JPS59204135A - Preparation of light olefin - Google Patents

Abstract

PURPOSE:In converting methanol and/or dimethyl ether to light olefins, to raise selectivity for the desired compound, to control precipitation of carbon on a catalyst, and to improve catalytic life, by using a mixed catalyst of specific zeolite. CONSTITUTION:In converting methanol and/or dimethyl ether to 2-4C light olefins, a mixed catalyst consisting of offretite-erionite zeolite or clinoptilolite as a main component and 0.05-1wt%, preferably 0.1-0.5wt% zeolite having an entrance of main void consisting of 10-membered oxygen ring and >=5Angstrom size of pore based on the main component is used, to give the desired compound industrially advantageously. Preferably the reaction temperature is 300-500 deg.C, the gas space velocity is 500-20,000hr<-1>, and the pressure is normal pressure- 10atm., and preferably the raw material is diluted with an inert gas and fed onto the catalyst.

Description

[Detailed Description of the Invention] Koichitel is converted using a zeolite catalyst to convert it into carbon atoms having 2 to 4 carbon atoms (
The present invention relates to a method for producing light olefins (hereinafter abbreviated as 02 to C4).

The method of converting methanol and/or dimethyl ether with a zeolite catalyst to produce hydrocarbons is well known. It also produces light olefins such as ethylene, propylene, butylene, etc., which are important as petrochemical raw materials. Regarding the method, for example, there is JP-A-51-122,005, which describes a control index of tO ~ 12.0 and a method using silica.
Crystalline aluminosilicate zeolites with an alumina ratio of 12-4ooo and a crystal density in the form of dry hydrogen form of more than t b y / oc, for example the so-called ZB
The methanol conversion reaction is carried out at low severity using what is known as M-5 zeolite as a catalyst to
A method is disclosed in which a light olefin of No. 1 is obtained with a selectivity of 50 to 60 inches by weight.

Furthermore, according to JP-A No. 53-58,499, a methanol conversion reaction is carried out using 28M-54 zeolite, which is an onretite to erionite zeolite, as a catalyst to obtain light olefins at a rapid production rate of 80% or more by weight. However, it has been reported that carbon precipitation on the catalyst is severe and the activity decreases several hours after the start of the reaction.

As described above, offretite erionite zeolites and the like convert methanol and/or dimethyl ether to produce light olefins with high selectivity, but carbon precipitation on the zeolite catalyst is severe and the activity is greatly reduced. In addition, zeolites in which the entrance of the main cavity is composed of a 10-membered oxygen ring and the pore size is 5x or more, for example, zeolites known as so-called Z B M -5 zeolites, are Although carbon precipitation is small, the selectivity to light olefins is not satisfactory, and large amounts of paraffins and aromatic compounds are produced.

In order to selectively produce light olefins, which are important as petrochemical feedstocks, from methanol and/or dimethyl ether, a catalyst with less carbon deposition on the zeolite catalyst and less reduction in activity is required. The zeolite catalyst, whose activity has decreased due to carbon precipitation, can absorb oxygen-containing gas by 300%
It is known that carbonaceous substances can be burned and removed by flowing under conditions of ~600°C and their activity can be restored.
Reducing the frequency of reprocessing is economical.

It is of great industrial significance.

The present inventors have conducted intensive studies on a method for producing light olefins by converting methanol and/or dimethyl ether with a zeolite catalyst, and have found that the method has high selectivity to light olefins, and furthermore, there is less carbon precipitation on the catalyst. They discovered a catalyst that takes a long time before regeneration treatment is required, and completed the present invention.

That is, the present invention provides a method for producing light olefins by converting methanol and/or dimethyl ether, the main component being offretite erionite yarn zeolite or clinoptilolite, and the main component being Zeolite whose inlet consists of 10 PL oxygen rings and whose pore size is 5X or more is
, 05 to 1.0 is used.

According to the uninvented method, the main cavity is composed of 10 starved oxygen rings and the pore size is 5X. By mixing the above-mentioned zeolites, an industrially extremely advantageous process is achieved in which the period until regeneration treatment is required can be significantly extended without substantially impairing the high selectivity.

Although the reason for the mixing effect of zeolites of X or more is not clear, it is presumed that carbon precipitation in these zeolite-caseolite catalysts is suppressed. Of course, if a zeolite other than zeolite whose main cavity consists of a 10-membered sulfuric ring and whose pore size is 5x or more is added, no effect will be achieved.

The present invention will be explained in more detail below.

In the method of the present invention, a zeolite whose main cavity is composed of a 10-membered oxygen ring and whose pore size is 5x or more is mixed with offretite erionite zeolite or clinoptilolite and used as a catalyst. Each of these is commonly referred to as a crystalline aluminosilicate;
Natural and synthetic products are already widely known. Examples of offretite erionite zeolites include offretite, erionite, Z8M-54 zeolite, and zeolite T. Z SM-54 zeolite is described in JP-A No. 55-5B, No. 499, and zeolite
This is what is described in No. 69. Furthermore, offretite is disclosed in Japanese Patent Application No. 57-14, which is currently being filed by some of the inventors of the present application.
No. 783 can be easily prepared. In addition, as a zeolite whose main cavity is composed of a 10-membered oxygen ring and whose pore size is 5X or more, the so-called z
Mention may be made of SM-5m zeolite.

ZSM-5 zeolite is described, for example, in U.S. Pat.
No. 2,886, and further published in [Nature (
Nature), Volume 272, March 30th issue.

45th page (1978)] describes its crystal structure.

If, for example, ferrierite is used as the zeolite to be mixed with the zeolite, the mixing effect of the present invention cannot be obtained. In 7-elierite, the main cavity entrance consists of a 10-membered ring, but the pore size is less than 5x.

The entrance of the main cavity in the zeolite consists of a 10-membered oxygen ring,
A method of mixing zeolite with a pore size of 5x or more, such as Z 8 M-5 zeolite, is as follows:
Physical mixing, which is commonly practiced, may be used. For example, ZSM-5 zeolite is added to the zeophyte, and then mixed well with a larva to form a catalyst. Alternatively, both may be mixed in a slurry state.

The proportion of zeolite mixed with the zeolite whose main cavity entrance is composed of a 10-membered oxygen ring and whose pore size is 5x or more is 0.05 to 1 by weight relative to the zeolite.
．． 0 is good, preferably a1 to α5. If the amount of zeolite mixed is less than 105, there is no mixing effect,
Moreover, if it exceeds 1.0, the selectivity for light olefins will decrease, and the object of the present invention will not be achieved.

When these zeolites are used as catalysts in the present invention, some or all of the cation sites are converted into protons by a conventional method. In this case, the zeolites to be mixed may be proton-converted separately, or both may be mixed and then proton-converted at the same time.

These zeolites are used as catalysts as they are, or mixed with diluted substances and shaped as appropriate. In addition, dilution v/JJX
The carrier may be an inorganic compound commonly used as a carrier, such as montmorillonite.

Clays such as kaolinite or amorphous silica.

Examples include gold@oxides such as alumina and silica-alumina.

These zeolite catalysts may be used as is, but
Usually 300-800℃, preferably 400-600℃
1 under gas flow, preferably live air flow, at a temperature range of
It is better to bake for ~10 hours.

It is desirable that methanol and/or dimethyl ether, which are raw materials, be diluted with an essentially inert compound, that is, an inert gas, in order to increase the selectivity of the light olefins supplied directly in gaseous form. As the inert gas, for example, nitrogen, hydrogen, helium, water vapor, carbon dioxide, etc. may be used, and nitrogen is usually used.

Apart from that, the concentration of methanol and/or dimethyl ether is 1 to 99% by volume, preferably 5 to 50% by volume.

The reaction temperature is preferably in the range of 300 to 500°C. If the temperature is less than 500°C, the conversion rate of methanol and/or dimethyl ether will be low, and if the temperature exceeds 500°C, the proportion of methane produced will increase, which is undesirable. The reaction pressure is not particularly limited, but is usually in the range of normal pressure to 10 atm.

The raw material mixture has a gas hourly velocity of 50Q to 2G, 0
[10 hr-', preferably 1,000 to IQ, 00
Supplied in the range of 0 hr.

In carrying out the present invention, there are no restrictions on the type of apparatus used, and a conventional fixed bed may be used, but a fluidized bed or moving bed may also be used.

The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A methanol conversion reaction was carried out using a mixture of offretite and Z SM-5 zeolite as a catalyst.

An off-left having the following chemical composition was prepared according to Japanese Patent Application No. 57-14,783.

(128(TMA)20・Q, 3ONa20uQ, 42
20・A/203 醗7.1Si02 (Anhydrous Basin (TMA: Tetramethylammonium ion)) It was confirmed by powder xi diffraction that the obtained zeolite was off-left.
It was used after being baked at ℃ for 3 hours.

The BET specific surface area was 448 m''/f.

On the other hand, 28M-
5 zeolite was prepared. The obtained zeolite is ZSM
-5 zeolite was confirmed by powder X-ray diffraction. This ZSM-5 zeolite was subjected to ion exchange treatment using a 1N ammonium chloride aqueous solution under heating conditions of 95° C. for 5 hours. Furthermore, under air circulation, 540
It was used after being baked at ℃ for 5 hours.

BKT specific surface area is 294 m! , now, and as a result of chemical analysis, the 5i02 /AIt Os ratio is 5 Q, 8 m
It was ol/mol.

The military ratio against Off Left is [Z to be L60]
SM"-5 zeolite was added to the off-left, the two were mixed well, and the resulting mixture was used as a catalyst.

The methanol conversion reaction was carried out using a fixed bed microreactor (made of quartz, 5 m$ x 200 mL) filled with a catalyst [11f', using a mixed gas of methanol:nitrogen = 1 nia as a raw material, at a reaction temperature of 410°C, and a gas hourly space velocity of! ,0OOhr-
”, conducted under normal pressure conditions.

All reaction products were analyzed by gas chromatography. The reaction results are shown in Table 1.

Table 1 1) Proportion of methanol converted to hydrocarbons 2) Proportion of methanol converted to dimethyl ether 3) Methanol standard comparative example 1 Using only the off-left as shown in Example 1 as a catalyst,
The methanol conversion reaction was carried out under exactly the same reaction conditions as in Example 1. The reaction results are shown in Table 2.

Comparative Example 2 A methanol conversion reaction was carried out under exactly the same reaction conditions as in Example 1 using only the ZEIM-5 zeolite shown in Example 1 as a catalyst. The reaction results are shown in Table 2.

Table 2 1) Proportion of methanol converted to hydrocarbons 2) Proportion of methanol converted to dimethyl ether 3) Methanol standard Example 2
A methanol conversion reaction was carried out by mixing the methanol. Erionite was a natural product (produced in Nevada, USA) and was subjected to ion exchange treatment at 95° C. for 5 hours in a 1N ammonium chloride water bath. The obtained slurry was filtered, washed with water, and heated at 120°C for 1
It was dried for 5 hours, and then baked at 540° C. for 3 hours under air circulation for use.

28M-5 zeolite similar to that used in Example 1 was added to erionite at a weight ratio of [L2], the two were thoroughly mixed, and the resulting mixture was used as a catalyst. .

The methanol conversion reaction has a gas hourly space velocity of 1.000 hr-
1, and the other conditions were exactly the same as in Example 1.

The reaction results are shown in Table 3.

Comparative Example 6 A methanol conversion reaction was carried out under exactly the same reaction conditions as in Example 2 using only the erionite shown in Example 2 as a catalyst.

Table 5 1) Proportion of methanol converted to hydrocarbons 21 Proportion of methanol converted to dimethyl ether 3) Methanol standard Example 3 A catalyst was prepared by mixing ZBM-5 with zeolite l-T,
A methanol conversion reaction was carried out. Zeolite T was prepared by the method shown in Japanese Patent Publication No. 36-1 λ569.

The prepared zeolite was confirmed to be Zeolite T by powder bed X-ray diffraction. Zeolite T is Example 2
Ion exchange and calcination treatment were performed using the method shown in .

Add zsM-s zeolite similar to that used in Example 1 to zeolite T at a weight ratio of 0.4, mix the two well, and use the resulting mixture as a catalyst. did.

The methanol conversion reaction was carried out under exactly the same reaction conditions as in Example 2.

The reaction results are shown in Table 4.

Example 4 A methanol conversion reaction was carried out using a catalyst consisting of clinoptilolite mixed with Z'SM-5 zeolite.

Clinoptilolite is a natural product (produced in Itaya, Yamagata Prefecture),
Ion exchange and calcination treatment were performed by the method shown in Example 2. Its chemical composition was as shown below.

ClO2Na, O-(LIDK, 0-AJ, 0.
-5.2 S (anhydrous base) Also, the 13ET specific surface area was 241 m''.

ZSM-5 zeolite similar to that used in Example 1 was added to clinoptilolite at a weight ratio of α30, the two were thoroughly mixed, and the resulting mixture was used as a catalyst. used.

The methanol conversion reaction was carried out under exactly the same reaction conditions as in Example 2. The reaction results are shown in Table 4.

Table 4 1) Proportion of methanol converted to hydrocarbons 2) Proportion of methanol converted to dimethyl ether 3) Methanol standard comparative example 4 Comparative example 4 of Example 3 and Example 3 using only Zetite T shown in Example 3 as a catalyst. The methanol conversion reaction was carried out under exactly the same reaction conditions.

Immediately after the start of the reaction, the methanol conversion rate to hydrocarbons was 100%, and the light olefin selectivity was 77.4.
m01% (based on methanol), but the activity significantly decreased after 6 hours, and the methanol conversion rate to hydrocarbons was 15.6%.

Comparative Example 5 A methanol conversion reaction was carried out under exactly the same reaction conditions as in Example 4 using only the clinoptilolite shown in Example 4 as a catalyst.

Immediately after the start of the reaction, the methanol conversion rate to hydrocarbons was 100%, and the light olefin selectivity was 85.2.
m01% (methanol standard), but at 6 o'clock, 1 liter
The activity decreased markedly after 6 hours, and the conversion rate of methanol to hydrocarbons was 6.5 hours.

Example 5 A methanol conversion reaction was carried out in exactly the same manner as in Example 1, except that the amount of ZSM-5 zeolite mixed was adjusted to the weight ratio cti to offretite. One hour after the start of the reaction, the proportion of methanol converted to hydrocarbons was 100 mol, and the selectivity for light olefins was 81.2 mol (based on methanol).
Met. After 15 hours, the methanol conversion rate was 51
．． At 5%, the selectivity for oyster olefins is 84.9 m01
% (based on methanol).

Example 6 The reaction was carried out in the same manner as in Example 1 except that the weight ratio of ZSM-5 zeolite to offretite was 8 mL. One hour after the start of the reaction, the proportion of methanol converted to hydrocarbons was 100%, and the selectivity of light olefins was b4. o moxl (based on methanol). After 30 hours, the methanol conversion rate was 440 cm, and the selectivity for light olefins was a 1.2 moxl.
(based on methanol).

Procedural Amendment Statement August 60, 1980 Kazuo Nobuwakasugi, Commissioner of the Japan Patent Office 1988 Patent Application No. 74930 2 Name of Invention Method for Manufacturing Light Onfin 6 Relationship with the Amendment Case Patent Application Address: 4560 Oaza Tomita, Shinnanyo City, Yamaro Prefecture, 746 Phone number: (585) 3-11 4. Date of amendment order 6. Subject of the amendment 7. Contents of the amendment (1) Name of the invention on page 1 of the specification The column ``Method for producing soft olefins'' is corrected to ``Method for producing light olefins.''

Q) Engraving of the specification (no change in content) 8 List of attached documents Printed specification 1 procedural amendment form August 30, 1980 Display Patent Application No. 7'4930 of 1988 2 Name of the invention Process for producing light olefins 6 Matters to be amended f'1. Relationship with Patent Applicant Telephone Number (585) 3311 4 Sleeve Correction Order 1 Coin: 1 Voluntary Amendment 6 Scope of Claims of Specification Subject to Amendment 7 Contents of Amendment Attachment Toshi Attachment 2 Claims (]) A method for producing light olefins by converting methanol and/or dimethyl ether,
A zeolite whose main component is offretite erionite zeolite or clinoptilolite, whose main cavity entrance is not a 10-membered oxygen ring, and whose pore size is 5% or more. , weight ratio, 0.05~
A method for producing light olefins, characterized by using a mixed catalyst added at a ratio of 10%.

(2) The method according to claim (1), wherein the weight ratio is 0.1 to 5.

(3) Reaction temperature is 500-500℃, gas hourly space velocity is 500-20.000 hr-1, pressure is 1 from normal pressure.
Claim No. (1) or υ in which the reaction is carried out at 0 atmospheric pressure
) Method described in section.

(4) The method according to claim 11, wherein methanol and/or dimethyl ether is diluted with an inert gas and then supplied.

Claims (4)

[Claims] (1) A method for producing a soft olefin by converting methanol and/or dimethyl ether, wherein the main component is offretite erionite zeolite or clinoptilolite, and the entrance of the main cavity is 10% relative to the main component. A zeolite consisting of member oxygen rings and having a pore size of 5x or more is mixed in a weight ratio of [105 to 10
A method for producing a soft olefin, characterized by using a mixed catalyst added in a certain proportion. (2) The method according to claim 11, wherein the weight ratio is 0.1 to α5. (3) Reaction temperature is 500-500°C, gas hourly space velocity is 500-20. OD Ohr-”, pressure is 1 from normal pressure
5% allowance for carrying out the reaction at 0 atmospheric pressure Claims No. 11) to (2)
The method described in section. (4) A method according to claim flJ, in which methanol and/or dimethyl ether are diluted with an inert gas and supplied.