JPS60193937A - Production of alcohol by hydration of olefin - Google Patents

Abstract

PURPOSE:To suppress the harmful side reactions in the production of an alcohol by hydrating an olefin in the presence of a ferrierite catalyst, and to elongate the life of the catalyst, by using a catalyst calcined at a specific temperature in the presence of steam. CONSTITUTION:A ferrierite calcined at 400-900 deg.C, preferably 600-800 deg.C for 0.5-24hr, preferably 2-10hr in the presence of steam, preferably a hydrogen ion-type ferrierite wherein at least a part of the cation is hydrogen ion, is used as the catalyst for the hydration of an olefin, preferably ethylene, propylene or butene. An alcohol can be produced by this process, suppressing the side reactions such as the polymerization and coking of the olefin, keeping the catalytic property stably for a long period, and maintaining long catalytic life.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing alcohols by hydration of olefins. More specifically, the present invention includes:
This invention relates to a method for producing a corresponding alcohol by reacting an olefin with water using ferrierite, a type of crystalline aluminosilicate, as a catalyst.

Many methods have been known for producing corresponding alcohols by hydration of olefins. For example, a typical method is a method using mineral acids such as sulfuric acid and phosphoric acid. In the production of ethanol by the hydration reaction of ethylene, a gas phase method using a phosphoric acid catalyst supported on a carrier such as silica gel is industrially employed. However, this method requires a lot of energy to recover unreacted ethylene and separate and purify the produced ethanol due to the low conversion rate of ethylene, and the supported phosphoric acid elutes, reducing the activity. For,
There are also problems such as corrosion, which requires constant addition of phosphoric acid.

Furthermore, in the production of impropatol or butanol by the hydration reaction of propylene and butenes, a liquid phase method using sulfuric acid is still used industrially. However, this method has drawbacks such as requiring a large amount of energy to concentrate and regenerate the sulfuric acid used, and the equipment being severely corroded by the acid. For this reason, there has been a strong desire to develop a highly active iso-acid catalyst to replace this.

Attempts to use solid acid catalysts for the aqueous phase of olefins include, for example, complex oxides made of silica, alumina, zirconia, titanium oxide, molybdenum oxide, tungsten oxide, etc., and metal phosphates such as aluminum phosphate, zirconium phosphate, etc. There are methods of using crystalline aluminosilicates, generally called zeolites, such as salts of zeolites (acid salts, mordenai) and YaM zeolites. However, the methods using these conventionally proposed catalysts have problems such as weak acid strength, insufficient activity, and gradual decline in activity when reacted at high temperatures.
Industrially, it was not satisfactory.

The inventors of the present invention were aware of this situation, and as a result of intensive investigation, they discovered that ferrierite, a type of crystalline aluminone ricade, has extremely high catalytic performance for the hydration reaction of olefins. Heading, first patent application 1984-1
In No. 79101, a method for producing alcohol by hydration of an olefin was proposed, characterized by using ferrierite as a catalyst.

In order to further improve the catalytic performance of ferrierite, the present inventors have conducted various studies, and as a result, we have developed a long-life catalyst that suppresses side reactions such as olefin polymerization and coking, and exhibits stable performance over a longer period of time. I came to find out.

That is, in the present invention, when producing alcohol by hydration of olefin, in the presence of water vapor, 400 to 900
The present invention provides a method for producing alcohol, characterized in that ferrierite calcined at °C is used as a catalyst.

Although the reason for the effect of calcination treatment in the presence of water vapor is not clear, it is thought that this effect is due to the change in the solid acid properties of ferrierite due to the action of water vapor at high temperatures. It is well known that when scale ion type mordenite or the like is treated with steam at high temperature and then treated with acid under harsh conditions, there is a phenomenon in which aluminum atoms contained in the zeolite structure are removed.

It is also known that this dealumination treatment affects the properties of zeolite catalysts, for example, JP-A-58-1
No. 24723 discloses that dealuminated mordenite and the like are highly active in the aqueous phase of olefins. However, this publication does not mention the catalyst life at all, nor does it contain any description regarding ferrierite.

In the method of the present invention, even if ferrierite is subjected to steam treatment at high temperature and then acid treatment, the amount of aluminum atoms contained in ferrierite hardly changes,
It was confirmed that the calcination treatment in the presence of steam in the present invention is completely different from ordinary dealumination treatment. Therefore, in the method of the present invention, the calcination treatment in the presence of steam changes the solid acid properties that ferrierite originally had, and as a result, the selectivity of the olefin hydration reaction improves, and the olefin hydration reaction improves. It is thought that harmful side reactions such as polymerization and coking were suppressed, leading to an improvement in catalyst life.

Ferrierite calcined in the presence of steam is a long-life catalyst that can maintain stable catalytic performance over a very long period of time, and the present invention provides an extremely excellent method for producing alcohol.

The present invention will be explained in more detail below.

In the method of the present invention, ferrierite is used as a catalyst, and ferrierite is usually a crystalline aluminosilicate having a chemical composition expressed by the following formula in molar ratio of oxides.

M/n　O・ht,o,・(5-100)SiO.

However, M is a cation of valence n, and the coefficient of M2//no is around 1.

The crystal structure of ferrierite is described in the Journal of Catalysis.
) Volume 35, pages 256-272 (published in 1974).

That is, ferrierite is a zeolite having a main cavity consisting of a 10-membered ring of oxygen atoms with an effective pore diameter of about 5X.

Generally, the crystal structure of such zeolites is determined by X-ray diffraction and is distinguished from other zeolites by its powder x#11 diffraction pattern.

Table 1 shows the powder X-ray diffraction measurement results of ferrierite described in the above-mentioned literature as a typical powder X-ray diffraction pattern of 7-elierite.

Table 1? , 41 100 200 ZOO24020 6,5624011 A72 12310 5.41 12220 397 45051 592 57420 583 27411 175 40550 565 34510 552 45040 547 582 02 A30 1524G 115 28312 504 20451 194 10530 2.88 10620 2.56 3350 In addition to the above-mentioned document, the method for synthesizing ferrierite is described in Japanese Patent Application Laid-Open No. 1983
This method is disclosed in Japanese Patent Application No. 127898, Japanese Patent Application Laid-Open No. 55-85415, Japanese Patent Application No. 176077-1980, and the like. In the method of the present invention, the 7-elierite used as a catalyst can be produced by any of these methods.

For example, (1) alkali metal hydroxide or alkaline earth metal hydroxide, alumina or alkali metal aluminate, colloidal silica sol or alkali metal silicate, and N-methylpyridine hydroxide in a molar ratio of the oxides. It is expressed as the following composition 5i02 /At203-5~16
0 (MO+%O)/SiOt”=α07~1.8
(%O+R20)/Rx O= (15~20H,O/
(M, /nO+R,O) −50 to 170 (here, M
represents an alkali metal or alkaline earth metal of valence n, and R represents N-methylpyridine. ) and heating the aqueous gel at a temperature of about 140 to 160°C for several days, (2)
3 to 15w as aluminum At, O, in anhydrous terms
Ferrierite is produced by crystallizing a granular amorphous aluminosilicate homogeneous compound containing α4 to 17 wt% as alkali metals A and O (A represents an alkali metal) in water or an aqueous alkali metal hydroxide solution. One example is a method of synthesizing.

The 7-elierite used in the method of the present invention is used in a hydrogen ion form. For this purpose, hydrogen ions can be produced by conventionally known ion exchange treatment, that is, by first ion-exchanging them into ammonium ions using ammonium chloride, etc., and then by calcination or treatment in an aqueous solution of mineral acids such as hydrochloric acid. Ion exchange can be done directly. The hydrogen ion exchange rate, that is, the degree of ion exchange to hydrogen ions, is usually about 30% or more of the exchangeable cations, especially about 709
The above is preferable. If the hydrogen ion exchange rate is less than 30%, the solid acidity of ferrierite will not be sufficiently exhibited, and therefore the hydration activity of the olefin will be low.

Note that when the synthesized ferrierite contains organic cations such as N-methylpyridine, it is preferable to remove the organic cations in order to further increase the hydrogen ion exchange rate. For this purpose, ferrierite containing organic cations is heated at 400 to 700°C under air circulation.
Preliminary firing treatment may be carried out for 1 to 10 hours within the range of 1 to 10 hours.

In the method of the present invention, ferrierite used as a catalyst is calcined in the presence of steam. There are no particular restrictions on the firing method, and the firing process may be performed in the presence of water vapor, for example, while circulating a mixed gas of water vapor and air. At this time, the concentration of water vapor is not particularly limited, but is particularly preferably 20% or more. Firing temperature is 400-900
The temperature range is preferably from 600 to 800°C. If the temperature is less than 400°C, the effect of the present invention due to the presence of water vapor cannot be expected, and if it exceeds 900°C, there is a high possibility that the crystal structure of ferrierite will be destroyed, which is not preferable.

There is a close relationship between water vapor concentration and firing temperature; if the water vapor concentration is high, a large effect can be expected even if the firing temperature is low, and if the water vapor concentration is low, a higher firing temperature is required. be. For example, ferrierite fired at 700°C in the presence of air containing 30% water vapor and ferrierite fired at 600°C in the presence of air containing 50% water vapor have almost the same effect. Observed.

The time required for firing is preferably in the range α5 to 24 hours, preferably in the range 2 to 10 hours. α If the time is less than 5 hours, the effect of steam calcination cannot be obtained, and if the calcination treatment exceeds 24 hours, the crystal structure of ferrierite may be destroyed.

In the method of the present invention, there is no particular restriction on the shape of the catalyst, and a molded catalyst may be used, but it may also be used as a powder. The molding method may be a conventional method, such as a compression molding method, an extrusion molding method, a spray drying granulation method, and the like. When molding, a substance inert to this reaction may be added as a binder or molding aid for the purpose of increasing its mechanical strength. For example, silica, alumina, silica-alumina, clays, graphite.

0 to 8 stearic acid, starch, polyvinyl alcohol, etc.
It can be added in an amount of 0%, preferably 2 to 30%.

The olefin hydration reaction of the present invention can be carried out in either gas phase or liquid phase, and reaction methods include conventionally known methods such as fixed bed flow system, fluidized bed system, and stirred suspended bed system. Any reaction method can be adopted. Various kinds of olefins can be used as raw materials, but those having 2 to 8 carbon atoms are generally suitable, especially those having 2 to 4 carbon atoms.
lower olefins, namely ethylene and propylene.

Butenes etc. are suitable.

The hydration reaction of olefins is an equilibrium reaction with the dehydration reaction of alcohol, which is its reverse reaction, and lower temperatures and higher pressures are generally more advantageous for producing alcohol. However, the situation differs significantly depending on the type of raw material olefin. Further, from the viewpoint of reaction rate, higher temperatures are more advantageous. Therefore, it is difficult to uniformly define suitable reaction conditions, but the reaction temperature is usually in the range of 50 to 350°C.
A range of about 100-300°C is particularly preferred.

If the reaction temperature is less than 50°C, a sufficient reaction rate cannot be obtained,
Further, if the temperature exceeds 650°C, not only is it disadvantageous in terms of equilibrium theory, but also side reactions such as olefin polymerization reaction proceed, which is undesirable.

Further, there is no particular restriction on the reaction pressure, but the higher the pressure, the more advantageous it is from the viewpoint of equilibrium theory. However, from an industrial economic point of view, it is undesirable for the reaction pressure to become too high. Therefore, the reaction pressure is usually 1 atm to 60
A range of 0 atm is preferred, and a range of 1 atm to 250 atm is particularly preferred.

The molar ratio of water to raw olefin is also an important factor that greatly influences the reaction, along with reaction temperature and pressure. The larger the molar ratio of water to olefin, the more advantageous it is in terms of equilibrium, and a high conversion rate of olefin can be obtained, but if the molar ratio of water is too large, the concentration of alcohol in the resulting product liquid will be low. , separation and purification of alkotyl from the product liquid requires a lot of energy, which is economically disadvantageous. On the other hand, when the molar ratio of water to olefin is reduced, a highly concentrated alcohol bath solution can be obtained, but the conversion rate of olefin becomes low and side reactions such as olefin polymerization occur. Therefore, the molar ratio of water to olefin is about 0.2-100
The mo1/mol range is good (0.3~50 no.

A range of 1 is particularly preferred.

The raw material olefin contains saturated hydrocarbons such as methane, ethane, and propane, erthyl compounds such as diethyl ether, ketones such as acetone, inert gases such as nitrogen and carbon dioxide, hydrogen and other gases, etc. It is fine and there is no particular problem.

In the method of the present invention, the contact time depends on the reaction mode.

Although it is difficult to specify uniformly because it varies depending on the conditions, etc., taking the case of a gas phase fixed bed flow reaction method as an example, the gas hourly space velocity (GH8V) of raw material olefin and water is 10 to 1.
ao 00hr-” is good, 100~50o a h
r-” is particularly preferred.

The alcohol produced by the reaction can be separated and purified from the product liquid by a conventional method, and unreacted olefin can also be recovered and recycled.

Below, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited only to these examples. Incidentally, the equilibrium column 'reach rate' used in the examples indicates the catalyst performance, and represents a numerical value calculated by the following formula.

Example 1 A 1-sulfuric acid acidic aluminum sulfate aqueous solution (ht, o, ~4.4
4v/v%, H, 1304=2s, bqw/v%) and sodium silicate aqueous solution (Na, O-&56w/y%,
SiO,=”2αOOW/V%.

A40H-(L22W/v%), α25
1/hr and α75 t/hr feed rates simultaneously and continuously and allowed to react under stirring.

The residence time of the reaction slurry was 60 minutes, the pH of the slurry was 6.2, and the reaction temperature was 32°C.

The slurry product overflowing from the reaction tank was separated into solid and liquid and thoroughly washed with water to obtain a homogeneous compound having the following composition.

Na, O: 5.2 wt% (dry base) A4
03: 7.13wt% (dry base) Sin,
: 87.7 vrt% (dry base) H,O:
59.7 wt% (wet base) CL 89 w
The homogeneous compound 555.69 was added to an aqueous sodium hydroxide solution 5052 having a concentration of t% and stirred to prepare a starting slurry. Pour this slurry into an autoclave and
Crystallization was carried out by holding at 80° C. and its autogenous pressure for 72 hours.

Thereafter, the mixture was cooled to room temperature, and the solid crystals formed were filtered, washed with water, and dried. As a result of powder X-ray diffraction measurement using the 0ulCα double line of the zeolite, the results are shown in Table 2.
It coincided with the y-s turn.

Table 2 9.40 9.40 100 12.50 7.07 28 12.80 A91 27 1i0 6.60 26 15.40 5.75 15 15.70 5.64 13 22.30 59857 2Z56 59441 252058527 2568 A75 48 24.46 56333 25.20 155 80 25.77 54565 2&50 A36 17 2496'5.30 18 2EL58 A12 28 29.42 50325 3α38 2.94 11 3 [LL6 288 10 Further, as a result of elemental analysis, it had the following composition.

1.03 Na, O, Az, O, s19.3 Sin.

This crystal was subjected to ion exchange treatment at 90° C. for 5 hours in a 2N ammonium chloride aqueous solution. Wash with water.

After drying, it was baked at 540° C. for 3 hours under air circulation.

As a result of elemental analysis, it had the following composition.

Q, 01 Na, O・AL20. *19. I Sin.

This crystal powder was subjected to steam calcination treatment at 70-0° C. for 6 hours while circulating air containing a large amount of water vapor. After the steam calcination treatment, the ferrierite was acid-treated using a 6N hydrochloric acid aqueous solution, and its composition was confirmed by elemental analysis: 0.01 Na, OIIAL20. @ 19.45
in2, indicating that dealumination has not progressed.

Further, the powder X-ray diffraction pattern hardly changed before and after the steam treatment, and the crystallinity of the steam fired product was about 95.5% based on the synthesized ferrierite.

Acid clay (Mizusawa Chemical Co., Ltd.) as a binder was added to the steam fired crystal powder to a concentration of 120 wt%, an appropriate amount of water was added, and the mixture was extruded into a 3-inch diameter at 120°C.
Dry for an hour. Further, it was fired at 500° C. for 3 hours under air circulation.

Ethylene hydration reaction was carried out using this catalyst. The catalyst 21.4d was placed in a Pyrex reaction tube (20 mm φ x 50
0 ml, ) and the catalyst was fed with a mixture of water to ethylene molar ratio t Omol/mol. The reaction conditions were 230°C under normal pressure.

GH8V=15oohr-1. All reaction products were quantified using a gas chromatograph.

The results are shown in Table 6. Almost no change over time was observed even after 10 hours had passed after the start of the reaction, and no by-products of butene or hexene due to the polymerization of ethylene were observed.

Example 2 6aBt of N-methylpyridine iodide, 22.59% of sodium hydroxide, and 111% of sodium aluminate were dissolved in 7202% of water. Next, silica sol (Si023
0% by weight) was added to prepare a reaction mixture having the following compositional molar ratio.

S i02 /A t20s =3 EL 8(Na2
o+R2o)/st, o□=0.39H,O/(Na
, O+R20: = 1o 6Na2o/R20=
2.0 (where R is N-methylpyridine) The reaction mixture was placed in a 21 autoclave and heated at a temperature of 150 °C for 6
It was heated for several days to crystallize. Then cool to room temperature,
Filter the formed solid crystals and wash with water.

Dry. Powder X due to the CuKα doublet of the zeolite
As a result of the ray diffraction measurement, the X-ray diffraction pattern shown in Table 2 was obtained, which matched that of ferrierite.

Further, as a result of elemental analysis, it had the following composition.

0.27 R,0-(173x,oeAL,o,*2a
3 sio.

This crystal was fired at 540°C for 3 hours under air circulation, and then subjected to ion exchange treatment and firing treatment in the same manner as in Example 1. As a result of elemental analysis, it had the following composition.

α02 Na, O*A4,0. e27.65i02 This crystal powder was subjected to steam calcination treatment in the same manner as in Example 1, further molded, and calcination treatment was performed to prepare a catalyst. Using this catalyst, ethylene hydration reaction was carried out under exactly the same reaction conditions as in Example 1. The results are shown in Table 3.

Comparative Example 1 Using the ferrierite synthesized in Example 1, no steam calcination treatment was performed, and the other operations were exactly the same.
An air-calcined catalyst was prepared.

Using this catalyst, ethylene hydration reaction was carried out under exactly the same reaction conditions as in Example 1. The results are shown in Table 3 together with Example 1.2. When this catalyst was used, the initial activity was high, but the activity changed significantly over time. Also, butene, which is a polymer of ethylene.

By-products of hexenes were observed.

Table 3 Examples 3 to 5 Using the ferrierite synthesized in Example 1, while circulating air containing 30% water vapor concentration, 500.6
A catalyst calcined at 00,800'Q was prepared. Ethylene hydration reaction was carried out using these catalysts. The reaction conditions are exactly the same as in Example 1. The results are shown in Table 4.

Table 4 Examples 6 to 8 Using the ferrite synthesized in Example 1, the steam calcination temperature was set to 700°C, and the steam concentration was set to 10.
Catalysts were prepared with different concentrations of 50 and 100%. Ethylene hydration reaction was carried out using these catalysts. The reaction conditions are exactly the same as in Example 1. The results are shown in Table 5.

Comparative Example 2 Using the ferrierite synthesized in Example 1, a catalyst was prepared by performing a calcination treatment at 700° C. while circulating air containing no water vapor.

Ethylene hydration reaction was carried out using this catalyst.

The reaction conditions are exactly the same as in Example 1. The result is the fifth
Shown in the table.

Table 5 Example 9 Using the steam calcined catalyst prepared in Example 6, the synthesis of impropatol by hydration of propylene was carried out. The molar ratio of water to propylene is 1. Om
o'vrnox feedstock was GH8V1500hr-
1 to the catalyst, and the reaction temperature was 150°C.

The reaction pressure is normal pressure. The reaction results showed that the equilibrium attainment rate was 75.6% after 1 hour of reaction time, and 75.4% after 10 hours.
Met.

Note that no hydrocarbon by-products were observed.

Example 10 Using the steam calcined catalyst prepared in Example 1, 1llee-butanol was synthesized by hydration of 1-butene. The molar ratio of water to 1-butene is 1.0
mol/mob of feedstock to GH8V750 hr-
1 to the catalyst, and the reaction temperature was 150°C.

The reaction pressure is normal pressure. The reaction result is reaction elapsed time 1
Equilibrium attainment rate is 87.0% in hours and 84.8% in 10 hours.
Met.

The 5ec-butanol selectivity was 993%, and no hydrocarbon by-products were observed.

Example 11 Using the steam calcined catalyst prepared in Example 5, tert-butanol was synthesized by hydration of imbutene. The molar ratio of water to isobutine is to
Moz/mo1 feedstock was fed to the catalyst at GH8V750 hr''. Reaction temperature was 110°C.

The reaction pressure is normal pressure. As a result, the equilibrium attainment rate was 72.4% after 1 hour of reaction time, and 72.4% after 10 hours.

The selectivity of tert-butanol was 99.7%, and no hydrocarbon by-products were observed.

As can be seen from the above examples, the method of the present invention not only achieves significantly higher equilibrium attainment rate and selectivity than conventional methods, but also has the advantage of being able to produce alcohol stably over a long period of time. It has both.

Procedural amendment May 30, 1980 Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office 1 Display of the case 1982 Patent Application No. 49193 2 Name of the invention Process for producing alcohol by hydration of olefin 6 Relationship with the case Patent Applicant Address 4560 Oaza Tomita, Shinnanyo City, Yamaro Prefecture 746 Telephone Number (585) 3311 6. “Detailed Description of the Invention” column of the specification to be amended 7. Contents of the amendment Page 7, line 11 of the specification cylinder ``For ferlinyrite described in the above document'' is changed to ``for copper described in the above document.
7 Elierite using a double line...'' is corrected.

Claims (3)

[Claims] (1) A method for producing alcohol, which comprises using ferrierite calcined at 400°C to 90Q°C in the presence of water vapor as a catalyst when producing alcohol by hydration of olefin. (2) Claim M (1) At least a part of the exchangeable cations of ferrierite are hydrogen ions.
) The manufacturing method described in section 2. (3) The production method according to claim 1) or (2), wherein the olefin is ethylene, propylene or butenes.