JP2001131096A - Method for dehalogenating a hydrocarbon containing a carbon-carbon double bond and a method for regenerating alumina used therefor - Google Patents

Abstract

(57) [Summary] [Problem] A trace amount of a halogen compound and a non-conjugated carbon
Provided is a method for suppressing isomerization of a double bond generated as a side reaction when halogen is removed by bringing an organic compound having a carbon double bond into contact with alumina. SOLUTION: A trace amount of halogen, which is characterized in that a sufficient amount of an organic basic substance is present in a reaction system to suppress isomerization of a carbon-carbon double bond of an organic compound, particularly a hydrocarbon, is removed. And a method for regenerating alumina used for the method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing trace amounts of fluorine remaining as impurities in an olefinic compound in the form of an organic substance, an inorganic substance or a mixture thereof using an alumina-containing inorganic treating agent. It is intended to provide a novel method for substantially suppressing the non-conjugated carbon-carbon double bond of the olefinic compound from being isomerized.

[0002]

2. Description of the Related Art In U.S. Pat. No. 4,605,808, a molecule having a vinylidene terminal structure can be produced by polymerizing isobutene using a boron trifluoride complex catalyst using an alcohol as a complexing agent. It has been proposed to obtain butene polymers with a proportion. A butene polymer containing a high proportion of this terminal vinylidene structure is industrially useful because a maleation reaction with maleic anhydride or the like proceeds at a high rate. The maleated butene polymer is eventually used as an additive in fuel oils or lubricating oils, so that it burns at the time of use or disposal and is released into the atmosphere as a combustion gas.

However, C obtained from naphtha decomposition
_When butadiene raffinate obtained by extracting butadiene from the _four fractions is used as a raw material for isobutene and polymerized with a boron trifluoride complex catalyst using alcohol as a complexing agent, for example, several tens of fluorines are contained in the resulting butene polymer. It is recognized that 〜 to several hundred ppm of the organic fluorine compound remains as an impurity. Residual fluorine such as a fluorine compound is released into the atmosphere during combustion and may cause air pollution in some cases. Therefore, it is desired to reduce the residual fluorine. In addition, although the description has been given using a boron trifluoride complex catalyst using alcohol as a complexing agent as an example, chlorine may remain even when isobutene or butadiene raffinate is polymerized by aluminum chloride or its complex catalyst, and the same problem occurs. There is.

[0004] For general purification method of contacting a C ₄ olefin and polymers such as alumina, several conventionally proposed because of its excellent adsorption ability of the alumina it has been made. However, for example, a butene polymer containing a high proportion of a terminal vinylidene structure and containing tens to hundreds of ppm of organic fluorine as fluorine as impurities obtained according to the description of the above-mentioned U.S. Patent is brought into contact with alumina. With the progress of the treatment, the isomerization reaction of the terminal vinylidene structure shown in the following formula [1], which is a side reaction, becomes remarkable, and in the case of long-term operation, the content of the terminal vinylidene structure is reduced by the alumina treatment. There was found. CH ₃ (CH ₃ ) ₂ C [CH ₂ (CH ₃ ) ₂ C] _n CH ₂ C (CH ₃ ) = CH ₂ → CH ₃ (CH ₃ ) ₂ C [CH ₂ (CH ₃ ) ₂ C] _n CH = C (CH ₃ ) ₂ ········ [1] When a separately prepared butene polymer not containing a fluorine compound is treated with alumina in the same manner, the isomerization reaction of the above formula [1] is not so significant. Since it is not remarkable, this phenomenon that the content of the terminal vinylidene structure decreases cannot be explained assuming that alumina itself has an isomerization reaction accelerating effect.

[0005] In the above example has been described for the removal of fluorine compounds content of terminal vinylidene structure is included in the high-butene polymer, the remaining unreacted C ₄ fraction polymerized by fluorine-containing catalysts of butadiene raffinate Have similar problems. That is, the remaining unreacted C
₄ fraction, to generally accept the useful 1-butene as a comonomer for the density adjustment of burning or high density polyethylene as a fuel as well fuel after separated off, similarly unreacted C ₄ fraction The concentration of residual fluorine mixed therein becomes a problem. Also in this case, although defluorination with an alumina-containing inorganic substance is effective and economical, 1-butene may be isomerized by the alumina treatment in the same manner as in the above formula [1]. In particular, when the unreacted C ₄ fraction is used as a source of 1-butene, 2 to 1-butene
-It is an important issue to suppress isomerization to butene.

The present inventors have conducted intensive studies on the above-mentioned isomerization phenomenon. As a result, a new acid site is formed on alumina by fluorine atoms fixed on alumina separately from the acid site originally contained in alumina. As a result, it was found that the isomerization ability of alumina itself deteriorated, and as a result, the above-mentioned isomerization reaction was accelerated. That is, it is presumed that the fluorine atom fixed to alumina forms a new strong Lewis acid point on alumina, and the newly formed strong Lewis acid point becomes non-conjugated carbon-carbon during the contact treatment for defluorination. It is thought that the double bond isomerization reaction is promoted. Such isomerization ability increases according to the total amount of fluorine removed by the defluorination treatment, that is, the fluorine fixed to the alumina by the contact treatment with the alumina.

Here, for example, Japanese Patent Publication No. Hei 6-28725 proposes purifying an olefin with an alumina compound impregnated with an alkali metal or an alkaline earth metal. That is, it is described that the isomerization of olefin can be suppressed by impregnating with an alkali metal or an alkaline earth metal. However, the method of adding an alkali metal or an alkaline earth metal proposed in the above publication is not only unfavorable because it is recognized that the ability to remove halogen represented by fluorine is rather lowered, and furthermore, There are significant drawbacks.

That is, in the case of using alumina whose isomerization ability is suppressed to a low level by previously impregnating a certain amount of an alkali metal or the like as proposed in Japanese Patent Publication No. Hei 6-28725, even if defluorination treatment is performed, Even if possible, a new strong Lewis acid point is formed by the treatment, and an alkali metal or the like for neutralizing the strong acid point cannot cope with the increase of the acid point, and thus becomes insufficient. As a result, isomerization of the carbon-carbon double bond starts to occur gradually according to the total amount of fluorine removed by a certain amount or more. However, the use of alumina impregnated with a large excess of an alkali metal or an alkaline earth metal in advance is not preferable because adverse effects due to an excessive alkali are caused and the ability to remove halogen represented by fluorine is rather lowered. As described above, in the case of alumina previously impregnated with an alkali metal or the like proposed in Japanese Patent Publication No. 6-28725, the removal of fluorine is insufficient, and even if removal is possible, the life is reduced. Has the fatal problem of being much shorter. The suppression of the isomerization ability of alumina intended by the present invention,
This is because the strong Lewis acid sites newly formed by the defluorination treatment are selectively neutralized, thereby weakening or detoxifying the isomerization ability.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problem of residual organic compounds containing trace amounts of halogen compounds such as fluorine compounds as impurities and having at least one non-conjugated carbon-carbon double bond in the skeleton. In order to reduce the fluorine concentration, when contacting with an inorganic treating agent containing alumina, the isomerization of the carbon-carbon double bond caused by new strong Lewis acid sites formed in the process of defluorination is suppressed. Another object of the present invention is to provide a method for performing a contact process while performing a contact process.
Still another object is to provide a method of selectively reducing the increased isomerization ability and using the alumina again for the contact treatment with respect to alumina having the defluorination ability even though the isomerization ability is increased by the defluorination treatment. .

[0010]

[Means for Solving the Problems] As described above,
Simply contacting the olefin containing residual fluorine as an impurity with alumina under appropriate conditions simply increases the isomerization ability of alumina by a newly generated Lewis acid in accordance with an increase in the amount of defluorination treatment, Eventually, the alumina treatment will need to be discontinued due to the increased isomerization capacity, despite the remaining defluorination capacity. The present inventors sequentially and selectively neutralize Lewis acid sites newly generated by using an organic basic substance to render them harmless by neutralization or the like, thereby substantially detoxifying the isomerization ability and preventing an increase in the isomerization ability. Solved the above problem.

That is, a first aspect of the present invention is to convert an organic compound containing a trace amount of a halogen compound and having one or more non-conjugated carbon-carbon double bonds in one molecule into a treating agent containing an aluminum atom. In removing halogen by contacting, a trace amount of halogen characterized by coexisting a sufficient amount of an organic basic substance in the reaction system to suppress the isomerization of the carbon-carbon double bond of the organic compound. And a method for removing it. The second aspect of the present invention relates to the method of the first aspect of the present invention, wherein the treating agent is an inorganic solid treating agent containing a component represented by the composition formula Al ₂ O ₃ , and the method for removing a trace amount of halogen. A third aspect of the present invention relates to the method for removing a trace amount of halogen according to the second aspect of the present invention, wherein the inorganic solid treating agent is alumina. A fourth aspect of the present invention relates to the method for removing a trace amount of halogen according to the first aspect of the present invention, wherein the halogen compound is a fluorine compound. The fifth of the present invention
The first aspect of the present invention relates to a method for removing a trace amount of halogen, wherein the organic basic substance is ammonia or organic amines. A sixth aspect of the present invention is the method according to the first aspect, wherein the contact temperature between the treating agent and the organic compound is 0 ° C. or more and 350 ° C.
The present invention relates to a method for removing a trace amount of halogen at a temperature of not more than 20 ° C, preferably not more than 20 ° C and not more than 300 ° C. Seventh of the present invention
Carries out halogen removal by continuously contacting an organic compound containing a trace amount of a halogen compound and having at least one non-conjugated carbon-carbon double bond in one molecule with a treating agent containing an aluminum atom. Wherein, in the organic compound, the trace amount characterized by continuously or intermittently supplying a sufficient amount of an organic basic substance to suppress the isomerization of the carbon-carbon double bond of the organic compound And a method for removing halogen.

An eighth aspect of the present invention is that when a butene polymer having a high content of vinylidene terminal by polymerization of isobutene with a halogen-containing catalyst is brought into contact with a treating agent containing an aluminum atom to remove halogens, In addition, the present invention relates to a method for removing a trace amount of halogen, which comprises coexisting a sufficient amount of an organic basic substance to suppress isomerization of a terminal vinylidene group. A ninth aspect of the present invention provides a butene polymer having a high terminal vinylidene content obtained by polymerizing isobutene with a halogen-containing catalyst,
When halogen is removed by continuous contact with a treating agent containing an aluminum atom, a sufficient amount of an organic basic substance is continuously or intermittently contained in a butene polymer to suppress isomerization of terminal vinylidene groups. And a method for removing a trace amount of halogen. A tenth aspect of the present invention is the eighth or ninth aspect of the present invention, wherein the isobutene is less than 50% by weight of 1-butene,
Less than 50 wt% 2-butene, less than 100 wt% isobutene, less than 50 wt% butanes, and 10 wt%
A C ₄ feedstock comprising less than butadiene, to a method for removing halogen traces.

An eleventh aspect of the present invention is that a residual halogen content is 1 ppm or more and a terminal vinylidene group content is 60%.
When performing the halogen removal by contacting the above butene polymer with a treating agent containing an aluminum atom, while coexisting a sufficient amount of an organic basic substance in the reaction system to suppress the isomerization of the terminal vinylidene group. By performing halogen removal, the residual halogen content is 40 ppm or less,
And the terminal vinylidene group content is 6% of the content before the treatment.
The present invention relates to a method for producing a butene polymer maintained at 0% or more. A twelfth aspect of the present invention relates to the method for producing a butene polymer according to the eleventh aspect of the present invention, wherein the residual fluorine content in the butene polymer after the treatment is less than 40 ppm. A thirteenth aspect of the present invention is the eleventh aspect of the present invention,
The present invention relates to a method for producing a butene polymer, wherein the content of terminal vinylidene groups in the butene polymer after treatment is maintained at 70% or more of the content before treatment.

In the fourteenth aspect of the present invention, when a monoolefin containing a trace amount of a halogen compound is brought into contact with a treating agent containing an aluminum atom to remove halogen, isomerization of a carbon-carbon double bond of the monoolefin is carried out. The present invention relates to a method for removing a trace amount of halogen, which comprises coexisting a sufficient amount of an organic base compound in a reaction system to suppress the reaction. In the fifteenth aspect of the present invention, when a monoolefin containing a trace amount of a halogen compound is continuously contacted with a treating agent containing an aluminum atom to remove halogen, a carbon-carbon double bond of the monoolefin is contained in the monoolefin. The present invention relates to a method for removing a trace amount of halogen, which comprises continuously or intermittently supplying a sufficient amount of an organic base compound to suppress isomerization of halogen. A sixteenth aspect of the present invention relates to the method for removing a trace amount of halogen according to the fourteenth or fifteenth aspect of the present invention, wherein the monoolefin containing a trace amount of a halogen compound is a monoolefin that has been contacted by a halogen-containing catalyst. . A seventeenth aspect of the present invention is directed to the sixteenth aspect of the present invention, wherein the monoolefin which has been subjected to the contacting action with the halogen-containing catalyst is converted into the remaining unreacted C by producing the butene polymer from the C ₄ feedstock using the halogen-containing catalyst. _The present invention relates to a method for removing trace amounts of halogen, which is _four fractions.

An eighteenth aspect of the present invention is to contact a treating agent containing an aluminum atom, which has an increased isomerization ability of a non-conjugated carbon-carbon double bond of an organic compound by immobilizing a halogen, with an organic basic substance. The present invention also relates to a method for regenerating a treatment agent containing aluminum, which is characterized in that the isomerization ability of the treatment agent is reduced. The nineteenth aspect of the present invention
In an eighteenth aspect of the present invention, the present invention relates to a method for regenerating a treatment agent containing aluminum, wherein the treatment agent is an inorganic solid treatment agent containing a component represented by a composition formula: Al ₂ O ₃ . Twentieth of the present invention
In the nineteenth aspect of the present invention, relates to a method for regenerating a treatment agent containing aluminum, wherein the inorganic solid treatment agent is alumina.

According to the method of the present invention, the isomerization of a non-conjugated carbon-carbon double bond, which is a side reaction of interest, from an olefinic compound containing residual halogen, for example, residual fluorine as an impurity, is substantially caused. In addition, halogens such as fluorine can be effectively and economically removed. Further, it is possible to reduce the isomerization ability once increased without decreasing the dehalogenation ability, for example, the defluorination ability.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The organic compound to be treated in the present invention is:
It has one or more isomerizable non-conjugated carbon-carbon double bonds per molecule and contains trace amounts of halogen compounds such as fluorine compounds and chlorine compounds as impurities which can be adsorbed on alumina. As long as the organic compound is inert to alumina, the organic compound can have a heteroatom such as oxygen or phosphorus, or various functional groups such as an aromatic ring in a molecule. The molecular weight is not particularly limited, and the low molecular weight side is a C ₄ olefin, for example, butene or more,
The high molecular weight side can include from oligomer regions such as dimers to polymers. Specifically, an organic compound having a molecular weight of about several hundred thousand can be used. The organic compound has a non-conjugated carbon-carbon double bond, but may also contain an aromatic ring double bond or a conjugated double bond as long as it does not affect the treatment. Also, two or more non-conjugated carbon-carbon double bonds may be contained in one molecule as long as they can be isomerized.

Examples of the above organic compounds include unsaturated hydrocarbons having at least one non-conjugated carbon-carbon double bond capable of isomerization. Examples of such olefinic compounds are 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, vinylcyclohexane, 4-methyl-1-pentene, 2,4,4-trimethyl-1-pentene, 1-decene And low molecular weight monoolefins. Further, an olefin oligomer such as polyisobutene having a vinylidene structure at a terminal obtained by polymerizing an olefin such as isobutene as a monomer is exemplified. That is, as the molecular weight, C ₄ lower molecular weight region from the order of the molecular weight of several thousand oligomers such olefins can further comprise a wide range up to hundreds of thousands of polymer. When the raw material olefinic compound is liquid and has a high viscosity, it is preferable to dilute with an inert solvent in order to increase the contact efficiency with a treating agent containing an aluminum atom such as alumina. Examples of such an inert solvent include aliphatic hydrocarbon solvents such as normal hexane and isohexane. As long as the viscosity is appropriate, a light polymer described later can also be used.

The trace amount of the halogen compound as an impurity contained in the organic compound is mainly generated due to a halogen-containing catalyst used in the production of the organic compound. In some cases, impurities caused by impurities other than the above may be included. In the case of a fluorine compound, there are an inorganic fluorine compound, an organic fluorine compound or a mixture thereof, for example, an inorganic fluorine compound such as hydrogen fluoride, boron trifluoride, silicon tetrafluoride,
Examples include organic fluorine compounds such as fluoro-2,4,4-trimethylpentane, but are not particularly limited thereto. When the halogen is chlorine, there are inorganic chlorine compounds, organic chlorine compounds and mixtures thereof. For example, inorganic chlorine compounds such as hydrogen chloride and aluminum chloride, 2-chloro-2,4,4-trimethylpentane And the like. Further, it may be a high-molecular-weight fluorocarbon, for example, a fluorocarbon equivalent to a monomer or a dimer or more in molecular weight by-produced when olefin is polymerized using a fluorine-based catalyst. The content of these halogen compounds, for example, fluorine compounds is usually very small, and the boiling point and the like are close to the boiling points of the above organic compounds. Therefore, it is difficult to separate and remove them by ordinary separation means such as distillation.

The amount of the halogen compound contained in a trace amount is not particularly limited, but is generally up to several hundred ppm in terms of a halogen atom, and may be contained up to about several weight% in some cases. Since both are so-called impurities with respect to the main organic compound, they need to be removed as described above. Generally, it is difficult to remove a halogen compound having a content of ppm level because of its small amount.
The method of the present invention can be preferably applied to such a low content.

Among the organic compounds used in the present invention,
Examples of the olefin oligomer and butene polymers having terminal vinylidene structure obtained by polymerizing C ₄ fraction by fluorine-containing catalysts as described above. This butene polymer contains fluorine as an impurity in an amount of several ppm or more in terms of fluorine atoms, usually about 10 to several hundred ppm, and the fluorine is considered to form an organic fluorine compound, specifically, a fluorinated hydrocarbon. . Further, the C ₄ fraction unreacted C ₄ fraction after the polymerization also can be subject to processing of the present invention because it is intended to include fluorine minor compounds. Note that fluorine in this case is also considered to be an organic fluorine compound.

Next, the production of the butene polymer will be described. In the polymerization zone (reaction zone) equipped with a reactor, isobutene or C containing
Manufactured by continuously polymerizing _four feedstocks.
As the continuous reactor, any type that can perform appropriate heat removal and stirring, such as a stirring type reactor and a loop type reactor, can be adopted. From the polymerization zone, a reaction solution containing the unreacted components, the produced butene polymer, and the catalyst flows out.

[0023] Representative examples of C ₄ feedstock, for example in order to produce lower olefins ethylene and propylene, etc., naphtha, kerosene, gas oil, hydrocarbon pyrolyzing cracker or catalytic cracking fluid catalytic cracking of butane (F
From C ₄ fraction flowing out CC) system, which was removed by extraction or the like butadiene (butadiene raffinate) are exemplified. C ₄ fraction typical composition of the unsaturated component, from about 1 to 40 wt%, preferably from about 10 to 40 wt% of 1-butene, about 1 to 40 wt% of 2-butene, about 1
0-80 wt%, preferably about 40-70 wt% isobutene, and less than about 10 wt%, preferably about 0.5 wt%.
Wt% or less butadiene, and about 1
It is made of 0 to 30 wt% of butanes (to 100 wt% the sum of the C ₄ fractions). This not limited particularly as long as the composition range may be a C ₄ fraction containing isobutene contained in the decomposition product from the FCC as well the cracker. In addition, as long as the composition is within the above-mentioned composition range, a composition whose composition is changed by an appropriate means can be used. Specifically, the composition is changed by distillation, the isobutene concentration is increased by adding isobutene, the isobutene is oligomerized by light polymerization to reduce the isobutene concentration, or the reaction is carried out by a reaction such as catalytic hydroisomerization. -Those having a reduced butene concentration, those having a composition changed by various physical or chemical operations, and the like can be used. C ₄ fraction,
The higher the isobutene content, the better. However, for example, butadiene raffinate also has a maximum isobutene content of about 70% by weight. Usually lower the _{C 4} fraction from such FCC.

As a catalyst in the polymerization reaction of isobutene, a fluorinated catalyst is used. In this case, a small amount of a fluorine compound is mixed into the product butene polymer. In addition, aluminum chloride or a complex catalyst thereof can be used, and in this case, a chlorine compound is mixed as an impurity. The fluorinated catalyst to be used is not particularly limited as long as a trace amount of a fluorinated compound is mixed in the product by its use. Specifically, in addition to a boron trifluoride-based catalyst, a catalyst obtained by contacting a divalent nickel compound with a hydrocarbyl aluminum halide and trifluoroacetic acid, for example, an interaction between nickel heptanoate and dichloroethyl aluminum and trifluoroacetic acid Those formed by the action are exemplified. This divalent nickel-based fluorinated catalyst is disclosed in
No. 3726 is proposed.

A preferred fluorinated catalyst is a boron trifluoride catalyst. In this case, boron trifluoride is fed into the polymerization zone at a ratio of 0.1 to 500 mmol per 1 mol of the raw material isobutene. I do. The molecular weight of the butene polymer obtained according to the present invention can be adjusted by adjusting the reaction temperature and the amount of catalyst charged. If the amount of boron trifluoride as a catalyst is less than this range, the reaction is difficult to proceed, while if it is more than this, the molecular weight of the butene polymer becomes low and the cost of the catalyst increases, which is not economical.

A more preferred boron trifluoride-based catalyst is
A complex catalyst using an oxygen-containing compound as a complexing agent. Examples of the oxygen-containing compound that forms a complex with boron trifluoride include water, alcohols, and ethers such as dialkyl ethers. Water, alcohols, dialkyl ethers or a mixture thereof can be fed to the polymerization zone as a complexing agent in a total amount of 0.03 to 1,000 mmol per 1 mol of isobutene in the raw material. When the amount of the complexing agent is larger than this range, the reaction hardly proceeds. On the other hand, when the amount is smaller than this range, a large amount of side reactions and the like occur, and thus both are not preferable.

The above-mentioned water, alcohols, dialkyl ethers and the like all form a complex with boron trifluoride in the reaction system. Therefore, a method of separately preparing a complex comprising boron trifluoride and a complexing agent such as water, alcohols, dialkyl ethers or a mixture thereof and boron trifluoride outside the polymerization zone, and supplying this to the reaction system is adopted. Alternatively, a method in which boron trifluoride and the complexing agent are separately supplied to form a complex in the polymerization zone can be employed as one of the polymerization modes of the present invention. Thus, even when boron trifluoride and the complexing agent are separately supplied to the polymerization system, the supply ratio of boron trifluoride, water, alcohols and dialkyl ethers as the complex component to the C ₄ hydrocarbon feedstock Can be in the same range as described above. In order to produce a stable butene polymer that responds quickly to fluctuations in the water and isobutene concentrations in the raw material, the amount of boron trifluoride and the molar ratio with the complexing agent must be quickly adjusted to the above changes. It is advantageous to adjust
It is more preferable to supply water, alcohols, dialkyl ethers or a mixture thereof to the reaction system separately from boron trifluoride.

Specific examples of alcohols and dialkyl ethers as complexing agents are as follows. Examples of the alcohols include aromatic or C _{1 to} C ₂₀ aliphatic alcohols. Specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol or benzyl alcohol, Cyclohexanol, 1,4-butanediol and the like can be mentioned. The above C
₁ -C ₂₀ carbon skeleton of the fatty alcohols, without limiting the branching degree, straight chain alkyl group, sec-, branched alkyl group or alicyclic alkyl group tert- etc., or even an alkyl group containing a ring No problem. These alcohols can be used alone or in a mixture at an appropriate ratio.

Examples of the dialkyl ethers include aromatic or C _{1 to} C ₂₀ aliphatic dialkyl ethers having the same or different hydrocarbon groups. Specifically, dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, methyl propyl ether, ethyl propyl ether, dibutyl ether, methyl butyl ether, ethyl butyl ether, propyl butyl ether, dipentyl ether, or phenyl methyl ether, phenyl ethyl ether , Diphenyl ether, cyclohexylmethyl ether, cyclohexylethyl ether and the like. The above C _{1 to} C
The skeleton of the hydrocarbon group No. ₂₀ is not limited in the degree of branching, and may be a linear alkyl group, a branched alkyl group such as sec- or tert- or an alicyclic alkyl group, or an alkyl group containing a ring. These dialkyl ethers can be used alone or in a mixture at an appropriate ratio. In addition,
One or more complexing agents such as water, the above-mentioned alcohols and dialkyl ethers can be used by mixing at an appropriate ratio.

The polymerization using a boron trifluoride-based catalyst is a liquid phase polymerization, and the polymerization temperature is in the range of -100 ° C to + 50 ° C, preferably -50 ° C to + 20 ° C. If the temperature is lower than this range, the polymerization rate of isobutene is suppressed. On the other hand, when the temperature is higher than this, side reactions such as isomerization and rearrangement reaction occur, and it becomes difficult to obtain the target product of the present invention.

As the type of polymerization, either a batch type or a continuous type can be used to produce a butene polymer having a high content of a vinylidene terminal structure. However, from the viewpoint of industrial production, a continuous method is more economical and efficient. Therefore, the continuous polymerization will be described below as an example. In general, the contact time of the feedstock with the catalyst is important in the continuous method, and in the polymerization reaction according to the present invention, the contact time is desirably in the range of 5 minutes to 4 hours. If the contact time is less than 5 minutes, a sufficient conversion of isobutene cannot be obtained, and excessive equipment is required to remove the heat of reaction. On the other hand, if it exceeds 4 hours, there is a large economical loss, and since the catalyst comes into contact with the catalyst for a long time, side reactions such as isomerization and rearrangement of the produced butene polymer are promoted. Therefore, neither case is preferable.

After the polymerization, the reaction liquid containing the unreacted components and the produced butene polymer and catalyst flows out from the polymerization zone as described above. In the next step, the catalyst is deactivated with an appropriate deactivator, for example, water, alkaline water, alcohol, or the like, in the above reaction solution according to a conventional method. After deactivation of the catalyst, if necessary by performing the neutralization and water washing to remove catalyst residues to give a butene polymer by removing the C ₄ component of unreacted by performing appropriate distillation. The butene polymer thus obtained can be further appropriately distilled to be separated into a light component (hereinafter sometimes referred to as “light polymer”) and a heavy component.

As described above, liquid vinyl polymerization of isobutene using boron trifluoride as a polymerization catalyst and water, alcohol, dialkyl ether or the like as a complexing agent allows a terminal vinylidene group to be added to all terminal groups. A butene polymer containing a high proportion of 60 mol% or more can be obtained. However, this butene polymer contains residual fluorine derived from the catalyst in a concentration of 1 ppm or more, usually 5 ppm or more, sometimes up to several hundred ppm in terms of fluorine atoms. This residual fluorine is an organic fluorine which is difficult to remove even by deactivation and subsequent washing with water by a conventional method. Next, the alumina treatment for defluorination performed in the present invention will be described.

In the present invention, the halogen compound contained in the organic compound is removed by contact with a treating agent containing an aluminum atom. The halogen atoms in the halogen compound are fixed in the treating agent containing aluminum, and as a result, the halogen is removed. The treating agent containing an aluminum atom is preferably an inorganic solid treating agent containing a component represented by the composition formula Al ₂ O ₃ . Al ₂ O ₃
Natural or synthetic inorganic substances can be used as long as they contain the component represented by Specific examples of the inorganic solid processing agent include alumina and silica / alumina. Preferably, it is alumina. These may be molded using an appropriate binder. For example, commercially available alumina can be appropriately ground and classified for use. The surface area of the solid processing agent is not particularly limited, but is usually in the range of 1 to 500 m ² / g. In addition, as long as the effects of the present invention are not impaired, alumina is appropriately impregnated with an alkali metal, an alkaline earth metal, or another metal, an oxide, a hydroxide, or another form, or appropriately supported by another method. Modified ones can also be used. However, usually, such supporting / modifying is not particularly required, and alumina having a content of an alkali metal such as sodium or an alkaline earth metal of 0.5% by weight or less is used. Alumina that does not or hardly carry or modify in this way is inexpensive,
In this respect, the present invention is an advantageous method.

The butene polymer to be brought into contact with the inorganic solid treating agent containing alumina must be after the catalyst has been deactivated. However, whether or not distillation is performed after deactivation and washing with water is required. There are no restrictions. If the viscosity is high,
In order to increase the contact efficiency with alumina, it is preferable to dilute with an inert solvent. Examples of such an inert solvent include aliphatic hydrocarbon solvents such as normal hexane and isohexane, and the recovered light polymer can also be used as a solvent.

The temperature at which the solid inorganic treating agent containing alumina is brought into contact with the butene polymer depends on the type of treating agent and the amount of the organic basic substance used, but is preferably 0 ° C. to 350 ° C., more preferably. Is 20 ° C-3
It is in the range of 00 ° C. When the processing temperature is higher than this range, the residual halogen concentration is reduced, but decomposition of the olefinic compound to be processed starts to occur, while when the temperature is low, the residual halogen concentration is not reduced, Any of them is not preferable because a sufficient reduction effect cannot be obtained.

The contact time between the alumina-containing solid inorganic treating agent and an organic compound such as a butene polymer is not particularly limited as long as the residual halogen can be reduced, but is usually preferably in the range of about 1 minute to 10 hours. If the length is shorter than this range, the contact is generally insufficient. If the length is longer, the equipment cost increases, which is not preferable. As a method for contacting, either a batch type or a continuous type is possible. In the case of a continuous system, a method such as a fixed bed system or a fluidized bed system can be used. The direction of the flow can be either an upflow or a downflow.

When an organic compound such as a butene polymer is brought into contact with a treating agent containing an aluminum atom for dehalogenation, a strong acid site is newly generated by a halogen atom, for example, a fluorine atom fixed to the treating agent. However, there is a phenomenon that a non-conjugated carbon-carbon double bond in an organic compound causes isomerization due to the strong acid point. For example, when the organic compound to be dehalogenated is a butene polymer or the like containing a large amount of a terminal vinylidene group, the halogen is removed by the dehalogenation treatment, but the position of the double bond of the vinylidene group moves. And the content of high vinylidene groups is reduced. In addition, when butene-1 or the like is a target of the dehalogenation treatment, a side reaction of butene-1 being isomerized to butene-2 is observed.

As a countermeasure, in the present invention, an organic basic substance is allowed to coexist in the reaction system for the dehalogenation treatment. That is, it contains a trace amount of a halogen compound and contains 1
An organic compound having at least two non-conjugated carbon-carbon double bonds is contacted with a treating agent containing an aluminum atom to remove halogen, and suppresses isomerization of the carbon-carbon double bond of the organic compound. For this purpose, halogen is removed while a sufficient amount of an organic basic substance coexists in the reaction system. In addition, a method in which a treating agent for dehalogenation, for example, alumina is previously treated with an organic basic substance is less effective because the isomerization reaction is caused by strong acid sites newly generated by dehalogenation.

As a specific method for coexisting an organic basic substance, for example, when dehalogenation is performed by continuously contacting an organic compound with alumina using a fixed bed or a fluidized bed, a fluid comprising an organic compound is used. A method in which an organic basic substance is continuously supplied and coexisted therein can be adopted. In the case of continuous contact, the organic basic substance can be appropriately and intermittently supplied into the fluid. In the case of intermittently supplying the organic basic substance, the contact treatment between the organic compound and alumina proceeds, and as a result, the organic basic substance before or immediately after the isomerization ability of alumina starts to increase. Is preferably started.

Further, the dehalogenation treatment is continued without the coexistence of an organic basic substance, and when the dehalogenation ability is maintained at a certain level but the isomerization ability of alumina is increased by immobilization of halogen, It is also possible to regenerate alumina by contacting an organic basic substance, thereby reducing isomerization ability while maintaining dehalogenation ability. As one of the methods, for example, after a certain amount of an organic compound is continuously dehalogenated in a fixed bed format, the supply of the object to be treated is stopped, and an organic basic substance is separately supplied into the system. By contacting with alumina, the increased isomerization ability can be reduced to regenerate the alumina treating agent. Alternatively, after performing a dehalogenation treatment of a certain amount of an organic compound in a batch system, the organic compound is extracted, and instead, an organic basic substance is charged and brought into contact with alumina to reduce the increased isomerization ability. To regenerate the alumina treating agent.

Since the amount of the organic basic substance used here is generally very small, it is usually preferable to dilute it with an inert gas or liquid and bring it into contact with alumina. Inert gas or liquid other than gas such as nitrogen and air,
Examples thereof include aliphatic hydrocarbon solvents such as normal hexane and isohexane. The light polymer can be recovered and used as a diluent. Of course, the organic compound itself to be subjected to the dehalogenation treatment can be used as the diluent.

Examples of the organic basic substance used in the present invention include ammonia and other basic nitrogen-containing compounds. Specific basic nitrogen-containing compounds include primary, secondary and tertiary organic amines. is there. These may have a weak acid moiety such as a carboxyl group in the molecule. Examples of organic amines include methylamine, dimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, diisobutylamine, sec-butylamine, tert-butylamine, tri-n-octyl. Amines such as amine, di-2-ethylhexylamine, allylamine, diallylamine, triallylamine, aniline, benzylamine, ethylenediamine, hexamethylenediamine, tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylpentamine and the like; 3- (methylamino ) Propylamine, 3- (dimethylamino)
Amines such as propylamine and 3- (dibutylamino) propylamine; 3-methoxypropylamine;
Oxyamines such as ethoxypropylamine, 3- (2-ethylhexyloxy) propylamine, N-methylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, N -Methyldiethanolamine, N- (2-aminoethyl) ethanolamine, 3-
Examples thereof include hydroxylamines such as amino-1-propanol, and pyridines such as pyridine and aminopyridine.Also, amino acids such as β-alanine are effective. Absent. Preferred are basic substances classified as weak bases.

After performing the dehalogenation treatment, the organic basic compound used in the present invention is usually separated from the organic compound to be subjected to the dehalogenation treatment. Therefore, it is preferable to select, for example, a compound having a sufficiently large boiling point difference from the organic compound to be treated, because the separation can be easily performed by using distillation, which is a simple separation operation.

The amount of the organic basic substance used may be an amount sufficient to suppress the isomerization of the non-conjugated carbon-carbon double bond in the organic compound. As described above, an organic basic substance is used to neutralize newly generated acid sites by the halogen atoms fixed to the treating agent containing an aluminum atom. It is difficult to accurately determine the strength as an acid point and the like.
The acid sites that influence the isomerization of the double bond are those having a strong acid strength, and the acid strength varies depending on each organic compound. In general, even if an organic basic substance is present in an excess amount in a reaction system, it does not significantly affect the dehalogenation treatment itself. As a disadvantage when the amount is excessive, it is uneconomical because a separation operation of a large amount of an organic basic substance is required after the dehalogenation treatment. Further, the degree of isomerization of a non-conjugated double bond in an organic compound is often easily determined by analyzing the organic compound using various instruments.

Therefore, as for the amount of the organic basic substance in the present invention, an amount sufficient to suppress the isomerization of the non-conjugated carbon-carbon double bond of the organic compound is to coexist. Specifically, the total of the halogen compound contained in the organic compound and the halogen atom fixed in the treating agent is 0.00001 mol or more, preferably 1 mol or more per 1 mol of the halogen atom present in the reaction system of the contact treatment. The organic basic compound in an amount of 0.0005 mol or more, more preferably 0.001 mol or more, can coexist in the reaction system of the treatment. If the above amounts are used together,
It is considered sufficient to suppress the isomerization of non-conjugated carbon-carbon double bonds in organic compounds. If the amount of the organic basic compound is less than this range, the isomerization ability cannot be sufficiently reduced, which is not preferable. When added in excess, it does not hinder the dehalogenation function, but is economically disadvantageous in that the cost for recovering the excess organic basic substance increases as described above. Therefore,
Usually, it is appropriate to limit the amount to 200 mol or less per 1 mol of residual halogen atoms in an organic compound such as an olefinic compound to be treated.

When the organic basic substance is intermittently supplied, an amount capable of suppressing the isomerization ability due to a strong acid point generated by fixing a halogen atom such as fluorine to alumina is used. Specifically, a halogen atom 1 fixed on alumina
0.00002 mol or more, preferably 0.1 mol per mol.
001 mol or more, more preferably 0.002 mol or more. When the amount of the organic base compound is smaller than this range, it is not preferable for the same reason as in the case of coexisting continuously. When added in excess, the dehalogenation function is hardly hindered, but is economically disadvantageous in that the cost for recovering the excess organic basic substance increases. Therefore, it is usually appropriate to limit the amount to 200 mol or less per 1 mol of halogen atoms fixed on alumina.

As a simple guide regarding the amount of the organic basic substance to be coexisted, when the residual halogen concentration (in terms of halogen atom) contained in the organic compound is at a level of several percent or less, the And 1 to 50,0
It can be selected from the range of 00 ppm, preferably 1 to 10,000 ppm. In addition, when determining the amount of the organic basic compound in the present invention, the amount of halogen to be fixed to the treating agent was determined by calculating or removing the amount to be removed based on the halogen content of the feedstock. The result can be used. For example, 100
In the case where the raw material containing halogen of ppm is continuously supplied to perform dehalogenation treatment and the target value is reduced to 5 ppm, 95 ppm of the difference is supplied as the amount of the halogen atom to be fixed as the amount of the above-mentioned amine or the like. Can be calculated. Similarly, even when a certain amount of halogen has been treated without coexisting with amines or the like, the difference between the halogen atom contents before and after the dehalogenation treatment is fixed as the amount of halogen, and the amine or the like to be supplied is similarly treated. The quantity can be calculated. Even if the result of this calculation indicates that the supply amount of the organic basic compound may be excessive, as far as such a calculation is concerned, the harm caused by the excess is negligible in practice.

Further, when the alumina having an increased isomerization ability is brought into contact with an organic basic substance for regeneration while reducing the isomerization ability while maintaining the dehalogenation ability, the halogen fixed on the alumina may be used. The amount is in the range of 0.00001 mol or more, preferably 0.0005 mol or more, per 1 mol of atom. In this case, there is no upper limit in the amount of the organic basic substance since it is a mere regeneration and does not perform a dehalogenation reaction. However, when it is used in an excessively large amount, it is uneconomical in terms of, for example, a recovery process for the excess amount. Usually, it is sufficient to uniformly contact up to 200 moles of an organic basic substance with respect to 1 mole of halogen atoms fixed on the alumina-containing inorganic substance. The conditions such as the temperature in the regeneration can be appropriately selected. The temperature can be selected, for example, from the range of -100 to + 400C. In the case where the dehalogenation treatment is not performed at the same time and only the regeneration for reducing the isomerization ability increased by the treatment of the organic basic substance is performed, a milder condition than in the case of the dehalogenation treatment can be selected.

After performing the contact treatment for dehalogenation,
An organic compound such as an olefinic compound having a reduced residual halogen concentration can be obtained by removing an excess of an organic basic substance or a solvent when a solvent or the like is appropriately removed by distillation or the like. By the dehalogenation treatment of the present invention, the residual halogen concentration in an organic compound such as an olefinic compound is 40 ppm or less, preferably 40 p
Organic compounds, such as olefinic compounds, reduced to less than pm and maintained at a low isomerization of non-conjugated carbon-carbon double bonds of less than 40%, preferably less than 30%, more preferably less than 20% Is obtained. That is, the non-conjugated double bond of the terminal vinylidene structure can be maintained at a rate of 60% or more, preferably 70% or more, more preferably 80% or more, as compared with that before the dehalogenation treatment. As described above, since substantially no residual halogen such as fluorine is present, even when the obtained organic compound such as an olefinic compound or a modified product thereof is burned, the emission of halogen such as fluorine into the atmosphere is prevented. Therefore, it is useful in terms of environmental protection.

[0051]

EXAMPLES <Example 1> (Polymerization Step) 4 liter circulating reactor, the butadiene raffinate C ₄ fraction of an ethylene cracker was fed per hour 4 l, 0.15 wt% relative to isobutene Of boron trifluoride and 0.14% by weight of ethanol were separately supplied to the reaction vessel. Reaction temperature -10
At ℃, the polymerization was carried out continuously. Table 1 shows the composition of butadiene raffinate. The analysis was performed by gas chromatography (the same applies hereinafter).

[Table 1]

(Deactivation, washing step) The reaction solution obtained above was treated with a 2% aqueous NaOH solution to deactivate and neutralize the catalyst, and further washed three times with deionized water. and dried to recover the unreacted C ₄ component by distillation. Unreacted C ₄ recovered
As a result of analyzing the components, the residual fluorine concentration was 4.5 ppm. The composition is shown in Table 2.

[Table 2]

(Defluorination step) Then, activated alumina (produced by PROCATALYSE, trade name: PSG-D25) was dried at 200 ° C. for 2 hours in a cylindrical container having a capacity of 10 liters and a fluid inlet at the bottom and a fluid outlet at the top. ) Is crushed and charged with a particle size of 2 mm to 3.5 mm.
Unreacted C ₄ collected earlier is connected to the fluid inlet of this cylindrical container.
A line for supplying the components was installed. Ammonia leave premixed so that 4ppm against unreacted C ₄ component was a defluorination material. Defluoridation temperature is 210
° C., ammonia and the mixture was unreacted C ₄ component flow rate per hour 100ml of, after the start defluorination process samples the gas outlet up to 1,000 hours per arbitrary time C ₄ component of 1-butene and The concentration of 2-butene and the concentration of residual fluorine were measured. Table 3 shows the time-dependent changes in the residual fluorine concentration and the terminal vinylidene content after the treatment.

[Table 3]

<Comparative Example 1> An experiment was performed in the same manner as in Example 1 except that ammonia was not added. The results are shown in Table 4, which clearly shows that 1-butene isomerized and 2-
It has changed to butene.

[Table 4]

<Comparative Example 2> Instead of alumina, a cylindrical container was filled with silica gel (trade name: Silbead N, manufactured by Mizusawa Chemical Industry Co., Ltd.) previously dried at 150 ° C under a stream of dry nitrogen, The experiment was performed under the same conditions as in Example 1 except that the treatment temperature was changed to room temperature.
The concentration of C ₄ component of the 1-butene and 2-butene after treatment has not changed compared with the previous process, but isomerization was observed, the residual fluorine concentration also in the initial process 4.
It was 0 ppm, and no removal effect was obtained.

<Example 2> (Polymerization step) Butadiene raffinate (same as in Table 1) from an ethylene cracker was supplied at a rate of 4 liters per hour to a 4 liter circulation type reaction vessel, and 0.15 weight per isobutene was added. % Boron trifluoride and 0.14% by weight
Of ethanol were separately supplied to the reaction tank. Polymerization was carried out continuously at a reaction temperature of -10 ° C. (Deactivation, washing step) The obtained reaction solution was treated with a 2% NaOH aqueous solution to deactivate and neutralize the catalyst, and further washed three times with deionized water. After washing, dry and unreacted C
By distilling off the _four components and the light polymer by distillation, a butene polymer having a number average molecular weight of 1,300, a terminal vinylidene group content of 91%, and a residual fluorine concentration of 76 ppm was obtained.

(Defluorination Step) Activated alumina (produced by PROCATALYSE, trade name: PSG-D25) dried under reduced pressure at 200 ° C. for 2 hours in a fixed-bed container having a capacity of 100 cc was pulverized to a particle size of 0.5 mm to 1.4 mm. Was charged. 100 parts by weight of the above-mentioned butene polymer and 400 ppm of triethylamine were added to this filled container, and 10 parts by weight of an isoparaffin solvent (trade name: Nisseki Isosol 300, manufactured by Nippon Petrochemical Co., Ltd.) was added to adjust the viscosity. Was used as a defluorinated raw material. The defluorination treatment conditions were a temperature of 170 ° C. and a WHSV of 1 hr ⁻¹ . After the start of the defluoridation treatment, the treatment liquid at the outlet of the filling container is discharged at an arbitrary time for 2,2 hours.
Sampling was performed until 030 hours, and the content of terminal vinylidene groups and the residual fluorine concentration of the butene polymer were measured.
The number average molecular weight was measured by GPC (manufactured by Shimadzu Corporation), and the vinylidene terminal content was measured by NMR (JEOL Ltd.).
) And the residual fluorine concentration was measured by a Wickbold-colorimetric method. Table 5 shows the time-dependent changes in the residual fluorine concentration and the content of the terminal vinylidene group after the treatment.

[Table 5]

[0058] <Example 3> neutralization, in the distillation after washing with water, only unreacted C ₄ component was distilled off, defluorination raw material butene polymer containing light polymer (residual fluorine concentration 1
88 ppm) and the amount of triethylamine added was 200
The experiment was carried out under the same conditions as in Example 2 except that ppm was used. The results are shown in Table 6.

[Table 6]

<Comparative Example 3> The processing temperature was lowered to 110 ° C. without adding triethylamine.
An experiment was performed in the same manner as in the above. The results up to 550 hours are shown in Table 7, and the isomerization of the vinylidene structure is progressing despite the lower temperature than in Example 1.

[Table 7]

<Example 4> (Polymerization step) As a catalyst and a complexing agent, 0.82% by weight of boron trifluoride, 0.89% by weight of diethyl ether and 0.02% by weight of ethanol based on isobutene were used. Polymerization was performed in the same manner as in Example 1 except that the polymerization was performed. (Deactivation / Washing Step) The same deactivation / water washing step as in Example 1 was performed to obtain a butene polymer having a number average molecular weight of 1,462, a vinylidene terminal group content of 88%, and a residual fluorine concentration of 7 ppm.

(Defluorination Step) The butene polymer obtained above was used as a defluorination raw material, and
A defluorination treatment was performed in the same manner as in Example 1 except that ammonia at a flow rate corresponding to a concentration of 0 ppm was mixed just before the entrance of the alumina filling container and supplied to the filling container under a pressure of 2 MPa. Table 8 shows the time-dependent changes in the residual fluorine concentration and the terminal vinylidene content after the treatment.

[Table 8]

<Comparative Example 4> Silica gel (trade name: Silbead N, Mizusawa Chemical Co., Ltd.) previously heated and dried at 150 ° C. in a dry nitrogen stream at 100 ° C. was added to 100 ml of the defluorinated raw material butene polymer obtained in Example 2 above. Industry
27 g) and stirred at room temperature for 1 hour. The terminal vinylidene group content of the butene polymer after the treatment is 91%.
No residual isomerization was observed, but the residual fluorine concentration after the treatment was 104 ppm, and when the molecular weight was large such as a butene polymer, fluorine could not be sufficiently removed even by treatment with silica gel.

[0063]

According to the method of the present invention, the isomerization of a non-conjugated carbon-carbon double bond, which is the largest side reaction, from an olefinic compound containing residual halogen as an impurity is substantially prevented. Halogen can be effectively and economically removed.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C07C 11/12 C07C 11/12 F term (reference) 2E191 BA12 BC01 BC05 BD00 4D017 AA05 BA20 CA05 CA11 CB01 CB10 DA01 EA01 EB03 EB07 EB10 4H006 AA02 AA05 AD17 AD40 BA09 BA30 BA50 BB11 BB61 BC34 BC51

Claims (20)

[Claims] 1. An organic compound containing a trace amount of a halogen compound and having one or more non-conjugated carbon-carbon double bonds in one molecule is contacted with a treating agent containing an aluminum atom to remove the halogen. A method of removing a trace amount of halogen, wherein a sufficient amount of an organic basic substance coexists in the reaction system to suppress the isomerization of the carbon-carbon double bond of the organic compound. 2. The method according to claim 1, wherein the treating agent is an inorganic solid treating agent containing a component represented by a composition formula of Al ₂ O ₃ . 3. The method according to claim 2, wherein the inorganic solid treating agent is alumina. 4. The method according to claim 1, wherein the halogen compound is a fluorine compound. 5. The method according to claim 1, wherein the organic basic substance is ammonia or organic amines. 6. The contact temperature between the treating agent and the organic compound is 0 ° C. or more and 350 ° C. or less, preferably 20 ° C. or more and 300 ° C.
The method for removing a trace amount of halogen according to claim 1, which is as follows. 7. An organic compound containing a trace amount of a halogen compound and having one or more non-conjugated carbon-carbon double bonds in one molecule is continuously brought into contact with a treating agent containing an aluminum atom to form a halogen compound. In performing the removal, a sufficient amount of an organic basic substance is continuously or intermittently supplied to the organic compound to suppress the isomerization of the carbon-carbon double bond of the organic compound. A method of removing a trace amount of halogen. 8. When the halogen removal is carried out by contacting a butene polymer having a high vinylidene terminal content obtained by polymerizing isobutene with a halogen-containing catalyst to a treating agent containing an aluminum atom, the butene polymer contains A method for removing a trace amount of halogen, comprising coexisting a sufficient amount of an organic basic substance to suppress isomerization of a vinylidene group. 9. When removing a halogen by continuously contacting a butene polymer having a high terminal vinylidene content obtained by polymerizing isobutene with a halogen-containing catalyst to a treating agent containing an aluminum atom, the butene polymer contains A method for removing the trace amount of halogen, comprising continuously or intermittently supplying a sufficient amount of an organic basic substance to suppress isomerization of the terminal vinylidene group. 10. The isobutene comprises less than 50% by weight of 1-butene, less than 50% by weight of 2-butene, less than 100% by weight of isobutene, less than 50% by weight of butanes and less than 10% by weight of butadiene. method for removing halogen traces according to claim 8 or 9 is a C ₄ feedstock. 11. A residual halogen content of 1 ppm or more,
And when a butene polymer having a terminal vinylidene group content of 60% or more is brought into contact with a treating agent containing an aluminum atom to remove halogen, a sufficient amount of an organic base for suppressing isomerization of the terminal vinylidene group. By removing halogens while coexisting a reactive substance in the reaction system, a butene polymer having a residual halogen content of 40 ppm or less and a terminal vinylidene group content of 60% or more of the content before the treatment is produced. how to. 12. The method for producing a butene polymer according to claim 11, wherein the residual fluorine content in the butene polymer after the treatment is less than 40 ppm. 13. The method for producing a butene polymer according to claim 11, wherein the content of the terminal vinylidene group of the butene polymer after the treatment is maintained at 70% or more of the content before the treatment. 14. When removing a halogen by contacting a monoolefin containing a trace amount of a halogen compound with a treating agent containing an aluminum atom, a sufficient amount of the monoolefin to suppress the isomerization of a carbon-carbon double bond of the monoolefin is used. A method for removing a trace amount of halogen, which comprises coexisting an appropriate amount of an organic base compound in a reaction system. 15. When removing a halogen by continuously contacting a monoolefin containing a trace amount of a halogen compound with a treating agent containing an aluminum atom, the monoolefin contains a carbon-carbon double bond of the monoolefin. A method for removing a trace amount of halogen, comprising continuously or intermittently supplying a sufficient amount of an organic base compound to suppress isomerization. 16. The method for removing a trace amount of halogen according to claim 14, wherein the monoolefin containing a trace amount of a halogen compound is a monoolefin that has been subjected to a contacting action with a halogen-containing catalyst. 17. monoolefins having received the contact action of the halogen-containing catalyst is a residual unreacted C ₄ fraction to produce a butene polymer from C ₄ feedstocks using a halogen-containing catalyst, claim 16. The method for removing a trace amount of halogen according to 16. 18. A treating agent containing an aluminum atom having an increased isomerization ability of a non-conjugated carbon-carbon double bond of an organic compound by immobilizing a halogen, is brought into contact with an organic basic substance, and A method for regenerating a treatment agent containing aluminum, wherein the isomerization ability is reduced. 19. The method for regenerating a treatment agent containing aluminum according to claim 18, wherein the treatment agent is an inorganic solid treatment agent containing a component represented by a composition formula: Al ₂ O ₃ . 20. The method for regenerating a treatment agent containing aluminum according to claim 19, wherein the inorganic solid treatment agent is alumina.