TW201601834A - Olefin oligomerization catalyst, and method for manufacturing olefin dimer - Google Patents

Abstract

Provided are [1] an olefin oligomerization catalyst characterized in that a portion of an acidic cationic exchange resin has undergone modification treatment with a nitrogen-containing compound, and [2] a method for manufacturing an olefin dimer, including a step for bringing a starting material olefin into contact with the oligomerization catalyst.

Description

Olefin oligomerization catalyst and method for producing olefin dimer

The present invention relates to an oligomerization catalyst for olefins and a process for producing an olefin dimer.

Diisobutylene dimer, diisobutylene (a mixture of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene) can be used as the oxygenated alcohol Raw materials, raw materials of isophthalic acid, raw materials of p-octylphenol, raw materials of rubber adhesion imparting agents, raw materials of surfactants, gasoline fuel additives, rubber chemicals, and the like.

Isobutylene (hereinafter also referred to as "DIB") is generally converted to isobutyl sulphate by reaction of FCC (flow contact decomposition) or a C4 fraction produced by an ethylene plant, and is derived from 1-butene or Separation of 2-butene, butane, etc., followed by thermal decomposition. Alternatively, after the isobutylene in the C4 fraction is made into MTBE (methyl tert-butyl ether) or TBA (third butanol), DIB is obtained by decomposition and dimerization. However, the former method generates a large amount of oligomers of terpolymers or tetramers other than the target DIB, and in addition to the low reaction selectivity of DIB, since sulfuric acid is used in the reaction, an expensive manufacturing apparatus using a corrosion-resistant material is required. . In addition, any method Both have many problems in the reaction steps and complicated processes.

Catalysts for producing DIB by dimerization of isobutylene are known as liquid or gas catalysts such as sulfuric acid, boron trifluoride, phosphoric acid, aluminum chloride, ion exchange resins, amorphous or crystalline aluminosilicates. Salt, clay, composite oxide and other solid acids.

For example, Patent Document 1 discloses that activated clay and acid white clay which are calcined at a temperature of 200 to 600 ° C are used as a catalyst to selectively react isobutene in a C 4 hydrocarbon mixture under specific conditions, followed by removal and purification. A method of recovering 1-butene and/or 2-butene from a C4 hydrocarbon mixture. However, the reaction disclosed in Patent Document 1 mainly produces a trimer of isobutylene and an oligomer of tetramer or more, and the formation of a dimer, that is, DIB, is extremely small. Further, when the activated clay and the acid white clay are fired at a temperature exceeding 200 ° C, the original crystal structure is disintegrated due to the detachment of the interlayer water or the crystal water, and the specific surface area and the acid amount are greatly reduced. Therefore, the catalyst used in Patent Document 1 is not considered to be suitable for selective manufacture of DIB.

Patent Document 2 discloses a selective oligomerization method of making isobutylene containing a mixture of isobutene and 1-butene with a specific mordenite. However, Patent Document 2 describes the conversion of isobutylene by selectively removing isobutylene without isomerization with 1-butene and maintaining the catalytic activity for a long period of time by bringing the mordenite into contact with the hydrocarbon mixture. However, it cannot be said that the dimer, that is, DIB, can be selectively produced in a high yield.

Patent Document 3 discloses the use of a catalyst obtained by exchanging a part of an ion exchange resin with a metal ion, and different from a C4 hydrocarbon mixture containing isobutylene. A method of selective oligomerization of butene. Further, in the examples of Patent Document 3 (Test 5 and Test No. 5-c), the concentration of 1-butene in the raw material was 11.8%, and when the concentration of isobutylene was 50.7%, Amberlyst partially neutralized to 40% by sodium ion was used. The isobutene conversion rate of the type 15 ion exchange resin was 74.4%, and the selectivity of DIB was 72.4% (the C8 selectivity was 77.2%, and the ratio of 2,4,4-trimethylpentene was 93.8%). ), a higher selection rate can be obtained. However, those skilled in the art will readily be able to speculate that this is because the n-butene concentration in the feed is low and the isobutene concentration is high.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2-42029

Patent Document 2: Japanese Patent Publication No. 62-41574

Patent Document 3: Japanese Laid-Open Patent Publication No. 2004-123714

For example, when an oligomer is produced using a C4 fraction containing isobutylene and n-butene as a raw material, in the conventional production method, particularly when the n-butene concentration in the raw material is high, or when the isobutene concentration in the raw material is low, It is difficult to selectively oligomerize isobutylene without the n-butene oligomerization. Moreover, when the olefin dimer is produced by dimerization of the raw material olefin, it is difficult to control the problem of stopping the reaction in the stage of dimerization.

The present invention is accomplished under the circumstances, and the object thereof is to provide an A catalyst for oligomerization of a raw material such as butene or the like, and a catalyst for oligomerization of an olefin of an olefin dimer and a method for producing an olefin dimer using the catalyst can be obtained in a high yield.

As a result of repeated active research to achieve the above object, the present inventors have found that an olefin dimer can be obtained in a high yield by using a catalyst which partially treats an acidic cation exchange resin with a nitrogen-containing compound in the production of an olefin dimer. Polymer. Further, it has been found that, particularly when a raw material olefin containing isobutylene is used, isobutylene can be selectively dimerized, and DIB which can be used as various industrial raw materials can be obtained with a high reaction selectivity.

The present invention has been completed based on this finding.

That is, the present invention provides the following.

[1] An oligomerization catalyst for olefins, characterized in that a part of an acidic cation exchange resin is modified by a nitrogen-containing compound.

[2] The oligomerization catalyst according to [1], wherein the nitrogen-containing compound is a basic nitrogen-containing compound.

[3] The oligomerization catalyst according to [1] or [2], wherein the acidic cation exchange resin is a sulfonic acid type strongly acidic cation exchange resin.

[4] The oligomerization catalyst according to any one of [1] to [3] wherein the modification ratio of the nitrogen-containing compound is from 1 to 50%.

[5] The method for producing an oligomerization catalyst according to any one of the above [1] to [4], wherein the method comprises the following steps (1) or (2); Suspending the aforementioned acidic cation exchange resin in a dispersion medium a step of dropping the nitrogen-containing compound over 0.2 hours or more while stirring; (2) adding the nitrogen-containing compound while stirring the acidic cation exchange resin, and forming 0.1 to 10 mole with respect to the nitrogen-containing compound After the amount of the acidic compound, stir the step for 0.1 to 10 hours.

[6] A method for producing an olefin dimer, which comprises the step of bringing the oligomerization catalyst according to any one of the above [1] to [4] into contact with a raw material olefin.

[7] The method for producing an olefin dimer according to the above [6], wherein the raw material olefin contains isobutylene.

[8] The method for producing an olefin dimer according to the above [6] or [7] wherein the raw material olefin is a mixture containing isobutylene alone or another olefin containing isobutylene and carbon number 4.

[9] The method for producing an olefin dimer according to any one of [6] to [8] wherein the temperature in the step is 20 to 150 °C. and

[10] The method for producing an olefin dimer according to any one of the above [6], wherein the step is carried out in a liquid phase, and the pressure in the step is 2 MPa or more.

According to the present invention, it is possible to provide an oligomerization catalyst which can inhibit the formation of a terpolymer of a olefin and a tetramer in the production of an olefin dimer, obtain an olefin of an olefin dimer in a high yield, and use the touch A method for producing a olefin dimer of a medium. Moreover, especially when using a raw material olefin containing isobutylene, The isobutylene can be selectively dimerized, and a DIB which can be used as a raw material for various industrial uses can be obtained with a high reaction selectivity.

[Olefin oligomerization catalyst]

The olefin oligomerization catalyst of the present invention (hereinafter also referred to as "the catalyst of the present invention" or simply "catalyst") is characterized in that a part of the acidic cation exchange resin is modified by a nitrogen-containing compound. When the catalyst of the present invention is brought into contact with the raw material olefin, generation of an olefin terpolymer or a tetramer can be suppressed, and an olefin dimer can be obtained in a high yield. Further, when a raw material olefin containing isobutylene is used, isobutylene can be selectively dimerized to produce DIB at a high reaction selectivity.

(acid cation exchange resin)

The acidic cation exchange resin used in the catalyst of the present invention is exemplified by a strongly acidic cation exchange resin and a weakly acidic cation exchange resin.

The strongly acidic cation exchange resin is exemplified by a sulfonic acid type strongly acidic cation exchange resin having a sulfonic acid group (RSO ₃ ^- H ⁺ ) as an acidic group. The weakly acidic cation exchange resin is exemplified by having a carboxylic acid group (R-COO ^- H ⁺ ), a phosphonic acid group (RP(O)(O ^- H ⁺ ) ₂ ), a phosphinic acid group (R). -PH(O)(O ^- H ⁺ )), arsenious acid group (R-OAsO ^- H ⁺ ), and phenate group (RC ₆ H ₄ O ^- H ⁺ ) are used as an acidic group.

In the present invention, an acidic cation exchange tree is based on a nitrogen-containing compound From the viewpoint of modifying a part of the fat to exhibit the function as an oligomerization catalyst for an olefin, a strongly acidic cation exchange resin is preferably used, and a sulfonic acid type strongly acidic cation exchange resin is preferably used.

The acidic cation exchange resin may be used singly or in combination of two or more.

Commercially available products of the acidic cation exchange resin are sulfonic acid type strongly acidic cation exchange resins "Amberlyst 15", "Amberlyst 16", and "Amberlite HX2071H" (all manufactured by Dow Chemical Co., Ltd.).

(nitrogen-containing compounds)

The catalyst of the present invention is obtained by modifying a part of the above acidic cation exchange resin by a nitrogen-containing compound. The nitrogen-containing compound means a compound having one or more nitrogen atoms in the molecule. Further, the phrase "modifying a part of the acidic cation exchange resin by a nitrogen-containing compound" means that the nitrogen-containing compound acts on the acidic cation exchange resin, and the acidic cation exchange resin has a partial acidic group neutralized or modified. .

From the viewpoint of the above modification treatment, the nitrogen-containing compound used in the catalyst of the present invention is preferably a basic nitrogen-containing compound. The basic nitrogen-containing compound is exemplified by, for example, ammonia; an aliphatic amine such as an alkylamine, a dialkylamine or a trialkylamine; an aromatic amine such as aniline or toluidine; or a heterocyclic ring such as pyridine, pyrimidine, pyrrazine or piperazine; Nitrogen-containing compounds; The above aliphatic amine is preferably an aliphatic amine having an alkyl group having 1 to 6 carbon atoms, and is exemplified by, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, n-hexylamine, dimethylamine, diethylamine. Diisopropylamine, three Methylamine, triethylamine, and the like.

In these, it is preferably immobilized in a catalyst by reacting with an acidic group such as a sulfonic acid group in an acidic cation exchange resin, and it is difficult to cause detachment or deterioration, and is preferably selected from ammonia and having an alkyl group having 1 to 6 carbon atoms. At least one of an aliphatic amine, an aromatic amine, and a heterocyclic nitrogen-containing compound is more preferably at least one selected from the group consisting of ammonia, triethylamine, aniline, and pyridine, and more preferably selected from the group consisting of triethylamine and pyridine. At least one of them is more preferably triethylamine.

The nitrogen-containing compound may be used alone or in combination of two or more.

The modification rate of the catalyst of the present invention by the above nitrogen-containing compound is preferably from 1 to 50%, more preferably from 5 to 35%, still more preferably from 5 to 25%. When the modification ratio is 1% or more, the catalyst becomes an appropriate acid strength for the production of the olefin dimer, and formation of a polymer other than the olefin dimer can be suppressed. When the modification ratio is 50% or less, the activity of the obtained catalyst is not excessively lowered.

In addition, in this specification, "the modification rate of a catalyst by a nitrogen-containing compound" means the reaction ratio of the nitrogen-containing compound with respect to the total amount of acidic groups in the acidic cation exchange resin used for the oligomerization catalyst. The rate of modification can be determined, for example, by titration.

[Method of Manufacturing Catalyst]

The method for producing a catalyst of the present invention is not particularly limited as long as it can modify a part of the acidic cation exchange resin by a nitrogen-containing compound, but preferably has the following steps (1) or (2), more preferably The steps of (1). Thereby, the acidity used in the treatment can be uniformly modified by the nitrogen-containing compound Between the cation exchange resins, or the surface of the ion exchange resin and up to the inside.

(1) a step of allowing the nitrogen-containing compound to be dropped over 0.2 hours or more while stirring the cation exchange resin in a dispersion medium, and (2) adding the nitrogen-containing compound while stirring the acidic cation exchange resin. The acidic compound is added in an amount of 0.1 to 10 mol% with respect to the nitrogen-containing compound, and then stirred for 0.1 to 10 hours.

(step 1))

The dispersion medium used in the step (1) is not particularly limited as long as it can suspend the acidic cation exchange resin, and is preferably water or a water-soluble organic solvent. Water is preferably used from the viewpoint of treatment with an acidic cation exchange resin. The water-soluble organic solvent is exemplified by an alcohol having 1 to 6 carbon atoms, a hydrocarbon or the like, and is preferably at least one selected from the group consisting of methanol, ethanol, isopropanol, hexane, and toluene.

These dispersion media may be used alone or in combination of two or more.

The amount of the dispersion medium for suspending the acidic cation exchange resin is not particularly limited, but is preferably from 3 to 15 times, more preferably from 4 to 8 times, based on the volume ratio of the acidic cation exchange resin. If it is three times or more, a suspension in which the acidic cation exchange resin is uniformly suspended can be prepared, and if it is 15 times or less, the modification treatment efficiency by the nitrogen-containing compound can be improved.

Step (1) From the viewpoint of uniformly modifying the acidic cation exchange resin, it is preferred to drip the nitrogen-containing compound dropwise over 0.2 hours or more while suspending the acidic cation exchange resin in the above dispersion medium. The dropping time of the nitrogen-containing compound is more preferably 0.5 hours or more. And, based on the point of view of productivity, The dropping time is preferably 3 hours or less, more preferably 2 hours or less.

The nitrogen-containing compound may also be dissolved in water or a water-soluble organic solvent and then dripped as needed. The water-soluble organic solvent is preferably an organic solvent exemplified as a dispersion medium for suspending an acidic cation exchange resin.

The reaction temperature in the case of carrying out the step (1) is not particularly limited, but is preferably in the range of 20 to 60 ° C from the viewpoint of productivity and economy. Further, the reaction time in the step (1) is preferably in the range of 0.5 to 2 hours after the completion of the dropwise addition of the nitrogen-containing compound.

(Step (2))

In the step (2), the acidic cation exchange resin is stirred, and the nitrogen-containing compound and the acidic compound in an amount of 0.1 to 10 mol% based on the nitrogen-containing compound are added, followed by stirring for 0.1 to 10 hours. Even if the acidic cation exchange resin is not uniformly modified by the nitrogen-containing compound, the acidic group of the acidic cation exchange resin can be uniformly modified by ion exchange with the acidic compound of the free acid.

The acidic compound used in the step (2) is preferably selected from the group having the same acidic group as the acidic group in the acidic cation exchange resin modified with the nitrogen-containing compound. For example, if the acidic cation exchange resin is a sulfonic acid type strongly acidic cation exchange resin, the acidic compound used in the step (2) is preferably a compound having a sulfonic acid group, and examples thereof include p-toluenesulfonic acid and the like.

These acidic compounds may be used alone or in combination of two or more.

The amount of acidic compound added is better than that of nitrogen-containing compound It is 0.1 to 10 mol%, more preferably 0.2 to 8 mol%, more preferably 0.5 to 5 mol%, and even more preferably 1 to 3 mol%. When the amount of the acidic compound added is 0.1 mol% or more based on the nitrogen-containing compound, the acidic cation exchange resin can be uniformly modified. Further, if it is 10 mol% or less, it is preferable from the viewpoint of economy of the acidic compound to be used, and the problem of the increase in the number of washings of the catalyst after the modification treatment and the disposal of the cleaning liquid can be reduced.

In the step (2), the order of addition of the nitrogen-containing compound and the acidic compound is not particularly limited, and either one may be preferred or may be added at the same time.

Although the method of adding the nitrogen-containing compound is not particularly limited, it is preferably added dropwise by the viewpoint of uniform modification of the acidic cation exchange resin. The preferred dropping time is the same as the aforementioned step (1).

The stirring time after the addition of the nitrogen-containing compound and the acidic compound is preferably from 0.1 to 10 hours, more preferably from 0.2 to 8 hours, still more preferably from 0.5 to 5 hours. When the stirring time is 0.1 hour or longer, the acidic cation exchange resin can be uniformly modified. Further, if it is 10 hours or less, it is preferable from the viewpoint of productivity.

The reaction temperature at the time of carrying out the step (2) is not particularly limited, but is preferably in the range of 20 to 60 ° C from the viewpoint of productivity and economy.

After the above step (1) or (2), the catalyst of the present invention can be obtained by filtration, washing, and, if necessary, drying treatment. The drying treatment conditions are not particularly limited as long as they do not cause deterioration of the catalyst, and the like, for example, a method of drying at a temperature of 50 to 120 ° C for 1 to 5 hours under reduced pressure.

[Method for producing olefin dimer]

The present invention further provides a process for producing an olefin dimer having a step of contacting a raw material olefin with the above-described catalyst of the present invention. In the production method of the present invention, by carrying out the above steps, the oligomerization reaction of the raw material olefin is efficiently performed, and the formation of a polymer other than the dimer is suppressed, whereby the olefin dimer can be obtained in a high yield. Further, when a raw material olefin containing isobutylene is used, isobutylene can be selectively dimerized to efficiently obtain DIB at a high reaction selectivity.

(raw material olefin)

The carbon number of the raw material olefin used in the production method of the present invention is preferably in the range of 3 to 5. The raw material olefin may be used alone or in a mixture of two or more kinds of olefins.

In particular, according to the production method of the present invention, when the raw material olefin is a mixture containing isobutylene alone or a mixture of isobutylene and other olefins having a carbon number of 4, it is possible to selectively dimerize isobutylene and to produce DIB at a high reaction selectivity. The effect is better.

A mixture containing isobutylene and other olefins having a carbon number of 4 can be exemplified by a mixed C4 fraction. The mixed C4 fraction is exemplified by, for example, an olefin fraction produced in an FCC process, an olefin fraction obtained by extraction or selective hydrogenation of a fraction produced in petroleum brain cracking, or the like. The ratio mixes the winners. Further, it can be prepared by adding or subtracting the content of the specific fraction by a conventional method such as distillation. For example, distillation (or reactive distillation) may be carried out using a raffinate or FCC-C4 fraction obtained by extracting butadiene from a C4 fraction produced by petroleum brain cracking to remove n-butenes and n-butylene. Alkenes and high concentrations of isobutylene Isobutylene-isobutane fraction.

The mixed C4 fraction generally contains components such as 1-butene, trans-2-butene, cis-2-butene, isobutylene, n-butane, isobutane, and butadiene.

Further, the mixed C4 fraction may be obtained by applying the prior treatment as shown in the following (1) to (3), removing impurities, and purifying the mixture.

(1) The diene such as butadiene in the mixed C4 fraction which is a cause of a decrease in the catalytic activity or a decrease in the purity of the diisobutylene can be removed by an extraction solvent such as N,N-dimethylformamide or acetonitrile. Alternatively, it is desirable to reduce the diene by selective hydrogenation of a hydrogenation catalyst such as Pd or Ni. Generally, it is based on 1000 mass ppm or less.

(2) The sulfur component and the basic nitrogen component which are causes of the decrease in the catalytic activity can be removed by washing with water or activated adsorbent such as activated alumina or activated carbon or molecular sieve.

(3) The C3 fraction which is a cause of the decrease in the purity of diisobutylene can be removed from the top of the column by distillation.

The method for producing the olefin dimer of the present invention is not particularly limited as long as it has a step of bringing the raw material olefin into contact with the catalyst of the present invention. This step can be carried out, for example, by supplying a raw material olefin to a reaction tube filled with the catalyst of the present invention, a method of contacting the catalyst, and the like. More specifically, it is preferably carried out under the conditions described below.

The temperature of this step is preferably from 20 to 150 °C. It is preferably 30 to 120 ° C, and more preferably 40 to 100 ° C. When the temperature is 25 ° C or more, the conversion ratio of the raw material olefin is increased, and productivity is improved. On the other hand, when it is 150 ° C or less, formation of by-products other than the olefin dimer can be suppressed. The removal of the heat of reaction or the control of the reaction is relatively easy.

Although this step can be carried out in a gas phase or a liquid phase, it is preferably carried out in a liquid phase from the viewpoint of efficiently contacting the catalyst with the raw material olefin to improve productivity. The pressure at this time may be a pressure which can maintain the liquid phase, and is usually atmospheric pressure or higher. The pressure at the time of performing the step in the liquid phase is preferably 1 MPa or more, more preferably 2 MPa or more, from the viewpoint of maintaining the liquid phase in a stable phase, and is preferably 10 MPa or less, more preferably 7 MPa or less, and more preferably from the viewpoint of economy. It is 5 MPa or less.

A solvent may be used in this step or may be solvent-free. When a solvent is used, from the viewpoint of solubility and separation property of the raw material olefin, a saturated hydrocarbon solvent is preferably used, and a saturated hydrocarbon solvent having 4 to 6 carbon atoms such as n-butane, n-pentane, n-hexane or cyclohexane is preferably used.

An adiabatic reactor or a multitubular reactor or the like can be used for this step. Further, in order to control the reaction temperature (heat removal), the reaction product liquid may be recycled to the reactor (mixed with the raw material) or diluted with a diluent. When the reaction product liquid is circulated to the reactor, the circulating liquid is preferably at least 4 mass ratios, more preferably at least 3 mass ratios, with respect to the raw material. When the circulation amount is 4 mass ratio or less, the reaction rate does not decrease due to a decrease in the concentration of the raw material, and a large amount of catalyst is not required.

Further, the reactor and the reaction form used in the step are not particularly limited, and a batch type, a semi-batch type, a continuous flow type reaction using a tank type reactor, or a flow reaction in a fixed bed, a fluidized bed, or a moving bed may be employed. Continuous flow reaction, etc.

In this step, the olefin feed to the catalyst feed rate space velocity of liquid at the reference volume (LHSV of) gauge, preferably 0.1 ~ 30hr ^-1, more preferably 0.2 ~ 20hr ^-1, and more preferably 0.5 ~ 15hr ^{- 1} . When the LHSV is 0.1 hr ^-1 or more, the conversion ratio of the raw material olefin is improved. And if the LHSV is 30hr ^-1 or less, using a mixed C4 olefin fraction as a starting material can be suppressed due to an increase of the conversion rate of n-butene, it is possible to select a high reaction rate obtained in high purity and DIB.

When this step is carried out in batch mode, the catalyst concentration is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, even more preferably from 0.5 to 2% by mass, based on the raw material olefin. When the catalyst concentration is 0.01% by mass or more based on the raw material olefin, the reaction rate is not excessively lowered, and the productivity is good. When the catalyst concentration is 10% by mass or less based on the raw material olefin, it is economically preferable, and when the mixed C4 fraction is used as the raw material olefin, the increase in the n-butene conversion can be suppressed.

The reaction time in this step (liquid residence time in the continuous flow type) is usually from 2 minutes to 15 hours, preferably from 2 minutes to 10 hours. It is better for 3 minutes to 5 hours, and more preferably 4 minutes to 1 hour. When the reaction time is 2 minutes or longer, the conversion ratio of the raw material olefin is increased. When the reaction time is 15 hours or less, the conversion of the n-butene can be suppressed when the mixed C4 fraction is used as the raw material olefin.

After the above steps, the unreacted raw material olefin and the oligomer component containing the produced olefin dimer can be separated and purified by a distillation method or the like to obtain a high-purity olefin dimer.

The production method of the present invention can be carried out when the raw material olefin is a mixture containing isobutylene alone or other olefin containing isobutylene and carbon number 4 The isobutylene selective dimerization is particularly suitable as a manufacturing method for DIB. The obtained DIB (2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene) can be used as a raw material of, for example, an oxygen-containing alcohol, a raw material of isodecanoic acid, A raw material of p-octylphenol, a raw material of a rubber adhesion imparting agent, a raw material of a surfactant, a gasoline fuel additive, a rubber drug, and the like.

Example

Next, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples.

Further, the analysis method of the reaction product in the present embodiment is as follows.

<Analysis method of reaction product>

The analysis of the reaction product was carried out using two gas chromatographs (GC). The "gas phase portion" is mainly used for the analysis of an isomer of a carbon number 4 olefin, and the "liquid phase portion" is mainly used for the analysis of an oligomer having a carbon number of 8 or more.

[gas phase]

GC device: "CP4900" made by Varian

Detector: TCD (4 channels)

. Channel 1

Pipe column: "MS-5A" (length 10m) made by Varian, temperature: 100 °C, carrier gas: Ar

. Channel 2

Column: PoraPLOT-Q (length 10m), temperature: 80 ° C, carrier gas: He

. Channel 3

Column: Al ₂ O ₃ /KCl (length 10 m), temperature: 80 ° C, carrier gas: He

. Channel 4

Column: CP-Sil 5CB (length 8m), temperature: 120 °C, carrier gas: He

[liquid phase]

GC device: "6850GC" manufactured by Agilent Technologies

Column: HP-1 (length 30m, inner diameter 0.25mm, film thickness 0.25μm)

Carrier gas: He (flow rate 1.5mL / min)

Injection temperature: 280 ° C

Split: 1/20

Oven: 50 ° C (for 5 minutes) → temperature 10 ° C / min → 300 ° C (for 10 minutes)

Detector: FID

Detector temperature: 300 ° C

Further, the isobutylene conversion ratio, the dimer selectivity, the diisobutylene (DIB) selectivity in the dimer, and the trimer selectivity were calculated based on the following formula.

Isobutylene conversion (%) = {1 - (amount of isobutylene in the reaction product [g / hr] / isobutene supply amount [g / hr])} × 100

Dimer selectivity (%) = (amount of dimer in the reaction product [g/hr] / total amount of oligomer in the reaction product [g/hr]) × 100

DIB selectivity (%) in the dimer = (amount of DIB in the reaction product [g/hr] / amount of all dimer (C8 component) in the reaction product [g/hr]) × 100

Trimer selectivity (%) = (trimer in the reaction product [g/hr] / total amount of oligomer in the reaction product [g/hr]) × 100

Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1-2 (modulation of olefin oligomerization catalyst) (Example 1-1)

60 mL of a sulfonic acid type cation exchange resin ("Amberlyst 15" manufactured by R&H Co., Ltd.) and 240 mL of ion-exchanged water were fed into a 500 mL three-necked flask, and the mixture was stirred at room temperature and slowly diluted with ion-exchanged water over 1 hour. A solution of 0.547 g of triethylamine (the amount of the sulfonic acid group in the sulfonic acid type cation exchange resin, the modification rate is 5%) to 20 times. After completion of the dropwise addition, the mixture was further stirred for 1 hour, and filtered to prepare a 5% triethylamine-modified ion exchange resin of an oligomerization catalyst.

(Example 1-2)

In Example 1-1, except that the amount of use of triethylamine was changed to 1.09 g (the amount of modification was 10% with respect to the sulfonic acid group in the sulfonic acid type cation exchange resin), the same as in Example 1 In the same manner, a 10% triethylamine modified ion exchange resin of an oligomerization catalyst was prepared.

(Example 1-3)

In Example 1-1, except that the amount of triethylamine used was changed to 20% triethylamine modified ion of the oligomerization catalyst was prepared in the same manner as in Example 1-1 except that 2.19 g (the sulfonic acid group in the sulfonic acid type cation exchange resin was changed to 20%) Exchange resin.

(Examples 1-4)

In the same manner as in Example 1-1, except that the triethylamine was changed to 0.427 g of pyridine (the amount of the sulfonic acid group in the sulfonic acid type cation exchange resin was changed to 5%). A 5% pyridine-modified ion exchange resin of an oligomerization catalyst was prepared.

(Example 1-5)

In the same manner as in Example 1-1 except that the triethylamine was changed to 0.854 g of pyridine (the amount of the sulfonic acid group in the sulfonic acid type cation exchange resin was changed to 10%). A 10% pyridine-modified ion exchange resin of an oligomerization catalyst was prepared.

(Examples 1-6)

In the same manner as in Example 1-1 except that triethylamine was changed to 1.71 g of pyridine (the amount of the sulfonic acid group in the sulfonic acid type cation exchange resin was changed to 20%). A 20% pyridine-modified ion exchange resin of an oligomerization catalyst was prepared.

(Examples 1-7)

In Example 1-1, except that aniline was diluted with methanol to 0.996 g (phase For the sulfonic acid type ion exchange resin, the sulfonic acid group has a modification rate of 10% by weight to 20 times, the solution is substituted with a solution of triethylamine diluted to 20 times with ion-exchanged water, and the ion for the ion exchange resin is used. A 10% aniline-modified ion exchange resin of an oligomerization catalyst was prepared in the same manner as in Example 1-1 except that 240 mL of the exchanged water was changed to methanol (all solvents were changed from ion-exchanged water to methanol).

(Examples 1-8)

In Example 1-1, except that 1.97 g of 28% aqueous ammonia (the sulfonic acid group in the sulfonic acid type cation exchange resin was used, the modification rate was 30%) was substituted for the dilution of triethylamine to 20 times with ion-exchanged water. A 30% ammonia-modified ion exchange resin of an oligomerization catalyst was prepared in the same manner as in Example 1-1 except for the resulting solution.

(Comparative Example 1-1)

In Example 1-1, except that the triethylamine was changed to 0.432 g of sodium hydroxide (the amount of modification was 10% with respect to the sulfonic acid group in the sulfonic acid type cation exchange resin), the same as in Example 1 The same as 1 , a 10% sodium metal exchange ion exchange resin was prepared.

(Comparative Example 1-2)

In Example 1-1, except that triethylamine was changed to calcium chloride. The same procedure as in Example 1-1 except that 2.38 g of the hydrate (the amount of the sulfonic acid group in the sulfonic acid type cation exchange resin was changed to 30%) was used. 30% calcium metal exchange ion exchange resin.

Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-4 (olefin dimerization reaction) (Example 2-1)

The treatment was carried out before the mixed C4 fraction obtained by petroleum brain lysis. The diene component such as butadiene in the C4 fraction is extracted and extracted with dimethylformaldehyde, and then selectively hydrogenated with a commercially available Pd catalyst to have a diene concentration of 10 ppm by mass or less. Next, the S component and the N component are removed by washing with water to 5 ppm by mass or less. The C3 component is removed from the top of the column by continuous distillation to serve as a raw material olefin.

Next, the catalyst obtained in Example 1-1 was vacuum dried at 80 ° C, and 40 mL was placed in a reaction tube (inner diameter: 14 mm, length: 95 cm) made of SUS.

A fixed bed high-pressure flow reactor was used as a reaction apparatus, and the mixed C4 raw material after the pretreatment was completed (composition: 47.0% of isobutylene, 20.5% of n-butene, 17.8% of 2-butene, 14.5% of butane, and 0.2% of other). The oligomerization reaction was carried out under the conditions of a temperature of 35 ° C, a pressure of 2 MPa, and an LHSV (liquid space velocity) of 0.8 hr ^-1 in a reaction tube made of SUS filled with the above-mentioned catalyst. After 48 hours from the start of the reaction, the reaction products (gas phase and liquid phase) at the outlet of the reactor were analyzed by a gas chromatograph. The results are shown in Table 1.

(Examples 2-2 to 2-8, Comparative Examples 2-1 to 2-3)

The reaction was carried out in the same manner as in Example 2-1, except that the oligomerization catalyst and the reaction temperature were changed as described in Table 1. The analysis results of the reaction products of the reactor outlet after 48 hours from the start of the reaction are shown in Table 1.

(Comparative Example 2-4)

The reaction was carried out in the same manner as in Example 2-1 except that the untreated Amberlyst 15 was used as the oligomerization catalyst, and the reaction temperature was changed to 35 °C. The analysis results of the reaction products of the reactor outlet after 48 hours from the start of the reaction are shown in Table 1.

As is clear from Table 1, when the reaction is carried out using the oligomerization catalyst of the present invention (Examples 1-1 to 1-8), the conversion of isobutylene can be improved, and the formation of the trimer can be suppressed, and the yield can be obtained in a high yield. Olefin dimer. Again, the original The diisobutylene in the olefin is also selectively dimerized, and DIB can be produced at a high reaction selectivity (Examples 2-1 to 2-8).

On the other hand, Comparative Examples 2-1 to 2-3 using a catalyst for treating an acidic cation exchange resin with a basic compound other than a nitrogen-containing compound, and a comparative example using an acidic cation exchange resin which was not subjected to modification treatment as a catalyst were used. 2-4, the dimer selectivity and the DIB selectivity are both low, and the selectivity of the trimer increases.

[Industrial availability]

According to the present invention, an oligomerization catalyst which can obtain an olefin of an olefin dimer in a high yield, and a method for producing an olefin dimer using the catalyst can be provided. Further, especially when a raw material olefin containing isobutylene is used, isobutylene can be selectively dimerized, and DIB which is useful as various industrial raw materials can be obtained with a high reaction selectivity.

Claims (10)

An oligomerization catalyst for olefins characterized in that a part of an acidic cation exchange resin is modified by a nitrogen-containing compound. An oligomerization catalyst for an olefin according to claim 1, wherein the aforementioned nitrogen-containing compound is a basic nitrogen-containing compound. An oligomerization catalyst for an olefin according to claim 1 or 2, wherein the aforementioned acidic cation exchange resin is a sulfonic acid type strongly acidic cation exchange resin. The oligomerization catalyst for an olefin according to any one of claims 1 to 3, wherein a modification ratio of the nitrogen-containing compound is from 1 to 50%. A method for producing an oligomerization catalyst for an olefin according to any one of claims 1 to 4, which is characterized by having the following steps (1) or (2); (1) the aforementioned acidic cation exchange resin a step of dropwise adding the nitrogen-containing compound to the dispersion medium for 0.2 hours or more, and (2) adding the nitrogen-containing compound while stirring the acidic cation exchange resin, and for the nitrogen-containing compound After 0.1 to 10 mol% of the acidic compound, the step of stirring for 0.1 to 10 hours is carried out. A process for producing an olefin dimer, which comprises the step of contacting an oligomerization catalyst according to any one of claims 1 to 4 with a raw material olefin. The process for producing an olefin dimer according to claim 6, wherein the raw material olefin contains isobutylene. A method of producing an olefin dimer according to claim 6 or 7, wherein the The raw material olefin is a mixture containing isobutylene alone or other olefin containing isobutylene and carbon number 4. The method for producing an olefin dimer according to any one of claims 6 to 8, wherein the temperature in the preceding step is from 20 to 150 °C. The method for producing an olefin dimer according to any one of claims 6 to 9, wherein the step is carried out in a liquid phase, and the pressure in the above step is 2 MPa or more.