JPS60158122A - Manufacture of para-diisopropylbenzene and use of same for manufacture of hydroquinone - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention relates to a method for selectively producing para-diisopropylbenzene by catalytic disproportionation of cumene and a method for converting the obtained para-diisopropylbenzene to hydroquinone.

[Prior Art 1 Para-diisopropylbenzene and hydroquinone have numerous industrial uses; para-diisopropylbenzene as a solvent and chemical intermediate, and hydroquinone as a photographic developer, drug, dye intermediate, and antioxidant. , has industrial uses as inhibitors and stabilizers. .

A method for the disproportionation of aromatic hydrocarbons in the presence of zeolite catalysts is described by Grandio et al.
Gas Sharna 7 Shiku Oil and Gas Jou
rnal) Volume 69, Number 48 (19) 1).

Furthermore, U.S. Patent Nos. 3,126,442 and 3,41
No. 3,374, @3,589,878, No. 3,5
No. 89,879 and No. 3,607,961 describe vapor phase disproportionation of toluene over various catalysts.

U.S. Pat. No. 4,011,276 discloses a ZSM-5 type crystalline aluminum/silicate zeolite modified by adding a small amount of magnesium oxide.
Discloses a process for the disproportionation of toluene to benzene and xylenes enriched in 5'14-mers using a catalyst containing M-5 type zeticite. U.S. Patent No. 4.01
No. 6,219 discloses a similar reaction to U.S. Pat. No. 4,011,276 using a catalyst that has been modified by adding at least 0.5% by weight of phosphorus to the catalyst. The operations in each of the above-mentioned patents describe a process for the selective production of para-xylene, which results in a significant reduction in toluene conversion, i.e., a disproportionality of toluene under conditions comparable to unmodified zeolite catalysts. can only be obtained by allowing the activity to decrease compared to the

1 Problem to be Solved by the Invention, α] In these prior art operations, the xylene product produced was of an equilibrium composition of about 24% heteroisomers, about 54% meta isomers, and about 22% orthoisomers. If the equilibrium concentration of the para isomer is exceeded, the production of the para isomer is achieved only at the expense of lower activity, ie, toluene conversion is significantly reduced. Among the xylene isomers, i.e., or)-xylene, meta-xylene and para-xylene, meta-xylene is the least desirable product, and ortho-xylene and para-xylene are the more desirable products. Para-xylene is useful in the production of terephthalic acid, which is an intermediate in the production of synthetic fibers such as gucron (trade name of polyester, manufactured by DuPont), and the larger the amount of para-xylene produced, the more worth it.

Mixtures of xylene isomers alone or in combination with ethylbenzene have hitherto been separated by expensive ultra-M dense distillation and multi-stage freezing steps. In practice, such operations involve high operating costs and have limited yields.

Means for Solving the Problems 1 According to one aspect of the present invention, the present invention provides a method for selectively producing para-diisopropylbenzene, characterized by contacting cumene with a ZSM-12 catalyst under disproportionation conditions. The present invention provides a method for selective disproportionation of cumene involving production.

Appropriate disproportionation conditions are 200-760°C (390-140°C
temperature below 0), atmospheric pressure -69961tPa (1000p
sig) and a space velocity of 0.08 to 2.0 weight hourly space velocity (WH8V). WH8 is based on the weight of the catalyst composition, ie, the total weight of active catalyst and catalyst binder. The effluent is separated and distilled to remove undesired products and to separate tubenzene, cumene and diisopropylbenzene. Unreacted cumene can be recycled.

In another aspect of the invention, the invention provides the steps of: (i) contacting cumene with a zsM-i2 catalyst under disproportionation conditions to selectively produce para-diisopropylbenzene and benzene; A selective process for producing hydroquinone, comprising: i) oxidizing para-diisopropylbenzene to the corresponding dihydroperoxide; and (iii) rearranging the dihydroperoxide product of step (ii) to produce hydroquinone and acetone. It is on offer.

[Function] The crystalline zeolite used in the method of the present invention is ZSM-12.
The characteristics and synthesis method of ZSM-12 are described, for example, in US Pat. No. 3,832,449 and European Patent B 1808.
It is described in the specification of No. 9.

When ZSM-12 was prepared in the presence of Aritsuki cations,
ZSM-12 becomes virtually catalytically inert. This is probably because the intracrystalline free space is blocked by the ion cations from the ZSM-12 forming solution. Catalytically inert ZSM-12 can be activated, for example, by heating at 540 DEG C. for 1 hour in an inert atmosphere, followed by base exchange with an ammonium salt, followed by calcination at 540 DEG C. in air. The presence of organic cations in the ZSM-12 zeolite forming solution is not absolutely necessary for the formation of zeolites. More commonly, base exchange is carried out with ammonium salts, followed by heating at 540° C. in air for about 15 minutes to about 2 hours.
It is desirable to activate this type of zeolite by dark calcination.

When zeolites are synthesized in alkali metal form, they can be conveniently converted to the hydrogen form by forming the ammonium form as a result of ion exchange with ammonium ions and calcining this ammonium form to obtain the hydrogen form. . In addition to the hydrogen type, the initial alkali metal is about 1.5
Other forms of zeolite reduced to less than % can be used.

That is, the initial alkali metal of the zeolite can be exchanged by ion exchange with other suitable ions of groups IB to ■ of the periodic table, including, for example, nickel, copper, zinc, palladium, calcium or rare earth metals. In carrying out the process, it is desirable to mix the crystalline zeolite described above into other materials (trenchment) that are resistant to the temperatures and other conditions used in the operation. The excavation is made of synthetic or naturally occurring materials as well as clay, silica and/or 4r, fK.
Contains inorganic substances such as oxides. The latter may be in the form of a natural product or a gelatinous precipitate or gel containing a mixture of silica and metal oxides). Naturally occurring clays that can be composited with zeolite include those of the montmorillonite and kaolin families, which include subbentonite and kaolin, known as Dixie, Macnamenoyoja, and 70-rig clays, or where the main mineral component is halloysite, Others include kaolinite, detsuite, nacrite or anauxisite. Such clays can be used in their raw, as-mined state or after prior firing, acid treatment or chemical modification.

In addition to the substances mentioned above, the zeolites used in the present invention include alumina, silica-alumina, silica-magnesia, silica-norkonia, silica-thoria, silica-beryria,
Silica-titania and ternary compositions such as silica-alumina-thoria, silica-alumina-norconia, silica-alumina-magnesia, and silica-magnesia-norconia can be composited with porous trenches. The trench may be in the form of a kogel. The relative proportions of the zeolite component and the inorganic oxide gelled cuttings, on an anhydrous basis, can vary widely from about 1 to 99%, more usually from about 5 to 80%, by weight of the dry composite.

The second optional component of ZSM-12 consists of a minor fraction, 0.05% to 50% of the weight of the catalyst composite, of difficult to reduce oxides. This type of oxide is similar to the oxide of phosphorus, as well as the periodic table [Fisher Scientific Research Institute], which acts to increase the para-selective properties in shift catalysts.
-(Fisber 5cientic(:ompan
y) Catalog number 5-702-10 J IA group,
Group IIA, lit Group A, Group IVA, Group VA, Group VIA, Group A, Group A, Group IB, Group B, Group IIIB, I
Oxides of Group VB or Group VB metals can be included. The most common difficult-to-reduce oxides used to modify the selectivity properties of catalysts are the oxides of phosphorus and magnesium. Thus, the catalyst is described in U.S. Pat.
No. 4, No. 4,049,573, No. 4.086, 2
87 and 4,128,592 using phosphorus compounds or magnesium compounds or both.

The phosphorus may be present, for example, at least partially in the form of phosphorus oxides in an amount of 0.25 to 25%, preferably 0.25% to 25% of the weight of the catalyst composite.
An amount of 7 to 15% can be mixed into the catalyst. The mixing can be easily carried out by bringing the zeolasate composite into contact with a solution of a suitable phosphorus compound, followed by drying and calcining to convert the zeolite components.

Suitable phosphorus-containing compounds include diphenylphosphine chloride, trimethylphosphite, phosphorus trichloride, phosphoric acid, 7z
Includes nylphosphine oxychloride, trimethylphosphite, diphenylphosphinic acid, diphenylphosphinic acid, diethylchlorothiophosphate, acidic phosphoric acid methyl ester and other alcohol-P205 reaction products.

Particularly preferred are ammonium phosphates, including ammonium hydrogen phosphate (NH,) 2HPo4 and ammonium dihydrogen phosphate NH,) (2PO,).Calcination is usually carried out in the presence of oxygen at a temperature of at least about 150°C.However,
Relatively high temperatures, ie up to 500°C or higher, are preferred.

Such heating is usually carried out for 3 to 5 hours, but can be extended to 24 hours or more.

Magnesium oxide is another suitable difficult to reduce oxide that can be incorporated into the zeolite complex in a manner similar to that used for phosphorus. Magnesium is present at least partially as magnesium oxide, with 0.2
It can be 5 to 25% by weight, or 1 to 15% by weight. Mixing of magnesium oxide as well as phosphorus is accomplished by contacting the zeolite complex with a suitable magnesium compound, followed by drying and calcining to convert the magnesium in the zeolite to the form of magnesium oxide.

Suitable magnesium-containing compounds include magnesium nitrate and magnesium acetate. Calcination times and temperatures are generally similar to those described above for calcination of phosphorus-containing catalysts.

In addition to treating the zeolite to incorporate phosphorus oxides and/or magnesium oxides, the zeolite can also be modified in a substantially similar manner to incorporate various other oxides into the zeolite that increase rose selectivity. can do. Such oxides include boron oxide (U.S. Pat.
67.920), antimony oxide (U.S. Pat. No. 3,
No. 979,472), beryllium oxide (U.S. Pat.
, 260,843), oxides of Group A metals of the Periodic Table (US Pat. No. 4,275,256), alkaline earth metal oxides (US Pat. No. 4,288,647), Periodic Table IB
oxides of group metals (U.S. Pat. No. 4.276.438),
Oxides of Group VIB metals of the periodic table (U.S. Patent J@4,27
8,827), oxides of metals from Group VIA of the periodic table (U.S. Pat. No. 4,259,537), oxides of Group IA elements of the periodic table (U.S. Pat. No. 4,329,533), oxides of cadmium (U.S. Patent No. 4,384,155), Periodic Table 1
Oxides of Group 11B metals (U.S. Pat. No. 4,276.437)
(No. 4,302), Group A metal oxides of the periodic table (U.S. Patent No. 4,302
, 620), oxides of metals of Group VA of the Periodic Table (U.S. Pat. No. 4,302,621), and oxides of elements of Group mA of the Periodic Table (U.S. Pat. No. 4,302,622).

The disproportionation reaction of the present invention makes it possible to obtain noisopropylbenzene products having, for example, at least 60% para isomer and, for example, less than 1% ortho isomer.

The operation of the invention can be carried out with the cumene reagent in the gaseous or liquid phase. The operation can be carried out in batch, semi-continuous or continuous operation utilizing fixed bed, fluidized bed or moving bed catalyst apparatus.

1 Example 1 The present invention will be further explained with reference to Examples below.

Steam treated 828M with silica/alumina ratio of 180
-12 catalyst was tested for cumene disproportionation. Zeolite (ZSM-12) was prepared by calcining the hydrogen form, ion-exchanging NH4+ ions, and final calcining. This zeolite is placed in 100% steam under atmospheric pressure,
Steam treatment was performed at 538° C. (under iooo) for 3 hours. Z
SM-12 was intimately mixed with 35% by weight alumina binder, then pressed into wafers, ground and sieved to a uniform particle size of 14-20 mesh.

The reaction conditions and results are summarized in Table 1. rc in Table 1
UJ represents cumene, rDIPBJ represents diisopropylbenzene, and rN P RB Z , Ilj: n-7''rohilhenzene, respectively.

As a raw material, the conversion rate of propylene oligomers is relatively low (3%) at 150°C, but
As the temperature increases by 2 (10°C and 250°C), the conversion also increases to 13% and 45%, respectively.

Approximately equimolar amounts of benzene and DIPB were produced.

At temperatures of 200°C and 250°C, the para isomer (46-3
5%) was observed.

The symbiotic acid benzene can be converted to cumene for recycling by alkylation with propylene. This can be a practical additional step, especially if a cumene plant can be conveniently installed.

The para-twinpropylbenzene product of the above example can be oxidized, for example with air, to the corresponding dihydroxyperoxide, and rearrangement of this dihydroxyperoxide with acid catalyst can give hydroquinone and acetone.

The meta isomer can be converted to resorcinol and acetone by analogous operations.

Claims (1)

[Claims] 1. A process for selective disproportionation of cumene involving the selective production of para-diisopropylbenzene, which comprises contacting cumene with a ZSM-12 catalyst under disproportionation conditions. 2. (i) Contacting cumene with ZSM-12 catalyst under disproportionation conditions to selectively produce para-diisopropylbenzene and benzene; (ii) producing para-diisopropylbenzene in step (i) with the corresponding catalyst; A method for selectively producing hydroquinone, comprising: (iii) rearranging the dihydroperoxide product of step (ii) to produce hydroquinone and acetone.