JP2587446B2 - Solid acid catalyst for alkylation - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a novel solid acid catalyst for the alkylation reaction of novel isoparaffins, especially isobutane, with olefins having a strong acid point, using a group III and / or group IV compound as a carrier. It is about.

[Conventional technology]

Alkylation reaction of isobutane with olefin is an important technology in the petroleum refining industry and widely implemented as a conversion process of light hydrocarbons into a heavy octane number gasoline fraction suitable for automobile fuels. I have.

Alkylation reactions are generally carried out industrially using sulfuric acid or hydrofluoric acid as a catalyst.However, since these methods are homogeneous reaction systems in which the raw materials or products and the catalyst are both liquid, the reaction is carried out. It requires a step of separating the product and the catalyst, which is very uneconomical. In addition, there are problems such as waste acid treatment, difficulties in handling catalysts, problems in toxicity and corrosiveness, and the like, and it is not always technically sufficient.

[Problems to be solved by the invention]

In order to solve the above-mentioned problems of the liquid catalyst used in the alkylation reaction of isoparaffin with olefin, there have been some research examples of solid acid catalysts active in the alkylation reaction in the past.

For example, JP-A-51-63386 discloses a Lewis acid-supported graphite-containing carbon system, and JP-B-57-3650 discloses an acid-type cation exchange resin system having a giant network structure, USP 3,251,902, 4,377,721, 3,65.
8,813 and JP-A-51-68501 include crystalline aluminosilicate zeolites, and JP-B-59-6181 and 59-40056 include zirconia and iron oxide. But,
These solid acid catalysts have not yet been put to practical use because the alkylate yield of the product is low, the octane number of the alkylate is low, the polymerization reaction of olefins occurs simultaneously, or the activity is greatly deteriorated.

From these facts, the emergence of a solid acid catalyst having a high alkylation activity, a high octane value of the product, and a long catalyst life is required.

[Means for solving the problem]

The present inventors have conducted intensive studies in order to solve the problems of the prior art, and as a result, have found a solid acid catalyst having excellent alkylation activity and selectivity, and have completed the present invention.

That is, the present invention provides a support comprising a hydroxide or an oxide of a Group III and / or Group IV metal on a Group IIb, Group Va, or Group V
A solid catalyst for alkylation of impalaffine by olefin containing at least one metal or a compound thereof and a sulfate group or a precursor of a sulfate group, which comprises at least one metal selected from the group consisting of Group Ia and Group VIIa; In addition, the catalyst has a high activity in the alkylation reaction of isopaline with olefin, and has a feature of being excellent in selectivity of trimethylpentane (TMP) which is a hydrocarbon having a high octane number among the alkylation reaction products.

[Action]

The group III metal hydroxide or oxide of the carrier used in the present invention is at least one metal selected from aluminum (Al), gallium (Ga), indium (In) and thallium (Tl). Oxides or oxides, and hydroxides or oxides of Group IV metals are derived from titanium (Ti), zirconium (Zr), hafnium (Hf), silicon (Si), germanium (Ge) and tin (Sn) The term refers to hydroxides or oxides of at least one selected metal, and among them, hydroxides or oxides of aluminum, tin, zirconium, and titanium are particularly preferable. These hydroxides or oxides are usually used, such as hydroxides precipitated by addition of an alkali such as aqueous ammonia to the Group III and / or Group IV metal salts, or oxides formed by thermal decomposition. Obtained by the method.

Group IIb is zinc, cadmium, mercury, group Va is vanadium, niobium, tantalum, group VIa is chromium,
Molybdenum, tungsten and Group VIIa refer to at least one element selected from manganese and rhenium or a compound thereof, and particularly preferably zinc, chromium or a compound thereof. Any of these can be introduced onto a carrier by a conventional technique such as an impregnation method or a coprecipitation method.

The amount of supported metal is 0.01 to 20 parts by weight per 100 parts by weight of the carrier.
Parts by weight, preferably 0.1 to 10 parts by weight, are suitable. The reason for this is that if the content is less than 0.01 parts by weight, the effect of the supported metal is small, and the excellent selectivity of the alkylated product is reduced.
If the amount is more than part by weight, there is a problem that the acidity decreases and the reaction rate decreases.

Sulfate or precursor of sulfate is sulfuric acid (H ₂ S
O ₄ ), ammonium sulfate [(NH ₄ ) ₂ SO ₄ ], ammonium sulfite [(NH ₄ ) ₂ SO ₃ ], ammonium hydrogen sulfate [(N
H ₄ ) HSO ₄ ], sulfuryl chloride (SO ₂ Cl ₂ ) and the like, but preferably sulfuric acid, ammonium sulfate and sulfuryl chloride are suitable. One example of the method for containing the sulfate group is that a dried Group III and / or Group IV metal hydroxide or oxide is used in an amount of 0.1 to 10 parts by weight of 0.1 to 10 parts by weight.
A method of immersing or flowing in an aqueous solution containing a sulfate group having a concentration of 01 to 10 mol, preferably 0.1 to 5 mol, and contacting the solution by flowing or the like may be mentioned.

According to the present invention, the introduction of the supported metal and the sulfate or sulfate precursor may be performed in any order. For example, a method in which a metal is introduced onto a carrier and then treated with a treatment agent containing a sulfate group or a sulfate group precursor, or a method in which a metal is introduced after treatment with a sulfate group or a sulfate group precursor is employed. can do.

In producing the catalyst of the present invention, 50 to 550 after metal loading
C., preferably 100 to 400 ° C. for 1 to 24 hours in air calcination, but according to the present invention, after the treatment with sulfate or sulfate precursor, 400-800.
It is necessary to stabilize the calcination at a temperature of 450 ° C., preferably 450 to 700 ° C. for 0.5 to 10 hours.

The catalyst produced by the above method has excellent alkylation reaction activity by contacting isoparaffin with olefin under the reaction conditions. Suitable Isoparafuin the alkylation reaction, isobutane (i-C ₄ H ₁₀₎
Olefins having 2 to 6 carbon atoms, preferably olefins having 2 to 4 carbon atoms, ie, ethylene (C ₂ H ₄ ), propylene (C
₃ H _6), butene (C ₄ H ₈₎ is suitable.

Suitable reaction conditions for the alkylation reaction using the catalyst of the present invention depend on the raw materials and the reaction scheme. The reaction is preferably carried out in the liquid phase, so that the reaction pressure is between 1 and
60 bar is suitable.

Further, the reaction temperature is -40 to 200 ° C, preferably -30 to 120 ° C.
° C is suitable. The isobutane / olefin ratio of the raw material to be supplied is suitably from 5/1 to 500/1 (Wt / wt). If the olefin concentration is too high, the polymerization of olefin will increase,
There is a possibility that the intended alkylation reaction may be inhibited.

Thus alkylate obtained reaction product is, C ₈ components, in particular remarkably excellent selectivity to trimethylpentane.

 The present invention is described in more detail in the following examples.

Example 1 ₂ kg of commercially available zirconium oxychloride (ZrOCl ₂ ) was added to pure water 15
, And ammonia water was gradually added dropwise with stirring until the pH reached 10, and the resulting zirconium hydroxide (Zr
After aging the precipitate of (OH) ₄ ] for 24 hours, it was filtered, washed, and vacuum dried (110 ° C.) to obtain about 700 g of a white powder. This white powder is impregnated with an aqueous solution of zinc nitrate [Zn (NO ₃ ) ₂ .6H ₂ O] (concentration of 0.3 parts by weight in terms of zinc element per 100 parts by weight of the carrier) 3, and a rotary evaporator is used. It was evaporated to dryness, dried and calcined (300 ° C). In the same manner, 3.0 and 9.0 parts by weight of zinc element were prepared. Each of these three types of supports is introduced into 1 molar sulfuric acid 7, and the excess sulfuric acid is filtered, dried, and calcined at 550 ° C. for 3 hours to obtain catalyst A (zinc 0.3 parts by weight) and catalyst B (same as above). 3.0
Parts by weight) and Catalyst C (9.0 parts by weight).

Table 1 shows the measurement results of acid strength by titration using a Hammett indicator in a benzene solvent.

With respect to the dry Zr (OH) ₄ 60 g in chromic nitrate _{[Cr (NO 3) 3 · 9H} 2 O ] aqueous solution (100 parts by weight of the carrier prepared in the same manner as in Example 1, in terms of chromium metal (Concentration of 3.0 parts by weight), 300 ml, and evaporated and dried in the same manner as in Example 1. Immediately after drying, the dried product was immediately transferred onto a filter paper of a Buchner funnel, allowed to flow down while sucking 0.5 mol of ammonium sulfate [(NH ₄ ) ₂ SO ₄ ] 1, dried, and calcined at 650 ° C. for 3 hours. I got Table 1 shows the measurement results of the acid strength.

Example 3 An aqueous solution of ammonium metavanamate (NH ₄ VO ₃ ) and an aqueous solution of manganese nitrate [Mn (NO ₃ ) ₂ .6H ₂ O] (carrier 100) were added to 60 g of dry Zr (OH) ₄ prepared in the same manner as in Example 1. Parts by weight converted to vanadium metal and manganese metal
Then, the mixture was impregnated with 300 ml (concentration of 1.0 part by weight) and evaporated to dryness and dried in the same manner as in Example 1. Immediately after drying, the dried product was immediately transferred onto a filter paper of a Buchner funnel, allowed to flow while sucking 0.5 mol of ammonium sulfite [(NH ₄ ) ₂ SO ₃ ] 1, dried, and calcined at 600 ° C. for 3 hours to obtain a catalyst E. , F were obtained. Table 1 shows the measurement results of the acid strength.

Example 4 Pure water 2 obtained by cooling 500 g of commercially available titanium tetrachloride (TiCl ₄ ) with ice
To pH 7.0, a precipitate was formed by dropwise addition of an aqueous NH ₃ solution until the pH reached 7.0, and the precipitate was aged, filtered, washed and dried to obtain Ti.
About 150 g of (OH) ₄ white powder was obtained. This dried Ti (OH) ₄
Was carried in the same manner as in Example 1 to carry zinc (3.0
Parts by weight) and then impregnated with sulfuryl chloride (SO ₂ Cl ₂ ) 1;
After air drying, the mixture was calcined at 550 ° C. to obtain a catalyst G. Table 1 shows the measurement results of the acid strength.

Example 5 After dissolving 500 g of commercially available zirconium oxychloride (ZrOCl ₂ ) and 500 g of titanium tetrachloride (TiCl ₄ ) in pure water 2,
An aqueous NH ₃ solution was dropped until 7.0 to form a coprecipitate,
Aged, filtered, washed and dried to Zr (OH) _4- Ti (OH)
_Thus, a composite hydroxide powder of No. ₄ was obtained. Also, 1000 g of commercially available zirconium oxychloride (ZrOCl ₂ ) and aluminum nitrate [Al
(NO ₃₎ After a 3 _· 9H ₂ O] 500g was dissolved in pure water 3, pH
An aqueous NH ₃ solution was dropped until 7.0 to form a coprecipitate,
Aged, filtered, washed and dried to Zr (OH) _4- Al (OH)
_Thus, a composite hydroxide of No. ₃ was obtained.

These Zr (OH) _4- Ti (OH) ₄ , Zr (OH) _4- Al (O
H) ₃ was loaded with zinc in the same manner as in Example 1 (1.0 parts by weight with zinc element), impregnated with 1 molar sulfuric acid, filtered off excess sulfuric acid, dried, and calcined at 600 ° C. for 3 hours. Thus, catalysts H and I were obtained. Table 1 shows the measurement results of the acid strength.

Example 6 150 g of dry Zr (OH) ₄ prepared in the same manner as in Example 1
Was introduced into 800 ml of 1 molar sulfuric acid, filtered, dried and calcined at 600 ° C. This was impregnated with 600 ml of an aqueous zinc nitrate solution, evaporated to dryness, dried, and calcined at 550 ° C. for 3 hours to obtain a catalyst J (0.3 parts by weight as a zinc element) and a catalyst K (3.0 parts by weight). Table 1 shows the measurement results of the acid strength.

Comparative Example 1 Dried Zr (OH) ₄ prepared in the same manner as in Example 1 was impregnated with an aqueous solution of zinc nitrate or chromium nitrate, evaporated to dryness, dried, and calcined at 550 ° C. for 3 hours. 0.3 parts by weight) and catalyst M (3.0 parts by weight as chromium element). Table 1 shows the measurement results of acid strength by titration using a Hammett indicator in a benzene solvent.

Comparative Example 2 Dry Zr (OH) ₄ or commercially available Al (OH) ₃ prepared in the same manner as in Example 1 was introduced into 1 molar sulfuric acid, filtered, dried, and calcined at 550 ° C. for 3 hours. Catalyst N and catalyst O were obtained. Table 1 shows the measurement results of the acid strength.

From Table 1, the hydroxides or oxides of Group IIa, Group Va, Group VIa, Group VIIa, and Group III metals and / or Group IV metals containing sulfate or sulfate precursors are calcined and stable. The resulting catalyst has an acidity function (H
It can be seen that o) is a solid acid catalyst having an acid strength higher than -12.7.

[Example 1] Using catalysts A to K prepared by the methods of Examples 1 to 6, an alkylation reaction was carried out in a fixed bed, pressurized liquid phase flow system.

In the reaction method, first, a predetermined amount of the dried catalyst was molded into a mesh of 16 to 28 and charged into a reactor. As pre-treatment, air is supplied to 400 ° C for 3 hours, then switched to nitriding, and set to a predetermined temperature and a predetermined pressure. Next, the supply of nitrogen was stopped, and isobutane (i-C ₄ ) and cis-2-butene (ci
supplied at a predetermined flow rate raw material liquid on the catalyst of s-2-C _4). The liquid composition at the outlet of the reactor was analyzed by a gas chromatograph as needed by using a liquid sampler, and the composition of the outlet reactor was determined over time.

 The reaction conditions for the alkylation reaction are as follows.

Reaction temperature: 0 ° C. Reaction pressure: 30 kg / cm ² G WHSV (raw material): 10 h ^-1 l-C ₄ / cic-2-C ₄ : 100 wt / wt Catalyst amount: 10 g Production after 1 h and 50 h after raw material supply The results of the product analysis are shown in Table 2. In Table 2, the conversion, the yield, and the selectivity are defined by the following equations, respectively.

Example 2 An alkylation reaction was carried out in the same manner as in Experimental Example 1 using the catalysts L to O prepared in Comparative Examples 1 and 2. Table 2 shows the results.

Experimental Example 3 Alkylation reaction of isobutane with cis-2-butene was performed under various reaction conditions using the catalyst B prepared by the method of Example 1. The reaction was carried out in the same manner as in Experimental Example 1. Table 3 shows the results.

Table 2 [Effect of the Invention From the results of Table 3, the catalyst is excellent in selectivity of the C ₈ and trimethyl pentane, is effective as a high-octane gasoline production catalyst for alkylation reaction since it has a long life of the present invention It has been found.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Shigeru Nojima 4-6-22 Kannon Shinmachi, Nishi-ku, Hiroshima City, Hiroshima Prefecture Inside the Hiroshima Research Laboratory, Mitsubishi Heavy Industries, Ltd. (72) Inventor Tetsuya Imai 4-chome Kannon Shinmachi, Nishi-ku, Hiroshima City, Hiroshima Prefecture No.6-22 Mitsubishi Heavy Industries, Ltd. Hiroshima Laboratory (56) References JP-A-61-242641 (JP, A) JP-A-61-153141 (JP, A) JP-A-61-68137 (JP, A) Kosho 59-40056 (JP, B2)

Claims (5)

(57) [Claims] 1. A support comprising a hydroxide or an oxide of a group III metal and / or a group IV metal, on a carrier comprising a group IIb, a group Va or a group VI
Group a, Group VII For the alkylation of isobutane with olefin, characterized by containing at least one kind of metal or a compound thereof and a sulfate group or a precursor of a sulfate group, and being stabilized by firing. Solid acid catalyst. 2. The group III metal hydroxide or oxide is aluminum, gallium, indium, thallium, and the group IV metal is at least one metal hydroxide selected from titanium, zirconium, hafnium, silicon, germanium and tin. 2. The solid acid catalyst according to claim 1, comprising a substance or an oxide. (3) Group IIb is at least one selected from zinc, cadmium, mercury, group Va is vanadium, niobium, tantalum, group VIa is chromium, molybdenum, tungsten, and group VIa is manganese or rhenium. The solid acid catalyst according to claim 1 or 2, comprising an element or a compound thereof. 4. The method according to claim 1, wherein the sulfate or the precursor of the sulfate is sulfuric acid.
At least one selected from ammonium sulfate, ammonium sulfite, ammonium hydrogen sulfate, and sulfuryl chloride;
4. The solid acid catalyst according to claim 1, 2 or 3, wherein said solid acid catalyst comprises a kind of substance. 5. The solid acid catalyst according to claim 1, wherein the calcination is stabilized at a temperature of 400 to 800 ° C.