JPS6210028A - Decomposition of di-sec-ether - Google Patents

Abstract

PURPOSE:To produce a secondary alcohol in high selectivity, by decomposing a di-sec-alkyl ether in the presence of a high-silica zeolite catalyst having a specific silica/alumina ratio. CONSTITUTION:A secondary alcohol (e.g. isopropanol, sec-butyl alcohol, etc.) can be produced by decomposing a di-sec-alkyl ether (e.g. diisopropyl ether, sec-butyl isopropyl ether, etc.) in the presence of a catalyst consisting of a zeolite having a silica/alumina (molar) ratio of >=10, especially preferably mordenite, zeolite Y or synthetic aluminosilicate having a silica/alumina (molar) ratio of 20-500. The olefin (e.g. propylene, butene-1, etc.) produced as a by- product of the decomposition reaction is also a useful chemical raw material.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing secondary alcohols. More specifically, the present invention relates to a method for producing a secondary alcohol using a di-secondary alkyl ether as a raw material.

BACKGROUND OF THE INVENTION Techniques relating to the decomposition of alkyl ethers have been previously investigated as a method for producing imbutylene by decomposing tertiary ethers, particularly methyl tert-butyl ether. This is attracting attention as an advantageous industrial process to replace sulfuric acid extraction as a separation method for tertiary olefins, but
There is no mention of a method for producing secondary alcohols by decomposition of primary ethers.

Tertiary ether can be decomposed by a method using an activated carbon catalyst in the gas phase (Japanese Patent Publication No. 54-41564), or by a gas phase decomposition method using a catalyst obtained by calcining silica-alumina at 700 to 1100°C (Japanese Patent Publication No. 54-41564). 60-21971), a method using an aluminum-containing silica catalyst (Japanese Patent Application Laid-Open No. 57-853)
No. 23), a method using a strong acid type ion exchange resin, etc., which uses carbon dioxide, tertiary olefin, and primary alcohol as the target products.

Problems to be Solved by the Invention Di-secondary alkyl ethers cannot be produced by dehydration condensation of secondary alcohols, reactions between di-secondary alkyl sulfates and secondary alcohols, etc. Are known.

The decomposition of secondary ether is performed using di-sec-butyl ether (EI).
BI! :), it is thought that the process proceeds as shown in the following equation.

5BK-+SBA+ Oj...(1)S
BA → ○−, +H snow 0 ・・・・・・(2) SBA
In order to obtain (secondary butyl alcohol) with high selectivity, the reaction of the above formula (2) is not preferred.

In general, secondary ethers have lower reactivity than tertiary ethers, so a high temperature reaction is required with ordinary solid acid catalysts such as alumina, clicker alumina, magnesia, and activated clay. ), and coking of the catalyst is likely to occur due to low polymerization of the butene produced.

On the other hand, ion exchange resins have high activity for ether decomposition reactions and can be used at temperatures below the resin's heat resistance temperature, but they are not necessarily suitable for highly selective production of 5BAO because the reaction of formula (2) above cannot be ignored.

Means for Solving the Problem Summary of the Invention As a result of various studies on methods for highly selectively producing secondary alcohols by decomposition of di-secondary alkyl ethers, it was discovered that high-silica zeolite catalysts exhibit excellent activity. Heading The invention has been completed.

That is, the present invention provides a di-secondary alkyl ether in which a high-silica zeolite catalyst having a silica/alumina ratio of 10 or more is used when producing a secondary alcohol using a di-secondary alkyl ether as a raw material. Concerning a method of decomposing ether.

High silica zeolite catalyst The catalyst used in the present invention is silica/alumina (molar ratio)
10 or more zeolite catalyst.

Particularly preferably silica/alumina (molar ratio) 20 to 50
0 mordenite, zeolite Y.

and synthetic aluminosilicates.

■Mordenite Mordenite forms a 12-membered oxygen ring at the entrance of the main cavity, and in addition to existing naturally, it can be synthesized, and as shown in the following formula, the silica/alumina (molar ratio) is 10. be.

α5~50M2/fLO@At! 03・10810.・
0 to 50) 1@0c formula, M is an alkali metal or alkaline earth metal, and n is the valence of the metal M. ] Such mordenite is treated by ■ dealkalization, ■ acid extraction, and ■
Preferably used is one in which the silica/alumina (molar ratio) is increased to 20 to 500 by a suitable combination of steam treatments to form a nonhydrogen type.

Dealkalization here means replacing some or all of the alkali metals or alkaline earth metals contained in mordenite with hydrogen ions, resulting in so-called hydrogen-type mordenite. Dealkalization is usually carried out by treating natural mordenite or synthetic mordenite with an aqueous solution of a water-soluble ammonium salt, such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate, etc. to convert the metal cations in mordenite into ammonium ions, and then calcination. This can be achieved by converting the metal cations in mordenite into hydrogen ions, or by treating natural mordenite or synthetic mordenite with an acid, such as an aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, etc., to convert the metal cations in mordenite into hydrogen ions. However, hydrogen-type mordenite is commercially available and can be synthesized, so dealkalization is not necessarily necessary.

The acid extraction treatment involves bringing the mordenite into contact with a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid, or an organic acid such as acetic acid or formic acid to extract alumina in mordenite. Contact with the above acids
It is desirable to conduct the heating at 20 to 120°C for 1 to 100 hours. The acid extraction treatment may be performed two or more times. Note that this acid extraction treatment can also serve as the above-mentioned dealkalization treatment.

Alkali metals or alkaline earth metals in soludenite are converted into metal oxides by dealkalization and acid extraction treatment (L4
It is desirable to keep it below the weight ratio.

The steam treatment that can be combined with the acid extraction treatment is a heat treatment of mordenite in the presence of steam at 150 to 800°C, preferably 300 to 700°C, for 15 to 50 hours, preferably 1 to 30 hours. .

According to the above method, the silica/alumina ratio is 20~50Ω.
This will bring about great effects in the present invention.

The mordenite used in the present invention exhibits the X-ray diffraction pattern shown in Table 1 below.

1559±(12+ 4.51±0.02
Strong 1α16±12 Strong 597±[Lo
2 Strongest 9.15 Master α1 Strongest 546±C
LO1 Strongest & 55±0.05 Strong 537± [LDl Strong 5.80±α05 Strong 522±αo1 Strong side, Journal of Physical Chemistry Vol. 80 (1976) pp. 60-64 as a method for preparing the catalyst, Tokuko Sho 44-5
1948, JP 46-37166, JP 56-160316, JP 57-10802
Publication No. 3, JP-A-58-164523, JP-A-Sho 5
It is described in 9-222451 to 2'22452 and the like.

■Zeolite Y Zeolite Y is a faujasite-based synthetic zeolite and forms a 12-membered oxygen ring. The catalyst used in the present invention is prepared by extracting and removing alkali metals or alkaline earth metals and aluminum contained therein from this zeolite Y to obtain the silica/alumina ratio described above.

Dealalization and dealumination are accomplished, for example, by contacting silicon tetrachloride. Specifically, after dehydrating and drying zeolite Y at 300 to 500°C, it is brought into contact with silicon tetrachloride vapor while raising the temperature from around room temperature.

It is desirable that the final temperature Fi is 400 to 600°C. By doing this, dealkalization and the silica/alumina ratio can be increased, but in order to further increase the silica/alumina ratio, the acid extraction treatment described above may be combined with a steam treatment if necessary. It is desirable that the amount of alkali metals or alkaline earth metals in zeolite I-Y be 0.4% by weight or less, and it is particularly effective to use silica/alumina ratios of 20 to 500. desirable.

The hydrogen type zeolite Y used in the present invention is the following
The X-ray diffraction diagram shown in the table is shown. The zeolite is also called ultra-stable Y zeolite, and its preparation method is described, for example, in Journal of Catalysis, Vol. 46, No. 100-
p. 106 (1977), Vol. 54, No. 285-288
(1978), etc.

Table 2 14.71±(12 Strongest 5410±αo7 Weak a83±1.2 Strong 5276±CL
O7 strong 7.43 ±12 strong 2.97
6±0.07 Weak 5.71±0.1 Strong 2.875±0.07 Medium 4.7110
．． 1 middle 2. a2o-t=o, o7
Strong 4.33±α1 Strong 2.720±(
LO5 Weak 5 86±Q, 1 Weak z65
5±cL05 Weak 5734±0.07 Strong 2.597±αo5 Medium ■Synthetic aluminosilicate (a) Synthetic aluminosilicate (a) has the general formula 0% [However, M is a metal cation, and n is the corresponding Indicates the valence of the cation. ] The entrance of the main cavity forms a 10-membered oxygen ring or a 12-membered oxygen ring.

Such crystalline aluminosilicates are known and can be prepared using, for example, aluminum compounds such as aluminum sulfate, silicon compounds such as sodium silicate, mineral acids such as sulfuric acid, and metal cations such as sodium chloride. It can be obtained by heating and contacting a reaction mixture containing a salt of , a cationic organic nitrogen compound such as tetrapropylammonium bromide, water, and the like.

As such synthetic aluminosilicate (a), for example, ZBM-5, 28M-11, 28M, which has a 10-membered oxygen term at the entrance of the main cavity developed by Mopil Oil Co., Ltd.
-12,28M -25,ZSM -35,28M-3
8 and the entrance of the main cavity is a 12-membered oxygen ring 28M-4
, ZSM-10, ZSM-20, 28M-43, etc. For example, ZSM-5 has the X-ray diffraction pattern shown in Table 3. These 7. The BM type aluminosilicate is described in detail in the following US patent (aS) specification, British patent (GB) specification or patent publication.

ZSM-5 (US 4702.886), 28
M-8 (GBl, 554,245 L ZBM-
11 (IT81709,979), 28M-1
2 (US 3,832,449), ZSM
-25 (US4.076.842), 28M
-35 (US 4,016,245), ZS
M-58 (U8 4,046,859), 28
M −4 (QB 1,297,256λZ8M −
10 (U8 1692.470), 28M
-20 (US3.972, 9B5), ZEIM
-45 (Japanese Patent Application Laid-open No. 54-68800).

11.3 ±α3 strong 4.63±11
Weak 1α2 ±13 Strong 4.
28±α1 weakz5 ±0.2 weak
586±11 Strongest 7.1-shi α2
Weak &75±0゜05 Ankylosis 0410.
2 Weak 563±α05 Medium 5.7
5±α1 weak 506±α05
Weak & 61±11 Weak 500±105
Strong S, 03±α1 weak Each of the above synthetic aluminosilicates) (a) usually has the general formula silica/alumina (molar ratio), but the proportions of each reagent used during synthesis are changed. By doing so, it is possible to make the ratio even higher.

Further, converting the synthetic aluminosilicate (a) into a hydrogen oxide can be easily achieved by dealkalization treatment and acid extraction treatment as in the case of mordenite.

■Synthetic Aluminum Non-Licade ('b) Synthetic Aluminum Non-Licade (b) has the general formula % [where M is a metal cation and n indicates the valence of the cation. ], the entrance of the main cavity forms a 10-membered oxygen term, and the X-ray diffraction pattern shown in Table 4 is shown.

Table 4 11.2 ±0.2 Strong 575shi c
L05 Strong 1 (LI ±0.2 Strong &73±105 Strong 7.5 ±115
Weak 565±0.05 Strong &0
1±α1 medium 505±Q, 05
5th grade 86±0.05 Strongest 500±
This synthetic aluminosilicate (b) is substantially free of inorganic reactive materials and has the following composition expressed in the following molar ratio: SiO! /At! Os=10~130, M27
, 0 / 8101 = Q, 03 ~ (L5, H2O-
/ M2/nO=100-1,000, X-/810
1 == (L O1-20 [wherein M and n are as defined above and 7%X- is the anion of the salt as a mineralizing agent] is prepared, It is prepared by heating and maintaining the mixture at the crystallization temperature until crystals form (described specifically in JP-A-58-45111).

By changing the ratio of each reagent used during preparation, the silica/alumina (molar ratio) of the above general formula can be arbitrarily obtained, but in order to further increase the ratio, as in the case of mordenite, Acid extraction treatment or zeolite)
As in the case of Y, it may be brought into contact with silicon tetrachloride.

Further, it can be easily converted into a hydrogen form by dealkalization treatment and acid extraction treatment, as in the case of mordenite.

Raw material The raw material used in the present invention is a di-secondary alkyl ether, but the concentration composition is not particularly limited as long as it is a fraction containing a di-secondary alkyl ether.

Diptyl ether, such as diptyle ether, is prepared by the sulfuric acid method,
Alternatively, it is produced as a by-product during the process of producing methyl ethyl ketone (MI[fK) from n-butene using a water utilization method, and is present in the fraction purged out of the system together with other by-products (dimers, etc.).

That is, in addition to the ether, an inert gas, paraffin, olefin, alcohol, aromatic compound, etc. may be contained.

Note that it is preferable not to contain hydrocarbons such as dienes and acetylenes, bases, carbonyl compounds, and the like. Di-secondary alkyl R1-0-R lazy ether is represented by R1, BZ, R
R2R1-0-14 (2) R4 may be branched if the alcohol formed from an alkyl group having 1 to 6 carbon atoms, which may be the same or different, is a secondary alcohol.

Representative examples of the secondary ethers represented by the above general formula and secondary alcohols and olefins obtained from them are shown below. Additionally, ethers with a large number of carbon atoms generally have high decomposition properties.

H2O-0-OH,OR diimpropyl ether inpropatool
Probile/Reaction Conditions The present invention can be carried out in either gas phase or liquid phase, and can be carried out either continuously or batchwise.

When the present invention is carried out in the gas phase, the temperature of the decomposition reaction is 50 to 30
0°C, preferably 80-150°C. The reaction pressure is usually 0 to 50 kl as long as the secondary ether is a gas.
il 7cm2G. During the gas phase decomposition reaction, water vapor may or may not be present, and can be selected depending on the situation, but it is generally expected to be more effective in maintaining activity when carried out in the presence of water vapor. That is, water is used in a H20/secondary ether (1 mole) ratio of 0 to 50. The reaction time varies depending on the catalyst, reaction temperature, etc., but in the case of a continuous method, the secondary ether supply rate per catalyst volume r, usv (hr-1
) is Q, 1-20, preferably [L5-5.

In addition, when carrying out in liquid phase, the decomposition reaction temperature is 50 to 300
'C1 is preferably 80 to 150°C. The reaction pressure may be any pressure that can maintain the liquid phase, and is usually 0 to 50 k.
ll/cm”G. Reaction time (LEEIV
, hr-1) is [Ll~2G, preferably α5~5
It is. Further, during the liquid phase reaction, an appropriate solvent can be selected and used, and water may be present.

As the solvent, oxyacids or derivatives thereof (γ-butyrolactone, r-ogynebutyric acid, etc.), sulfone derivatives (sulfolane, 2-methylsulfolane), etc. are used.

One preferred solvent is γ-butyrolactone.

When r-butyrolactone is used as an aqueous solution having a weight coefficient of 30 to 90, the selectivity for secondary alcohols is particularly improved.

When carrying out the present invention continuously, a known fixed bed reactor is usually used, and adiabatic type, heat exchange type 1, multi-tubular external heating type, etc. can be used.

The present invention is suitable for highly selectively producing di-secondary alcohols from di-secondary alkyl ethers, but the olefins produced at the same time are also useful chemical raw materials. Therefore, the second
If an olefin is required as well as a class alcohol, the ratio of the produced alcohol to the olefin can be adjusted as appropriate. For example, increasing the reaction temperature will increase the yield of olefins. However, if the temperature is increased further, olefin polymerization,
The conditions are chosen in each case, as cogging etc. on the catalyst occur.

The reaction product can be separated and recovered by a known method described in Japanese Patent Publication No. 60-21971.

Effects of the present invention By decomposing di-secondary alkyl ether in the presence of a silica zeolite catalyst, it is possible to obtain secondary alcohols with higher selectivity than with known catalysts for decomposing tertiary ethers. can.

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

In the text, the conversion rate of di-secondary alkyl ether and
The selectivity of grade alcohol is defined as follows.

Di-secondary ether conversion rate (%) 82nd alcohol selectivity (mol%) The catalysts used in Examples and Comparative Examples are explained below.

Catalysts A-D and Fij 1/16 inch (Kxtrudate) were compression-molded, catalyst E was a spherical product, and catalyst G-J was a powder, and after pulverization, 20 to 4
A particle size of 0 mesh was used.

Catalyst A: Synthetic mordenite (trade name: Zeolon 900'N&, manufactured by Two-Tone, USA) was added with 10 weight aqueous solution of ammonium chloride (11 weight percent) and 15 CC of the mordenite, and the mixture was stirred at 8° C. for 1.5 hours to separate the aqueous solution.

This operation was repeated 3 times, the mordenite was thoroughly washed with water, dried at 120°C, and then fired in air at 500°C for 3 hours to obtain 1 Ja10 content CL41.
A hydrogen-type mordenite (catalyst) having a molar ratio of 4 parts by weight lyka/alumina of 10 was prepared.

Catalyst B: 12 parts of 12N hydrochloric acid was added to the above catalyst A as a catalyst.
) 15cc was added, treated at 90°C for 20 hours, removed the aqueous solution, thoroughly washed with water, dried at 120°C, and fired in air at 700°C for 3 hours to obtain a hydrogen-type mordenite with a Nano content of 111 parts by weight and a silica/alumina molar ratio of 31. (Catalyst B) was prepared.

Catalyst C: The above catalyst was treated with air containing 10 parts of water vapor at 700°C for 3 hours (steam treatment), then treated with sufficient 12N hydrochloric acid at 90°C for 10 hours, the aqueous solution was removed, and washed with water. After drying at 700°C, hydrogen-type mordenite (catalyst C) having a nano content α08 weight ratio of chestnut/alumina molar ratio 104 was prepared.

Catalyst D = Steam treatment and 1 in the same manner as above using the above catalyst O
The 2N hydrochloric acid treatment was repeated three times to prepare a hydrogen-type mordenite (catalyst D) having a nano content of α0303 parts by weight and a lyca/alumina (mole ratio) of 201.

Catalysts A to D prepared in this manner show the same X-ray diffraction pattern and no change in mordenite structure.

Catalyst E: Macroporous cation exchange resin (catalyst M)
Amberlyst 15 (trade name, manufactured by Rohm and Haas) was used.

Catalyst F: Silica-alumina manufactured by Nikikki Chemical Co., Ltd. under the trade name N632-HN was used. The silica/alumina (molar ratio) is 5.

Catalyst G: Toyo Soda Kogyo Co., Ltd., trade name T8Z-551 (silica/alumina (-1 nil ratio) = 6) was used as the ultra-stabilized Y-zeolite.

Catalyst H: Add 5 CC of 1N hydrochloric acid per 12 of the catalyst to catalyst G, treat at 8 mC for 3 hours, separate the aqueous solution, and after washing with water,
Dry at 0°C, prepare in air at 600°C for 3 hours, and H! Ll O content (L
An ultra-stabilized Y zeolite (catalyst H) having 33 parts by weight of silica/alumina (molar ratio) was prepared.

Catalyst preparation: Ultra-stabilized Y zeolite (Nano content 11.2 parts by weight, silica/alumina [molar ratio] 73) was prepared using the same method as for catalyst (1) except that 2N hydrochloric acid was used for catalyst G.
catalyst) was prepared.

Catalyst ff: ZSM-5 zeolite was prepared according to the method described in US Pat. No. 3,965,207. That is, 7.4 parts by weight of sulfuric acid, 17.8 parts by weight of tetrapropylammonium bromide, and 86 parts by weight of sodium chloride were added to 195 parts by weight of pure water to prepare an aluminum sulfate solution. This aluminum sulfate solution was mixed with 142 parts by weight of water and 281 parts by weight of No. 5 water glass (Na Snow 09.5%, 810.2%).
6%) and mixed with stirring. The resulting mixture was transferred to a stainless steel autoclave and heated and maintained at 160° C. for 20 hours while stirring. The crystallized solid product was washed with water, dried at 120°C, and then calcined in air at 600°C for 3 hours.

The X-ray diffraction pattern of the obtained solid showed a ZSM-5 crystal structure. This ZSM-5
was treated with a 1N ammonium chloride solution, ion-exchanged, and calcined to prepare a water-based Z8M-s (catalyst J) having a 1Nalo content of 0.1% and a silica/alumina molar ratio of 111.

Examples 1 to 7, Comparative Examples 1 to 3 6 CC of catalyst was charged into a tubular reactor, and a di-sec-butyl ether fraction [di-sec-butyl ether (EBB386 heavy i
%, secondary butanol (8BA) 1 weight part, octene 1
Water was added to the 5-layer F-container and the mixture was brought into contact under normal pressure and under the conditions shown in Table 1.

A known cation exchange resin catalyst (Catalyst E) has a high conversion rate but a very low selectivity to 8BA.

Also, the silica/alumina ratio is low (1
(less than 0), both the conversion rate and selectivity are insufficient.

Examples 8-10 Same catalyst C as in Example 3! , 6CC was charged into a tubular reactor, di-sec-butyl ether fraction (di-sec-butyl ether 88% by weight, secondary butanol 1% by weight, octene 11 qb by weight) was fed, and the amount of water added was varied. , brought into contact under normal pressure.

The results are shown in Table 2.

Example 11 A similar test was conducted using the same catalysts C and 6CC as in Example 3 and using diisopropyl ether (PI) 1 feed with a purity of 98%. The results are shown in Table 3.

Examples 12-20 Into an autoclave filled with 5 tons of catalyst, 50 d of di-secondary butyl ether fraction (SDK 88 weight I 1%, 19BA I weight ratio, octene 11 weight %) and 150 ml of γ-butyrolactone (GBL) aqueous solution were added. The liquid phase reaction was carried out for 5 hours at ℃ and autogenous pressure. The results are shown in Table 4.

Table 4 Example-12B 80 7.2
32.4 61.313090 56
67.8 75.214 0 10 29.6
40.6 52.115C! 0 0
66.5 24.5160 0 52.6 2
&5 44.317 D 80 7.2
6Q, 7 79.818 H807,2Sa4
6 (L519, r 80 7.2 1a
2 51.22OA 80 7.2 a7
5 & 4 Example 21 A di-secondary butyl ether fraction (SBK 86 weight part, 5EA 1 weight part, octene 13 part) and an r-butyrolactone aqueous solution with a concentration of 80% by weight were continuously fed into a tubular reaction tube filled with catalyst C5t. 150℃, 45 kg7
cm''G, LH8'V = 4 (hr-li, H snow 0/8BK molar ratio = 45).

8BK conversion rate 50 hours after the start of the reaction was 4a9%, 8BA
The selectivity was 81.5 molar.

Claims (1)

[Claims] When producing a secondary alcohol using a di-secondary alkyl ether as a raw material, a high-silica zeolite catalyst having a silica/alumina ratio of 10 or more is used.
Decomposition method of class alkyl ether.