JP5410150B2 - Alkali metal salt of heteropolyacid and catalyst for olefin oligomerization comprising the same - Google Patents

Description

  The present invention relates to an alkali metal salt of a heteropolyacid, a catalyst for olefin oligomerization comprising the same, and a method for producing an olefin oligomer. In particular, it relates to a method for selectively producing an oligomer of isobutene from a mixed C4 fraction.

Olefin oligomers are useful compounds that are widely used as raw materials for fuel oils such as gasoline and diesel, lubricating oils, solvents, and other chemicals.
In particular, isoparaffins produced by hydrogenating isobutene oligomers are used in various solvents (household aerosols, (low odor) paints, (low odor) inks, flaw detection agents, metal extraction, agricultural chemicals, insecticides, ant-proofing agents, rust-proofing. Agent, antibacterial / antifungal agent, insect repellent, adhesive, sealing agent, release agent, metal paste, abrasive, diluent (olefin polymerization catalyst carrier, PVC sol compound, fragrance, car wax, home polish Cleaner), lubricant, cleaning agent (metal cleaning, wire solder cleaning, oil cleaning, grease cleaning agent, liquid crystal cell dirt and resin cleaning, flux cleaning agent, wax cleaning, various ink film peeling and cleaning, various cleaners ), Widely used as cosmetics.
Butene oligomers are generally polymerized by using the remaining fraction (so-called spent BB fraction) obtained by extracting butadiene from the C4 fraction (butane-butene mixture (BB) fraction) produced by naphtha cracking as a raw material. It is a liquid oligomer having an average molecular weight of about 100 to 2500.

  Various methods are known as a method for producing a butene oligomer using an acid catalyst. For example, as a homogeneous acid catalyst process, there is a method in which a raw material consisting of a BB fraction is passed through a liquid slurry in which a Friedel-Craft catalyst such as anhydrous aluminum chloride is suspended (see, for example, Patent Document 1). Further, as a heterogeneous solid catalyst process, there is a method of contacting a solid catalyst made of dry chlorinated alumina (see, for example, Patent Document 2). Furthermore, a method of contacting with a solid catalyst such as fluorinated alumina, alumina boron, silica alumina, solid phosphoric acid, chromium oxide, zinc oxide, zeolite, heteropoly acid is known (for example, see Patent Documents 3 and 4). Industrially, standard process, Cosden process, UOP “Catalytic Condensation”, ExxonMobil “EMOGAS”, IFP / Axens “Selectopol”, and the like have been put into practical use.

JP 60-124602 A JP-A-57-82325 Japanese Patent Laid-Open No. 56-40618 JP 2005-15383 A

  In homogeneous catalysts, strong Lewis acid catalysts such as aluminum chloride, boron trifluoride, sulfuric acid and the like are used, and thus there are industrial problems such as waste catalyst treatment and corrosion of manufacturing equipment.

  On the other hand, in the case of heterogeneous solid catalysts, silica alumina, phosphate diatomaceous earth, zeolite catalyst, etc. are used. Therefore, practical reaction conditions depend on the progress of side reactions such as isomerization, decomposition, and heavy product. A major problem is a decrease in economy and a significant decrease in activity due to the deposition of these products on the catalytic active sites.

  In addition, regarding the oligomer composition obtained by the catalytic reaction, in any conventional production method, the production ratio and isomer composition of each oligomer are almost determined if the raw material composition and the butene conversion rate are determined, regardless of which catalyst system is used. Therefore, there was a problem that it was not possible to increase the yield of isobutene oligomer alone by highly selectively oligomerizing only isobutene.

  The isobutene oligomer is, for example, a compound such as 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene (commonly called diisobutylene), and a dimer is a high octane gasoline group. It is particularly useful as a raw material for lumber, lubricating oil and chemicals. Also in trimers and tetramers, isobutene oligomers are particularly useful as raw materials for isoparaffin solvents and the like. Conventionally, since isobutene and n-butenes in a mixed C4 fraction are oligomerized at a specific ratio (reaction rate ratio), when it is desired to produce only isobutene oligomers without oligomerizing n-butenes. In addition, n-butenes were reacted and lost.

  In view of the above problems, the present invention is an excellent olefin oligomerization catalyst, particularly for olefin oligomerization, which can selectively oligomerize branched olefins when a mixture of branched olefins and linear olefins is used as a raw material. An object is to provide a catalyst.

According to the present invention, the following alkali metal salts of heteropolyacid and the like are provided.
1. Of a heteropolyacid represented by Li _x H _4-x SiW ₁₂ O ₄₀ , Na _x H _4-x SiW ₁₂ O ₄₀ or K _x H _4-x SiW ₁₂ O ₄₀ (x = 2.5 to 3.5) Alkali metal salt.
The catalyst for olefin oligomerization which consists of alkali metal salt of the heteropolyacid of 2.1 description.
3. 3. The olefin oligomerization catalyst according to 2, supported on a support.
4). 4. The catalyst for olefin oligomerization according to 3, wherein the carrier is silica (SiO ₂ ) or alumina (Al ₂ O ₃ ), and the support ratio of the alkali metal salt of the heteropolyacid is 1 to 20% by weight.
The manufacturing method of the olefin oligomer which oligomerizes a raw material olefin using the catalyst in any one of 5.2-4.
6). 6. The method for producing an olefin oligomer according to 5, wherein the raw material olefin is propylene or butene.
7). 6. The method for producing an olefin oligomer according to 5, wherein the raw material olefin is a C4 fraction by-produced from naphtha cracking.
8). The method for producing an olefin oligomer according to 5 or 7, wherein the raw olefin is a mixture of a branched olefin and a linear olefin, and the catalyst selectively oligomerizes the branched olefin from the raw olefin.
9. The manufacturing method of the olefin oligomer in any one of 5-8 in which the said olefin oligomer contains the 2, 3 and tetramer of the said raw material olefin.

  According to the present invention, an excellent catalyst for olefin oligomerization can be provided. In particular, when a mixed C4 raw material is polymerized to produce a butene oligomer, an olefin oligomerization catalyst capable of selectively increasing the isobutene oligomer can be provided.

Alkali metal salts of heteropolyacids of the present invention is represented by _{Li x H 4-x SiW 12} O 40, Na x H 4-x SiW 12 O 40 or _{K x H 4-x SiW 12} O 40. In the formula, x is 2.5 to 3.5.
When x is less than 2.5, the acidity of the heteropolyacid becomes too strong, and when an alkali metal salt of the heteropolyacid is used as a catalyst for olefin oligomerization, it is difficult to selectively oligomerize only isobutene. In addition, when x exceeds 3.5 and is 4 or less, the acidity of the heteropolyacid becomes too weak, and the oligomerization activity decreases. Preferably x is 2.6 to 3.4, more preferably 2.8 to 3.2.

The catalyst for olefin oligomerization of the present invention comprises the alkali metal salt of the above heteropolyacid.
The olefin oligomerization catalyst is usually used in a state of being supported on a carrier.
Examples of the support include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), silica alumina (SiO ₂ —Al ₂ O ₃ ), titania (TiO ₂ ), zirconia (ZrO ₂ ), and zeolites. Silica (SiO ₂ ) or alumina (Al ₂ O ₃ ) is preferable.

  When the catalyst is supported on the support, for example, the silica powder is impregnated with an aqueous solution of an alkali metal salt of a heteropolyacid, and then dried and calcined.

  The loading is usually 0.1 to 50% by weight, preferably 1 to 20% by weight. If it is less than 0.1% by weight, the acid amount is small, the acid strength is too weak, and the oligomerization activity may be lowered. If it exceeds 50% by weight, the acid amount is large and the acid strength is too strong, and there is a possibility that side reactions such as oligomerization of n-butenes and isomerization / decomposition of the generated oligomers become remarkable.

In the method for producing an olefin oligomer of the present invention, a raw material olefin is oligomerized using the above-mentioned catalyst for olefin oligomerization.
As the raw material olefin, ethylene, propylene, butenes (isobutene, 1-butene, trans-2-butene, cis-2-butene), pentenes, hexenes and the like can be used alone or in combination. . Preferred are butenes and propylene, and butenes are particularly preferred. In addition, a C4 (called BB, Raffinate or the like) fraction by-produced from naphtha decomposition or the like can be used.

  When the catalyst of the present invention oligomerizes a mixture of a branched olefin such as a C4 fraction and a linear olefin, a branched olefin oligomer is selectively obtained.

  The reaction type of oligomerization may be either a continuous flow type or a batch type. One reactor may be used, but two or more reactors may be used in combination in series or in parallel.

The reaction temperature varies depending on the type of raw material olefin and the catalyst used, but is usually 40 ° C to 200 ° C.
The reaction pressure is usually selected in the range of atmospheric pressure to 10 MPa, preferably 1 to 6 MPa, which is a pressure capable of maintaining the liquid phase.
The reaction time (liquid retention time in the case of a continuous flow system) is usually selected in the range of 10 minutes to 10 hours. The catalyst concentration in the case of the batch type is usually 0.1 to 10% by weight with respect to the raw material olefin.

  A solvent may be used for the reaction, or it may be carried out without a solvent. When using a solvent, saturated hydrocarbons such as n-hexane and cyclohexane are used.

  The olefin oligomer obtained by the method of the present invention includes 2, 3 and 4 olefins.

As described above, the catalyst of the present invention can selectively oligomerize branched olefins.
Further, since it is a solid acid catalyst process, there are no industrial problems such as waste catalyst treatment and apparatus corrosion that occur in a homogeneous acid catalyst process. Furthermore, the economic drop due to the progress of side reactions can be reduced.

Hereinafter, the present invention will be described in detail in Examples.
In each example, two gas chromatographs (GC) were used.
The “gas phase part” was mainly used for analysis of C4 isomers, and the “liquid phase part” was mainly used for analysis of C4 oligomers (C8 to C20 +).

<Examples 1-2 and Comparative Examples 1-3>
1. Gas phase detector: FID
Column: CP-Al ₂ O ₃ / KCl PLOT (25 m × 0.25 mm)
2. Liquid phase detector: FID
Column: HP-1 (30 m × 0.32 mm × 0.25 μm)
Oven: 40 ° C. (5 min.) → 10 ° C./min→280° C. (11 min)

<Example 3, Comparative Example 4>
1. Gas phase part GC: Varian CP4900
Detector: TCD 4ch.
<Column><Temperature><Carriergas>
Ch.1: MS-5A 10m 100 ℃ Argon
Ch.2: PoraPLOT-Q 10m 80 ℃ Helium
Ch.3: Al ₂ O ₃ / KCl 10m 80 ℃ Helium
Ch.4: CP-Sill 5CB 8m 120 ℃ Helium

2. Liquid phase part GC: Agilent 6850
Column: HP-1 (30 m, ID 0.25 mm, Film 0.25 μm), linear velocity: He 1.5 cc / min. , 26.5 cm / sec.
Inlet: 280 ° C., Split 20, 1 μL, Solvent: n-Hexane
Oven: 50 ° C. (5 min. Hold) → 10 ° C./min. → 300 ° C (10 min. Hold)
Detector: FID, 300 ° C

Example 1
[catalyst]
Diethyl ether was added to an aqueous solution of H ₄ SiW ₁₂ O ₄₀ (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.). The H ₄ SiW ₁₂ O ₄₀ ether hydrate layer formed in the lowermost layer was taken out, and the operation of evaporating to dryness with a rotary evaporator was repeated several times, followed by recrystallization and purification. This was subjected to suction filtration, and then evacuated at room temperature for 2 hours and at 65 ° C. for 4 hours to obtain H ₄ SiW ₁₂ O ₄₀ · 6H ₂ O. A 0.08 mol / dm ³ H ₄ SiW ₁₂ O ₄₀ aqueous solution was prepared using this H ₄ SiW ₁₂ O ₄₀ · 6H ₂ O.
An aqueous solution having an Na composition of 3 with respect to SiW ₁₂ O ₄₀ ⁴⁻ was obtained by dropping an aqueous solution of H ₄ SiW ₁₂ O _{40 into an} aqueous NaNO ₃ solution (about 0.1 mol / dm ³ ). This aqueous solution was added dropwise to SiO ₂ (AEROSIL 300 manufactured by Nippon Aerosil Co., Ltd., specific surface area 274 m ² / g) weighed so that the amount of heteropoly acid supported was 15% by weight, and the catalyst was repeatedly added and stirred by the incipient wetness method. Prepared. The obtained catalyst was dried and ground overnight at 100 ° C. and then calcined in a muffle furnace at 250 ° C. for 4 hours.

[reaction]
In a stainless autoclave with an internal volume of 30 cc, 0.1 g of catalyst, 4 cc (2.6 g) of solvent (n-hexane), and 8 cc (4.8 g) of mixed C4 (isobutene: 1-butene = 1: 1) as a raw material olefin While charging and stirring, the temperature was raised to 100 ° C. and reacted for 1 hour.
The obtained reaction product liquid was analyzed using a gas chromatograph (FID). The results are shown in Table 1. The conversion rate and yield were calculated from the following formulas.

  The isobutene conversion was 97%, whereas the n-butene conversion was only 8%, and isobutene was oligomerized with high selectivity.

Example 2
In Example 1, a catalyst was prepared in the same manner as in Example 1 except that LiNO ₃ was used instead of NaNO ₃ and a catalyst prepared using an aqueous solution having an Li composition of 3 with respect to SiW ₁₂ O ₄₀ ⁴⁻ was used. Were prepared and evaluated. The results are shown in Table 1. The n-butene conversion rate was only 4% while the isobutene conversion rate was 92%, and isobutene was oligomerized with high selectivity.

Comparative Example 1
In Example 1, a catalyst was prepared and evaluated in the same manner as in Example 1 except that a catalyst prepared using an aqueous solution having an Na composition of 1 with respect to SiW ₁₂ O ₄₀ ⁴⁻ was used. The results are shown in Table 1. The n-butene conversion was high, 23%.

Comparative Example 2
In Example 1, a catalyst was prepared and evaluated in the same manner as in Example 1 except that a catalyst prepared using an aqueous solution having an Na composition of 2 with respect to SiW ₁₂ O ₄₀ ⁴⁻ was used. The results are shown in Table 1. The n-butene conversion was high, 19%.

Comparative Example 3
In Example 2, a catalyst was prepared and evaluated in the same manner as in Example 1 except that a catalyst prepared using an aqueous solution having a Li composition of 2 with respect to SiW ₁₂ O ₄₀ ⁴⁻ was used. The results are shown in Table 1. The n-butene conversion was high, 18%.

Example 3
[reaction]
The catalytic reaction results were investigated using a fixed bed high pressure flow reactor. A 15% by weight Na ₃ HSiW / SiO ₂ catalyst used in Example 1 was molded into a SUS reaction tube (inner diameter 10 mm, length 100 cm), filled with 20 cc, and pretreated by heating to 250 ° C. under N ₂ flow. Then, under 3 MPa pressure, mixed C4 raw material (1-butene 13%, 2-butene 25%, isobutene 12%, butane 48%) was supplied at 80 cc / h (liquid) (LHSV = 4), 60 ° C. It was made to react with.

  The obtained reaction product (gas phase and liquid phase) was analyzed using a gas chromatograph. The results are shown in Table 2. The conversion rate and yield were calculated by the following formula.

  Tens of hours after the start of the reaction, the isobutene conversion was stable at 90%, and the n-butene conversion at that time was only 7%, and isobutene was oligomerized with high selectivity.

Comparative Example 4
In Example 3, a commercially available _SiO 2 _-Al 2 _{O 3} (molded) as a catalyst, except that the reaction temperature was changed to 100 ° C. was prepared in the same manner as in Example 3. The results are shown in Table 2. Tens of hours after the start of the reaction, the isobutene conversion was stable at 90%, and the n-butene conversion at that time was high at 16%.

  The alkali metal salt of the heteropolyacid of the present invention can be used as a catalyst for olefin oligomerization, and when this olefin oligomerization catalyst is used, a branched olefin can be selectively oligomerized. Branched olefin oligomers are useful as raw materials for high-octane gasoline bases, lubricating oils and chemicals.

Claims (11)

Of a heteropolyacid represented by Li _x H _4-x SiW ₁₂ O ₄₀ , Na _x H _4-x SiW ₁₂ O ₄₀ or K _x H _4-x SiW ₁₂ O ₄₀ (x = 2.5 to 3.5) An olefin oligomerization catalyst comprising an alkali metal salt. The alkali metal salt of the heteropolyacid is Li _x H _4-x SiW ₁₂ O ₄₀ Or K _x H _4-x SiW ₁₂ O ₄₀ The catalyst for olefin oligomerization of Claim 1 represented by these. The alkali metal salt of the heteropolyacid is Li _x H _4-x SiW ₁₂ O ₄₀ Or Na _x H _4-x SiW ₁₂ O ₄₀ The catalyst for olefin oligomerization of Claim 1 represented by these. The catalyst for olefin oligomerization according to any one of claims 1 to 3, wherein x is 2.6 to 3.5. The olefin oligomerization catalyst according to any one of claims 1 to 4, which is supported on a carrier. The catalyst for olefin oligomerization according to claim 5 , wherein the carrier is silica (SiO ₂ ) or alumina (Al ₂ O ₃ ), and the supporting ratio of the alkali metal salt of the heteropolyacid is 1 to 20% by weight. The manufacturing method of the olefin oligomer which oligomerizes a raw material olefin using the catalyst in any one of Claims 1-6 . The method for producing an olefin oligomer according to claim 7 , wherein the raw material olefin is propylene or butene. The method for producing an olefin oligomer according to claim 7 , wherein the raw material olefin is a C4 fraction by-produced from naphtha cracking. The method for producing an olefin oligomer according to claim 7 or 9 , wherein the raw olefin is a mixture of a branched olefin and a linear olefin, and the catalyst selectively oligomerizes the branched olefin from the raw olefin. The manufacturing method of the olefin oligomer in any one of Claims 7-10 in which the said olefin oligomer contains the 2, 3 and tetramer of the said raw material olefin.