the catalyst of the present invention, the reaction conditions have the advantage that the reaction can be carried out at a low temperature of 25 to 40 ℃ and a low pressure of 60 to 80 psig.

In addition, since the catalyst of the present invention is very excellent in reactivity and stability compared to the conventional one, it is very suitable for synthesizing C ₈ -olefin which is useful as a plasticizer by small polymerization of C ₄ -raffinate II as a raw material and as a by-product. The produced C ₁₂ -olefins can be used for the various applications listed above.

As described above, according to the present invention, since n-butene in C ₄ -resid oil, which is mass-produced as a by-product in the ethylene production process, can be used as a raw material, there is an industrially useful advantage.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by Examples.

Example 1

NiO-V ₂ O ₅ -Al ₂ O ₃ (NiO / V ₂ O ₅ / Al ₂ O ₃ molar ratio = 10/1/100)

To prepare a catalyst, a rotary evaporator was mixed with an aqueous solution of 5.8 g of Ni (NO ₃ ) ₂ ㆍ 6H2O and 0.48 g of NH ₄ VO ₃ in 20 g of Al ₂ O ₃ (Baker Chem.) Powder. After impregnation drying, air was flowed in a tubular furnace, heated to 400 ° C., fired for 4 hours, cooled, and cooled to room temperature.

The activating solution was prepared by mixing (CH ₃ ) ₂ AlCl: AlCl ₃ = 10: 4 molar ratio and dissolving it in toluene. This activating solution was used in all experiments below (20 wt% solution based on DEAC).

1 g of the catalyst above was taken in a 50 ml stainless steel vial equipped with a stirrer under nitrogen atmosphere, 3 ml of the activating solution was added thereto, and stirred for 24 hours. Then, the catalyst was washed three times with toluene purified by removing unreacted activating solution and removing water under nitrogen atmosphere and dried.

Take 30 g of liquefied 1-butene in a stainless vial containing a catalyst, place it in a constant temperature bath at 25 ° C., stir at a constant rate, remove the unreacted 1-butene and calculate the reactivity by measuring the weight of the product. It was. The reactivity resulted in 4.7 product g / Cat g / hr.

Example 2

NiO-V ₂ O ₅ -Al ₂ O ₃ catalyst powder of Example 1 was molded by tableting, sized 6-8 mesh (2.38-3.26mm), treated and dried with 10 ml of activation solution to prepare a final catalyst. .

10 ml of the catalyst prepared as described above was filled in a stainless steel tube reactor (1 inch inside, 20 cm long), and the reactor was installed in a 25 ° C. thermostatic bath, and then liquefied 2-butene at a pressure of 70 psig with a flow rate of LHSV = 1.4hr ⁻¹ The reaction proceeded while feeding.

GS and GC-Mass were used to determine the conversion, selectivity and product distribution over the reaction time. The results of the reaction are shown in Table 1.

TABLE 1

Example 3

20 g Al ₂ O ₃ (Baker Chem) powder and 5.8 g Ni (NO) to prepare a catalyst of NiO-CrO ₃ -Al ₂ O ₃ (NiO / CrO ₃ / Al ₂ O ₃ molar ratio = 10/1/100) ₃ ) ₂ ㆍ 6H ₂ O + 0.88g (NH ₄ ) ₂ CrO ₄ Aqueous solution was mixed, impregnated and dried in a rotary evaporator, and then molded using a tableting method to produce 6-7 mesh (2.38-3.26mm) catalyst. After sorting and firing in the same manner as in Example 2, treated with an activation solution, 10ml of the catalyst was charged in a stainless reactor, and the reaction was carried out under the same conditions as in Example 2. The results are listed in Table 2.

Example 4

20 g Al ₂ O ₃ powder and 5.8 g Ni (NO ₃ ) ₂ ㆍ 6H ₂ to prepare a catalyst of NiO-MnO-Al ₂ O ₃ (NiO / MnO / Al ₂ O ₃ molar ratio = 10/1/100) O + 0.88g Mn (SO ₄ ) .4H ₂ O aqueous solution was mixed, impregnated and dried in a rotary evaporator, molded and calcined in the same manner as in Example 2, and then treated with 10 ml of activating solution and dried. After the reaction was carried out under the same conditions as in Example 2. The reaction results are listed in Table 2.

TABLE 2

Example 5

Highly active τ-Al ₂ O ₃ (diameter 1 / to prepare a catalyst of NiO-V ₂ O ₅ -Al ₂ O ₃ (NiO / V ₂ O ₅ / Al ₂ O ₃ molar ratio = 10/1/100) 8 inches, 3 mm long pellets) 30ml was dipped in 0.2N NH ₄ VO ₃ aqueous solution for 2-3 seconds, flowing nitrogen in a tubular furnace and gradually increased the temperature and dried at 200 ℃ for 2-3 hours.

After cooling the dried NH ₄ VO ₃ -Al ₂ O ₃ pellet to room temperature, immersed in 2N Ni (NO ₃ ) ₂ aqueous solution for 2 ~ 3 seconds and gradually increased the temperature in the tubular furnace and calcined at 400 ℃ for 4 hours and then nitrogen Shed cool to room temperature.

10 ml of the catalyst thus prepared was taken to activate the catalyst with the activating solution of the composition used in Example 1 to prepare a final catalyst.

10 ml of the catalyst thus prepared was filled in a stainless steel tube reactor (1 inch inner diameter, 20 cm long), and the reactor was installed in a constant temperature bath at 25 ° C., and C ₄ -raffinate II was flown at a pressure of 70 psig. LHSV = 1.4hr ⁻¹ . The reaction proceeded while feeding. C ₄ used in this embodiment is a C ₄ raffinate Ⅱ produced as a by-product in the naphtha cracking process in the domestic-end C ₄ after a MTBE synthesis and separation from the residual butene -Ⅰ - a fraction of these compositions are n -Butane contains 39% and butene-2 61%. The reaction results are listed in Table 3.

TABLE 3

Comparative Example 1

Conventional catalysts for converting lower olefins to higher olefins are available, but among them, the catalyst known to have the highest reaction activity is a catalyst in which Al ₂ O ₃ -NiO of US Patent No. 4,613,580 is activated with an alkyl aluminum compound.

In order to compare the catalyst with the catalyst of the present invention, 20g Al ₂ O ₃ (Baker Chem) powder and 5.8g Ni (NO ₃ ) ₂ ㆍ 6H ₂ O dissolved in an aqueous solution of the same method as in Example 1 After impregnating and drying using a rotary evaporator, the air was flowed in the tubular furnace in the same manner as in Example 1, heated to 400 ° C., fired for 4 hours, cooled, and cooled to room temperature.

When the catalyst was activated, the same solution as in Example 1 was activated in the same manner, and the reaction conditions and the analysis method of the product were the same as in Example 1. As a result of the reaction, reactivity yielded 3.4 product g / Cat g / hr. When V ₂ O ₅ was added to NiO-Al ₂ O ₃ as a reaction accelerator, it was shown to be improved by about 38% under the same reaction conditions compared to the conventional catalyst.

Comparative Example 2

To compare the performance of the catalyst of the present invention with a conventional catalyst in a fixed bed reactor for the same purpose as Comparative Example 1.

Existing catalyst is Al ₂ O ₃ -NiO catalyst, Al ₂ O ₃ -NiO catalyst powder in Comparative Example 1 was molded by a compression method to perform a 10ml catalyst of 6 ~ 8 mesh (2.38-3.26mm) size selection In the same manner as in Example 2, the catalyst was calcined at 400 ° C. for 4 hours, flowed with nitrogen, and cooled to room temperature.

The calcined catalyst is left for 24 hours with the addition of 10 ml of activating solution, washed three times with dried toluene to remove excess alkyl aluminum and dried to prepare a final catalyst.

The catalyst thus prepared was filled with 10 ml in a stainless steel reactor (inner diameter 1 inch long 20 cm) and subjected to the reaction under the same reaction conditions as in Example 2 in a 25 ° C. thermostat, and the results are listed in Table 3.

Compared with the experimental results of the catalysts of the present invention, in which the catalyst synthesized in the same manner with Table 3, which is the result of the existing catalyst, was reacted under the same reaction conditions, the conversion rate of the reaction when V ₂ O ₅ of Table 1 was added to the catalyst as a reaction accelerator. It can be observed that the improvement of about 5%, and when the addition of CrO ₃ and MnO in Table 2 as the reaction accelerator, it can be observed that the conversion glass 2 ~ 3% improvement of the reaction.

On the other hand, these catalysts have the disadvantage that the catalyst life is not long. Catalysts in the present invention can be seen to decrease the reaction activity decrease compared to the conventional catalyst of Table 3 as shown in Table 2 and Comparative Example 1.

In particular, the catalyst added with V ₂ O ₅ shows that the deactivation of the catalyst is remarkably improved compared to the existing catalyst.

TABLE 4

Comparative Example 3

In this comparative example, an existing known catalyst Al ₂ O ₃ -NiO catalyst was applied to C ₄ -raffinate II produced in Korea. In order to prepare a conventional known catalyst, high activity τ-Al ₂ O ₃ (pellets having a diameter of 1/8 inch length 3 mm) was added to a 2N Ni (NO ₃ ) ₂ aqueous solution in the same manner as in Example 5 for 2-3 seconds. After immersion, nitrogen was flowed from the tubular furnace, and the temperature was increased and then fired at 400 ° C. for 4 hours, followed by nitrogen flow and cooled to room temperature. The catalyst was prepared by activating the catalyst in the same manner with the activation solution used in Example 5 taking 10 ml of the catalyst prepared as described above.

Thus prepared catalyst is connected in parallel to the same reaction tank in the same conditions as in Example 5 and the results of the reaction using the same C ₄ -raffinate II as a raw material are listed in Table 5. Comparing these results with those of Example 5, Example 5, which is the catalyst of the present invention, was found to be 2-5% higher in the initial conversion rate, and the catalyst of the present invention was superior in terms of deactivation of the reaction. Is showing.

TABLE 5

Claims (8)

C ₄ - fraction (C ₄ - raffinate Ⅱ) or 1-butene or a catalyst used in the production of the oligomer of 2-butene, Ⅴ the Periodic Table, Ⅵ, Ⅶ and Ⅷ group at least two transition metal catalyst component selected from A small polymerization catalyst of a low molecular weight olefin consisting of a porous carrier component consisting of any one or a mixture of two or more selected from Al ₂ O ₃ , SiO ₂ , MgO and ZrO ₂ and an organoaluminum halogen compound. The low-olefin catalyst of claim 1, wherein the porous carrier component is contained in a molar ratio of 4 to 20 times the metal catalyst component. The low-olefin catalyst of claim 1, wherein at least one of the metal catalyst components is a Ni compound of Group VIII. The low-olefin catalyst of claim 1, wherein the transition metal catalyst components of Groups V, VI and VIII are vanadium, chromium and manganese compounds, respectively. The low-polymerization of the lower olefin of claim 1 or 4, wherein the transition metal catalyst component of Group V, VI or Group V is contained in an amount of 5 to 20 mol% based on the Group VIII metal catalyst component. catalyst. The lower olefin catalyst of claim 1, wherein the organoaluminum halide compound is a mixture of (C ₂ H ₅ ) ₂ AlCl and AlCl ₃ in a molar ratio of 1: 0.4. At least two or more transition metal catalyst components selected from Groups V, VI, V and V on the periodic table are dissolved in a molar volume of 2 to 4 times with respect to the porous carrier to which they are added, and stirred as a porous carrier component. Al ₂ O ₃ , SiO ₂ , MgO ZrO _{2 The} catalyst is prepared by adding any one or a mixture of two or more thereof, and calcining it at 350-420 ° C., and then calcining the catalyst to dialkylaluminum halide, alkylaluminum dihalide and sikidoe mixture of any one or more organic aluminum halogen compound selected from the group consisting of aluminum halide into the organic aluminum halide of the amount corresponding to 2 to 10 mole relative to the catalyst component, activate the catalyst by then, dried under reduced pressure to C ₄ - to prepare a (raffinate ⅱ C ₄₎ or 1-butene or small polymerization catalysts of olefins used in the preparation of the oligomer of 2-butene fraction Way. Porous carrier component and organoaluminum comprising at least two or more transition metal catalysts selected from group V, VI, V and V on the periodic table and any one or a mixture of two or more selected from Al ₂ O ₃ , SiO ₂ , MgO and ZrO ₂ fraction (C ₄ - - raffinate ⅱ) or a method for preparing an oligomer of 1-butene or 2-butene C ₄ have a small catalytic polymerization of olefins made of a halogen compound.