JPH0222053B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for easily producing paratertiary butylphenol from isobutylene containing n-butenes and phenol with high yield and high selectivity.

Paratertiary butylphenol is obtained by removing butane from C ₄ hydrocarbons, which are usually by-produced during naphtha decomposition, and hydrocarbons containing butenes (hereinafter abbreviated as "mixed butenes"), which is treated with sulfuric acid.
It is known that it is produced from isobutylene and phenol obtained through purification distillation.

For example, when phenol is reacted with isobutylene using arylsulfonic acid as a catalyst, paratertiary butylphenol can be obtained in a relatively good yield (USP 3,932,537). It is also well known to produce paratertiary butylphenol using catalysts such as sulfuric acid, boron trifluoride, and aluminum chloride.

However, isobutylene is more expensive than mixed butene, and if inexpensive mixed butene can be used as it is for alkylation of phenol, it will be extremely useful industrially because the production cost of paratertiary butyl phenol can be reduced. However, with the commonly used catalysts and the above-mentioned arylsulfonic acids, if the reaction is carried out using mixed butene under conditions where isobutylene is used as a raw material and paratertiary butylphenol can be obtained in a relatively good yield, the desired reaction is not achieved. This method not only significantly reduces the yield of paratertiary butylphenol due to the reaction of 1-butene, but also produces secondary butylated by-products that are difficult to separate and purify. This is extremely disadvantageous for the production of Therefore, various methods using mixed butene as a raw material have been proposed.

For example, methods using mixed butenes include a method using aluminum phenoxide as a catalyst (BP1062298) and a method using a mixed oxide of titanium and zinc as a catalyst (Japanese Patent Laid-Open No. 14933/1983).
However, the former method requires complicated catalyst preparation and catalyst removal, and cannot be called an economical method for producing paratertiary butylphenol. In the latter method, more orthotertiary butylphenol is produced under atmospheric pressure, and secondary butylphenol is produced under pressure, making it difficult to implement industrially.

The present inventors have carried out various studies with the aim of establishing a method that can easily obtain high-purity paratertiary butylphenol with a small amount of secondary butylphenol as a by-product using inexpensive mixed butene as a raw material. .

As a result, when mixed butene is reacted with phenol at a relatively low temperature in the presence of arylsulfonic acid as an alkylating agent, only isobutylene in the mixed butene reacts selectively (first stage reaction), and this reaction product is transferred to silica. It has been found that the above object can be achieved by carrying out a rearrangement reaction (second stage reaction) at a slightly high temperature in the presence of a catalyst such as alumina or activated clay, and the present invention has been achieved based on this finding.

That is, the present invention selectively reacts isobutylene containing n-butenes with phenol at 20 to 120°C in the presence of an arylsulfonic acid catalyst, and then reacts silica alumina with or without removing the catalyst. A high-temperature reactor characterized by carrying out a rearrangement reaction at 80 to 200°C in the presence of at least one catalyst selected from the group consisting of activated clay, diatomaceous earth, rare earth-substituted zeolite, sulfuric acid, ion exchange resin, and boron fluoride. This is a method for producing pure paratertiary butylphenol.

When mixed butenes are reacted according to the method of the present invention, it is possible to react only isobutylene without substantially reacting butene-1 and butene-2. Isobutylenated phenols in which only isobutylene reacted in this way (paratertiary butylphenol, orthotertiary butylphenol, 2,6-ditertiary butylphenol, 2,4-ditertiary butylphenol,
2,4,6-tritarsiabutylphenol,
By carrying out a rearrangement reaction of tertiary butyl phenyl ether) using a second reaction catalyst, paratertiary butyl phenol can be produced with high yield and selectivity.

A further advantage of the process of the present invention is that it is not necessary to remove the catalyst of the first stage reaction prior to the second stage reaction. When the catalyst for the second stage reaction, such as activated clay, is removed by filtration or the like, the catalyst used in the first stage reaction is also removed from the reaction system.

Normally, when these sulfonic acid catalysts are used, the generation of wastewater from neutralization washing is unavoidable, and in systems containing unreacted phenol during the production of paratertiary butylphenol, contamination of phenol into the wastewater is unavoidable. The present invention is a method that facilitates industrial implementation from this viewpoint as well.

The raw material used in the method of the present invention, mixed butene, is
C ₄ hydrocarbons produced by extracting butadiene from C ₄ hydrocarbons produced from the steam cracking and catalytic cracking processes of naphtha and gas oil can be used;
Contains %. This mixed butene contains 1-butene, 2-butene, n-butane, and isobutane as components other than isobutylene. Mixed butene is
It is possible to charge the catalyst and phenol continuously or all at once into a reaction tank, but in order to remove C ₄ hydrocarbons that do not participate in the reaction, it is possible to carry out the reaction by combining continuous or intermittent introduction and exhaust. desirable. It is also possible to react the catalyzed phenol with mixed butenes in alternating current or cocurrent in the column. The amount of mixed butene used is 1/5 to 3/1, preferably 1/3 to 1/1 in terms of molar ratio to phenol as the amount of pure isobutylene.

The arylsulfonic acid catalyst used in the first stage reaction of the method of the present invention is as follows. That is, benzene, naphthalene, anthracene, phenanthrene sulfonic acid, disulfonic acid, trisulfonic acid, tetrasulfonic acid, etc., and these aromatic nuclei are alkyl groups, cycloalkyl groups, amino groups,
It may be substituted with one or more of a hydroxyl group, a halogen group, a nitro group, and a fluorinated alkyl group.

Specifically, benzenesulfonic acids include para-toluenesulfonic acid, orthotoluenesulfonic acid, metatoluenesulfonic acid, benzenesulfonic acid, dimethylbenzenesulfonic acid (2,5-
dimethylbenzenesulfonic acid, etc.), trimethylbenzenesulfonic acid, phenolsulfonic acid (paraphenolsulfonic acid, etc.), benzenedisulfonic acid, benzenetrisulfonic acid, methylbenzenedisulfonic acid, phenoldisulfonic acid, cresolsulfonic acid, chlorobenzenesulfonic acid ( parachlorobenzenesulfonic acid, etc.), fluorobenzenesulfonic acid, trifluoromethylbenzenesulfonic acid, dichlorobenzenesulfonic acid, bromobenzenesulfonic acid, chlorotoluenesulfonic acid, phenoltrisulfonic acid, oxytoluenesulfonic acid, pyrocatechinsulfone acid, resorcindisulfonic acid, nitrobenzenesulfonic acid,
Examples include nitrobenzene disulfonic acid, nitrotoluenesulfonic acid, nitroxylenesulfonic acid, dinitrobenzene disulfonic acid, dinitrotoluenesulfonic acid, cyclohexylbenzenesulfonic acid, and aminobenzenesulfonic acid.

Furthermore, examples of naphthalene sulfonic acids include α-naphthalene sulfonic acid, β-naphthalene sulfonic acid, 1,5-naphthalene disulfonic acid,
2,5-naphthalene disulfonic acid, 2,6-naphthalene disulfonic acid, 1,3,5-naphthalene trisulfonic acid, 2,5,7-naphthalene trisulfonic acid, 2,4,6-naphthalene trisulfonic acid, 2 , 4,6,8-naphthalene tetrasulfonic acid, NW acid (α-naphthol-4-sulfonic acid),
Schiefuric acid (β-naphthol-6-sulfonic acid), croseic acid (β-naphthol-8-sulfonic acid), topiasic acid (2-naphthylamine-1
-sulfonic acid), R acid (β-naphthol-3,6
- disulfonic acid), G acid (β-naphthol-6,
8-disulfonic acid), naphthionic acid (1-naphthylamine-4-sulfonic acid), 2S acid (1-amino-β-naphthol-4-sulfonic acid), H acid (8-disulfonic acid),
-Amino-α-naphthol-3,6-disulfonic acid), γ acid (2-amino-8-naphthol-6-
sulfonic acid), J acid (3-amino-8-naphthol-6-sulfonic acid), amino G acid (2-naphthylamine-6,8-disulfonic acid), Friend acid (4-naphthylamine-2,7-disulfonic acid) ),
Peryic acid (8-naphthylamine-1-sulfonic acid), 5-naphthylamine-1-sulfonic acid, 1
-Naphthylamine-8-sulfonic acid, 1-naphthylamine-4,8-disulfonic acid, 1-naphthylamine-2,4,8-trisulfonic acid, 1-naphthylamine-8-naphthol-4-sulfonic acid,
1-Nitronaphthalene-2-sulfonic acid, 2-nitronaphthalene-1-sulfonic acid, 1-nitronaphthalene-3-sulfonic acid, 1-nitronaphthalene-4-sulfonic acid, 1-nitronaphthalene-5
-Sulfonic acid, 2-nitronaphthalene-5-sulfonic acid, 1-nitronaphthalene-6-sulfonic acid, 1-nitronaphthalene-7-sulfonic acid, 1
-Nitronaphthalene-8-sulfonic acid, 2-nitronaphthalene-8-sulfonic acid, 6-methyl-1
-Nitronaphthalene-5-sulfonic acid, 8-methyl-1-nitronaphthalene-5-sulfonic acid, 5
-Methyl-1-nitronaphthalene-8-sulfonic acid, 7-methyl-1-nitronaphthalene-8-sulfonic acid, 1,3-dinitronaphthalene-5-sulfonic acid, 1,5-dinitronaphthalene-3-sulfonic acid , 1,8-dinitronaphthalene-3-sulfonic acid, 1,8-dinitronaphthalene-4-sulfonic acid, 1-nitronaphthalene-3,6-disulfonic acid, 1-nitronaphthalene-3,7-disulfonic acid, 1 -Nitronaphthalene-3,8-disulfonic acid, 1-nitronaphthalene-4,8-disulfonic acid, 2-nitronaphthalene-4,8-disulfonic acid, 1-nitronaphthalene-5,8-disulfonic acid, 1-nitro Naphthalene-3,6,8-
Trisulfonic acid, 1-nitronaphthalene-4,
Examples include 6,8-trisulfonic acid. Other examples include anthracene sulfonic acid and phenanthrene sulfonic acid.

These arylsulfonic acids can be used alone or in combination of two or more. The amount used is 0.01 to 20% by weight based on the phenol used.
Preferably it is 0.05 to 5%.

The catalyst for the rearrangement reaction in the second stage reaction is silica alumina, activated clay, diatomaceous earth, rare earth substituted zeolite, sulfuric acid, ion exchange resin or/and boron fluoride, but the amount used is based on the charged phenol. 0.05-20% by weight, preferably 0.1-5
%.

In the present invention, the first stage reaction is carried out at a temperature of 20 to 120°C, preferably 50 to 80°C. The second stage reaction is carried out at a temperature slightly higher than this, at 80-200°C, preferably at 100-200°C.
It is carried out at 150℃. Pressure is normal pressure or 15Kg/cm ²
Hereinafter, a pressure of preferably 5 kg/cm ² or less is suitable.

In addition to the raw materials, the method of the present invention can also be carried out in the presence of an inert solvent such as a hydrocarbon solvent or an ether solvent, or an inert gas such as nitrogen or carbon dioxide gas.

The alkylated phenol product, which is the first-stage reaction product according to the method of the present invention, is subjected to the next two-stage reaction with the first-stage reaction catalyst remaining, or after removal by adsorption or water washing as required.

During the alkylation reaction or isomerization (rearrangement) reaction in this method, orthotertiarybutylphenol, 2,4-ditertiarybutylphenol, and 2,4,6-tritertiarybutylphenol are produced as by-products in the method of the present invention. The reaction may be carried out by adding phenol. Furthermore, phenol may be newly added during the isomerization reaction.

Next, the present invention will be explained in more detail with reference to Examples. Note that percentages in the following Examples and Comparative Examples are based on weight.

Example 1 [First stage reaction] Phenol 378 was placed in a SUS autoclave.
g, paratoluenesulfonic acid 0.38g, raise the temperature while stirring and keep it at 50-58℃, and prepare mixed butene [composition (weight): isobutylene 48.4%, 1-butene 26.7%, 2-butene 16.3%, butane 7.8 %, butadiene 0.1%, propadiene 0.1%, propylene
0.1%] was introduced at a flow rate of 175 g/hr and reacted for 3.3 hours. The reaction was carried out under 2 kg/cm ² G, and unreacted mixed butene was exhausted from the outlet. The amount of reaction products is
It weighed 491g.

The molar ratio of reacted isobutylene to phenol at this time was 0.5, and the composition of the reaction product was 49.1% phenol, 14.1% orthotertiary butylphenol, and paratertiary butylphenol.
3.9%, 2,4-ditertyabutylphenol
7.5%, 2,6-ditertyabutylphenol
3.0%, 2,4,6-tritert-butyl phenol 2.9%, para-tert-butyl phenyl ether 1.8%, t-butyl phenyl ether 17.7%, and sec-butyl phenyl ether 0.03%. .

[Second stage reaction] Transfer the above reaction product to 1 flask, add 11.3 g of activated clay, and raise the temperature while stirring to 150℃.
The reaction was carried out for 1 hour. The composition of 489 g of the reaction product, excluding 193 g of phenol, is 2.95% orthotertiary butylphenol, 94.2% paratertiary butylphenol, 2.74% 2,4-ditertiary butylphenol, and 2,6-ditertiary butylphenol. Butylphenol 0, 2,4,6-tritertiarybutylphenol 0.12%, secondary butylphenol was not observed.

The presence of para-toluenesulfonic acid was not observed in the product from which the activated clay was removed after the reaction.

Example 2 [First stage reaction] 304 g of phenol and 0.15 g of α-naphthalene sulfonic acid were added to the stainless steel autoclave from 1, and the temperature was raised while stirring and kept at 68 to 77°C, and 42.2 g of the mixed butene from Example 1 was added. The mixture was introduced at a flow rate of /hr and reacted for 4.5 hours. The reaction was carried out under a pressure of 2 Kg/cm ² G, and unreacted mixed butene was exhausted from the outlet.

The molar ratio of reacted isobutylene to phenol at this time was 0.44, and the composition of the reaction product was 49.4% phenol, 23.3% orthotertiary butylphenol, and paratertiary butylphenol.
8.9%, 2,4-ditertiarybutylphenol
12.7%, 2,6-ditertyabutylphenol
2.8%, 2,4,6-tritertiary butyl phenol, 2.8%, and paratertiary butyltertiary butyl phenyl ether 0.2%.

[Second stage reaction] The above reaction product was transferred to a flask, and α-naphthalene sulfonic acid was removed using 2.5 g of an adsorbent (Kyoward 500SH). this mixture
The material was introduced into a 60 x 500 mm tubular fixed bed reactor packed with 300 g of silica-alumina catalyst having a composition of 75% SiO ₂ and 25% Ai ₂ O ₃ , and the reaction temperature was 170°C, contact time was 1 catalyst/hr raw material. The raw materials were supplied at the rate of .

The composition of the reaction product 386g obtained was phenol.
44.2%, orthotertiarybutylphenol 1.6
%, paratarsia butylphenol 52.6%,
2,4-ditertyabutylphenol 1.5%,
2,6-ditertyabutylphenol 0, 2,
4,6-tritarsiabutylphenol 0.1%,
No secondary butylphenol was detected.

Almost similar results were obtained in a reaction using zeolite substituted with a rare earth metal instead of silica alumina.

Example 3 [First reaction] Phenol was added to the SUS autoclave in step 1.
296.8g, 2.5-dimethylbenzenesulfonic acid 0.15
g was charged, the temperature was raised while stirring and maintained at 70 to 79°C, and the mixed butene of Example 1 was introduced at a flow rate of 49 g/hr and reacted for 4 hours. The reaction was carried out under a pressure of 2 Kg/cm ² , and unreacted mixed butene was exhausted from the outlet.

The molar ratio of reacted isobutylene to phenol at this time was 0.44, and the composition of the reaction product was 52.1% phenol, 23.4% orthotertiary butylphenol, and paratertiary butylphenol.
8.7%, 2,4-ditertyabutylphenol
10.8%, 2,6-ditertyabutylphenol
2.6%, 2,4,6-tritert-butylphenol 2.2%, total secondary butylphenol 0.2
It was %.

[Second stage reaction] Transfer the above reaction product to 1 flask and add concentrated sulfuric acid.
Add 160g and raise the temperature while stirring, and raise the temperature to 110℃.
Allowed time to react. The composition of 375 g of the reaction product is 39.0% phenol, 2.7% orthotertiary butylphenol, and paratertiary butylphenol.
56.9%, 2,4-ditertyabutylphenol
1.3%, 2,6-ditertiarybutylphenol 0, 2,4,6-tritertiarybutylphenol 0.1%. Total secondary butyl phenol was 0.1% or less.

Example 4 [First stage reaction] 376.6 g of phenol, 2,
Add 0.38 g of 4,6-trinitrobenzenesulfonic acid, raise the temperature while stirring, and keep it at 55-60.
The mixed butene of Example 1 was introduced at a flow rate of 188 g/hr and reacted for 3 hours. The reaction was carried out under normal pressure, and unreacted mixed butene was exhausted from the outlet.

The molar ratio of reacted isobutylene to phenol at this time was 1.18, and the composition of the reaction product was 15.4% phenol, 19.9% orthotertiary butylphenol, and paratertiary butylphenol.
8.4%, 2.4-ditertiarybutylphenol 46.4
%, 2,6-ditertyabutylphenol 2.4
%, 2,4,6-tritert-butylphenol 4.0%, and total secondary butylphenol 1.5%.

[Second stage reaction] 508 g of phenol and 9.4 g of boron trifluoride ether complex salt (BF ₃ purity 47%) were added to the above reaction product, the temperature was raised while stirring, and the mixture was reacted at 110° C. for 1 hour. The composition of 114 g of the reaction product is 37.3% phenol, orthotertiary butylphenol.
9.5%, paratarsia butylphenol 46.3%,
2,4-ditertyabutylphenol 6.8%,
2,6-ditertyabutylphenol 0.1%,
Total secondary butylphenol was 1.3%.

Example 5 [First stage reaction] 303.5 g of phenol and 0.15 g of parachlorobenzenesulfonic acid were placed in the glass reactor 1, and the temperature was raised while stirring and maintained at 65 to 70°C.
of mixed butene was introduced at a flow rate of 51.2 g/hr and reacted for 4 hours. The reaction was carried out under normal pressure, and unreacted mixed butene was exhausted from the outlet.

The molar ratio of reacted isobutylene to phenol at this time was 0.48, and the composition of the reaction product was 50.7% phenol, 20.3% orthotertiary butylphenol, and paratertiary butylphenol.
9.1%, 2.4-ditertiarybutylphenol 13.0
%, 2,6-ditertyabutylphenol 2.8
%, 2,4,6-tritertiary butyl phenol 2.6%, and paratertiary butyltertiary butyl phenyl ether 1.5%.

[Second stage reaction] An adsorbent (Kyoword) is added to the above reaction product.
After adding 3.0 g of 500SH), ±9.1 g of active diatomaceous material was added, the temperature was raised while stirring, and the mixture was reacted at 150° C. for 1 hour. 370g of catalyst removed from reaction product
The composition is 38.7% phenol, 2.3% orthotertiary butylphenol, 56.1% paratertiary butylphenol, 1.3% 2,4-ditertiary butylphenol, 0,2,4-ditertiary butylphenol. , 6-tritarsiabutylphenol 0.1%, and others 1.5%.

Example 6 [First-stage reaction] Add 299.9 g of phenol and 0.20 g of paraphenolsulfonic acid to the glass reactor of Example 1, raise the temperature while stirring, and maintain at 70 to 75°C. The mixture was introduced at a flow rate of 1, and reacted for 6 hours.
The reaction was carried out under normal pressure, and unreacted mixed butene was exhausted from the outlet.

The composition of the reaction product is 50.3% phenol, 25.4% orthotertiary butylphenol, 10.1% paratertiary butylphenol, 10.3% 2,4-ditertiary butylphenol, and 1.9% 2,6-ditertiary butylphenol. , 2,4,6-tritertiary butylphenol 2.0%, paratertiary butyltertiary butyl phenyl ether
It was 1.4%.

[Second stage reaction] 9.0 g of activated clay was added to the above reaction product, the temperature was raised while stirring, and the mixture was reacted at 130° C. for 1 hour.
The composition of the product after removing the catalyst from the reaction product is 38.4% phenol, 1.7% orthotertiary butylphenol, and 58.1% paratertiary butylphenol.
%, 2,4-ditertyabutylphenol 1.6
%, 2,4,6-tritertyabutylphenol 0.2%.

Example 7 [First stage reaction] Phenol 376 was placed in the SUS autoclave of 1.
g, prepare 1.88 g of paratoluenesulfonic acid,
The temperature was raised while stirring and maintained at 50 to 59°C, and the mixed butene of Example 1 was introduced at a flow rate of 293 g/hr and reacted for 3 hours. The reaction was carried out at 2 kg/cm ² G, and unreacted mixed butene was exhausted from the outlet.

The molar ratio of isobutylene to phenol reacted at this time was 1.03, and the composition of the reaction product was 25.6% phenol, 20.9% orthotertiary butylphenol, and paratertiary butylphenol.
4.7%, 2,6-ditertyabutylphenol
11.2%, 2,4-ditertyabutylphenol
19.2%, 2,4,6-tritert-butyl phenol 16.3%, tert-butyl phenyl ether 0.01%, secondary butyl phenyl ether
It was 0.2%.

[Second Stage Reaction] The above reaction product was transferred to a flask, and 11.3 g of activated clay was added thereto and reacted at 150° C. for 1 hour. After removing the catalyst from the reaction product, the reaction composition is 6.9% phenol, 2.4% orthotertiary butylphenol, and paratertiary butylphenol.
76.6%, 2,4-ditertiarybutylphenol
13.7%, 2,4,6-tritertiarybutylphenol 0.3%, and no secondary butylphenol was observed.

Comparative Example 1 (Example in which arylsulfonic acid is not used in the first stage reaction) Phenol 332.8 was added to the same experimental apparatus as in Example 1.
Pour 11.1 g of activated clay, raise the temperature to 120℃, and heat to 250℃.
introducing the mixed butenes of Example 1 at a flow rate of g/hr;
The reaction was allowed to proceed for 1 hour.

The composition of the reaction product at this time is phenol
33.2%, orthotertiarybutylphenol 3.3
%, paratarsia butylphenol 31.3%,
The contents were 3.0% 2.4-ditert-butylphenol, 8.8% ortho-secondary butylphenol, 14.4% para-secondary butylphenol, and 5.9% 2,4-disebutylphenol.

Comparative Example 2 (Example in which the first stage reaction is carried out at a relatively high temperature) 366 g of phenol was placed in the same experimental apparatus as in Example 1.
2,4,6-trinitrotoluenesulfonic acid 0.37
The mixed butene of Example 1 was introduced at a flow rate of 220 g/hr, and the mixture was reacted for 1 hour.

The composition of the reaction product at this time is phenol 29.6
%, orthotertiary butylphenol 2%, paratertiary butylphenol 30.4%, 2,4-
The contents were 2% ditertiary butylphenol, 10% ortho-secondary butylphenol, 7% para-secondary butylphenol, and 12% 2,4-disebutylphenol.

Claims (1)

[Claims] 1 In the presence of an arylsulfonic acid catalyst, isobutylene containing n-butenes and phenol are mixed at 20 to 120
selectively reacting isobutylene at °C and then removing or not removing the catalyst selected from the group consisting of silica alumina, activated clay, diatomaceous earth, rare earth substituted zeolites, sulfuric acid, ion exchange resins and boron fluoride. A method for producing high-purity paratertiary butylphenol, which comprises carrying out a rearrangement reaction at 80 to 200°C in the presence of at least one catalyst.