JP3323536B2 - Catalyst composition for catalytic cracking of lower alcohols - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalytic composition for catalytic cracking of aliphatic lower alcohols and a method for catalytic cracking of alcohols using the same.

[0002]

2. Description of the Related Art The rise in crude oil prices has increased the need to produce petroleum products such as gasoline, kerosene, light oil and heavy oil from non-petroleum hydrocarbon sources such as coal and natural gas.
Development of the manufacturing process has become an important issue.

[0003] One of the most important of the manufacturing process is
One is the MTG method via methanol developed by Mobile. In the MTG process, C ₁₀ by methanol as a starting material, is reacted under 250 to 450 ° C. The ZSM-5 zeolite with a special pore structure as a catalyst
The following gasoline-based hydrocarbons consisting of aromatics, olefins, and paraffins can be obtained. However,
In the MTG reaction using the ZSM-5 catalyst, a sharp decrease in the catalytic activity due to coke accumulation and a synthetic zeolite (ZS
M-5) In synthesizing a catalyst, it takes a long time to crystallize the catalyst, the reproducibility of the adjustment is not good, and the production cost is high. In the industry, gasoline is produced by catalytic cracking. There is a demand for the emergence of a catalyst which is effective for the above and a method for producing the same.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a catalytic composition for catalytic cracking which can produce a gasoline-based hydrocarbon by catalytically cracking a lower aliphatic alcohol without causing a rapid decrease in catalytic activity. Another object of the present invention is to provide an excellent catalytic cracking method for lower aliphatic alcohols using these catalyst compositions.

[0005]

Means for Solving the Problems Phosphate has a wide range of properties of an acid base, so that it is easy to form a non-stoichiometric compound, but an acid in which a relatively weak acid point and a weak base point act in concert. It has both a base function and an ion exchange property, and affects the activity and selectivity by the catalyst preparation method, so that the catalyst action is multifunctional. For this reason, various phosphates have been studied as catalysts for dehydration reaction, hydrogenation reaction and the like. The present inventors have conducted various studies on the use of phosphate as a catalyst for converting an aliphatic lower alcohol into a gasoline-based hydrocarbon, and as a result, have found that a calcium phosphate-based compound supporting a specific metal ion by ion exchange, It was found that by using a calcium phosphate-based compound in which a metal was dispersed and supported as a catalyst, the conversion of lower aliphatic alcohols to gasoline-based hydrocarbons selectively proceeded, and the life as a catalyst was long.

The calcium phosphate compounds used in the present invention are hydroxyapatite Ca ₁₀ (PO ₄ ) ₅ (OH) ₂ , tricalcium phosphate Ca ₃ (PO ₄ ) ₂ , calcium monohydrogen phosphate
CaHPO ₄ · 0~2H ₂ O, dihydrogen phosphate calcium Ca (H ₂ PO
_{4) 2 · 0~1H 2 O,} 2 calcium Ca ₂ P ₂ O _7, calcium metaphosphate Ca (PO _{3) 2,} fluoroapatite Ca ₁₀ (PO
₄ ) ₅ F ₂ , tetracalcium phosphate Ca ₄ (PO ₄ ) ₂ O, phosphoric acid 8
Calcium _{Ca 8 H 2 (PO 4)} 5 · 5H 2 O , and the like.

[0007] The metals and / or metal ions used include alkali metals such as rubidium and potassium; alkaline earth metals such as strontium and barium; titanium, manganese, iron, cobalt, copper, platinum, silver, lanthanum and cerium. , Vanadium, chromium, molybdenum, tungsten, rhenium, ruthenium, rhodium, iridium, palladium, gold, zinc and other transition metals; and aluminum, indium, silicon, germanium, tin, lead and other metals, and tin-based metals and the like; And / or metal ions. One or more metals and / or metal ions selected from these metals are supported on the calcium phosphate compound to obtain the catalyst composition of the present invention.

As a method for supporting a metal and / or metal ion on a calcium phosphate compound, a method generally used as a conventional supporting method such as an ion exchange method, an impregnation method, and a physical mixing method can be used. When synthesizing a system compound, a catalyst composition can also be obtained by coexisting one or more of these metals and / or metal ions. For example, one or two or more water-soluble metal salts selected from the above metals are added to an aqueous solution of calcium phosphate or an aqueous dispersion thereof,
After the stirring process under the reaction temperature such as heating or boiling, if necessary
The pH is adjusted and the sediment that precipitates is collected. Alternatively, one or more metals selected from the above metals are added to an aqueous solution of calcium phosphate or an aqueous dispersion thereof, and the mixture is sufficiently stirred at a reaction temperature such as room temperature, heating or boiling, and if necessary, the pH is adjusted. Then, a method of collecting a sediment that precipitates is used. In order to uniformly disperse the metal, a salt such as phosphoric acid, nitric acid, hydrochloric acid, or any other component is added to the aqueous solution or the aqueous dispersion as needed to uniformly disperse and fix the metal component in the catalyst composition. Is also possible. It is preferable to use a reaction time of one to several hours when heating or boiling, and one to several days when the reaction temperature is low. The precipitate thus obtained is sufficiently washed with water, dried, and, if necessary, baked and pulverized to be used as a catalyst. Drying is 100 ° C or more,
Preferably, it is necessary to carry out at a temperature of 200 to 400 ° C for 1 to 24 hours.

The amount of metal and / or metal ion supported on the calcium phosphate compound by these methods varies depending on the type of metal, the type of calcium phosphate compound, etc., but even if the amount of metal and / or metal ion supported is too small. If the amount is too large, the catalytic effect is reduced, so that it is 50% by weight or less, preferably 0.1% by weight based on the calcium phosphate compound.
About 30% by weight. These catalyst compositions are in the form of powder, or a suspension is granulated by a spray dryer or the like, or compression-molded, honeycomb-shaped by injection molding, or the like.
It can be used as a molded body molded into a Raschig ring or the like and, if necessary, fired at 1,400 ° C. or lower.

Another embodiment of the present invention is a catalytic cracking method for catalytically cracking a lower aliphatic alcohol using the catalyst composition to obtain a gasoline-based hydrocarbon. In the present invention, the lower aliphatic alcohol used as a raw material is a lower alcohol having 1 to 4 carbon atoms, which may be used alone or as a mixture, or may contain water. The catalysts of various shapes thus adjusted in the present invention can be used as they are, but usually,
It is preferable to use an air calcination as appropriate, and further a pretreatment such as an activation treatment. Examples of the activation treatment include a heat treatment in an inert gas and a reduction treatment with a reducing gas such as hydrogen gas. By these treatments, the catalytic activity can be improved, and the catalytic properties can be appropriately adjusted according to the type of lower aliphatic alcohol used as a raw material.

The catalytic decomposition reaction of the present invention can be carried out in various gas atmospheres, and examples of atmospheric gases include nitrogen, hydrogen, carbon dioxide, argon, helium and the like. The reaction system is not particularly limited, and can be carried out using various reaction systems such as a fixed bed, a moving bed and a fluidized bed, but the fixed bed is easy in terms of operation. The reaction temperature varies depending on the type of lower aliphatic alcohol used as a raw material, but lowering the reaction temperature decreases the yield of hydrocarbons in the gasoline base material, and lowers the catalytic activity due to coke at high temperatures. It is preferable to carry out the reaction at 200 to 600 ° C. because it promotes the reaction and increases the regeneration frequency of the catalyst. The feed rate of the raw material lower aliphatic alcohol per unit weight of the catalyst WHSV (g methanol / g catalyst · hr) is not particularly limited, but is preferably 15 or less, particularly 0.75 to 3 in order to obtain a high alcohol conversion. A range of 0.0 is preferred. Hereinafter, the present invention will be described specifically with reference to examples.

[0012]

Example 1 300 g of tricalcium phosphate was stirred and mixed in 2 liters of ion-exchanged water, and an aqueous solution in which 0.6 g of silver nitrate was dissolved was added to this suspension, followed by stirring for 2 days. Thereafter, dehydration, washing and drying at 350 ° C. were performed to obtain a powdery catalyst composition containing 0.1% of silver.

[0013]

Example 2 200 g of tricalcium phosphate was stirred and mixed in 2 l of ion-exchanged water, and an aqueous solution in which 20 g of copper nitrate was dissolved and an aqueous solution in which 27 g of zinc nitrate were dissolved were added to the suspension, and the mixture was stirred for 4 days. I do. After that, dehydration, washing,
After drying at 200 ° C., a powdery catalyst composition containing 2.5% of copper and 2% of zinc was obtained.

[0014]

Example 3 200 g of hydroxyapatite was stirred and mixed in 2 l of ion-exchanged water, and chloroplatinic acid was added to the suspension.
An aqueous solution in which 3.5 g is dissolved, an aqueous solution in which zinc nitrate is dissolved in 3 g, and an aqueous solution in which aluminum nitrate is dissolved in 13 g are added, and the mixture is stirred for one day. After that, dehydration, washing, 15
After drying at 0 ° C., a powdery catalyst composition containing 0.5% of platinum, 0.2% of zinc, and 0.3% of aluminum was obtained.

[0015]

Example 4 100 g of hydroxyapatite was mixed with stirring in 1 liter of ion-exchanged water, and the suspension was heated to 85 ° C. An aqueous solution in which 6.5 g of tin chloride is dissolved and an aqueous solution in which 30 g of titanium (IV) sulfate are dissolved are added to the suspension, and the mixture is stirred for 8 hours while maintaining the temperature at 85 ° C. Thereafter, dehydration, washing and drying at 400 ° C. were performed to obtain a powdery catalyst composition containing 3.5% of tin and 5.0% of titanium.

[0016]

Example 5 200 g of calcium diphosphate was stirred and mixed in 2 liters of ion-exchanged water.
An aqueous solution in which 9 g is dissolved, an aqueous solution in which 15 g of iridium (II) chloride is dissolved, an aqueous solution in which 35 g of rhodium (III) sulfate is dissolved, an aqueous solution in which 45 g of zinc nitrate is dissolved, an aqueous solution in which 150 g of magnesium sulfate is dissolved, and an aqueous solution in which 25 g of silver nitrate is dissolved Add each and stir for 5 days. Thereafter, dehydration, washing, and drying at 120 ° C., a powder containing 4% of barium, 4.5% of iridium, 4% of rhodium, 4% of zinc, 7% of magnesium, and 6.5% of silver. A catalyst composition was obtained.

[0017]

Example 6 200 g of calcium hydroxide was added to 3 liters of ion-exchanged water in which 9 g of silver nitrate and 12 g of zinc nitrate were dissolved, followed by stirring. An aqueous solution of phosphoric acid is added to this solution to prepare hydroxyapatite by a conventional method. After stirring for 3 days, the mixture was dehydrated, washed, and dried at 200 ° C. to obtain a powdery catalyst composition containing 1.7% of silver and 0.8% of zinc.

[0018]

Comparative Example 1 500 g of tricalcium phosphate was stirred and mixed in 5 l of ion-exchanged water, an aqueous solution in which 0.4 g of silver nitrate was dissolved was added to this suspension, and the mixture was stirred for 2 days. Thereafter, dehydration, washing, and drying at 350 ° C. were performed to obtain a powdery catalyst composition containing 0.04% of silver.

[0019]

Comparative Example 2 100 g of alumina was mixed with stirring in 1 liter of ion-exchanged water, and the suspension was heated to 85 ° C. An aqueous solution in which 6.5 g of tin chloride is dissolved and an aqueous solution in which 30 g of titanium (IV) sulfate are dissolved are added to the suspension, and the resulting mixture is added to the suspension.
Stir for 8 hours while maintaining at ° C. After that, dehydration, washing,
After drying at 400 ° C., a powdery catalyst composition containing 3.5% of tin and 5.0% of titanium was obtained.

[0020]

Comparative Example 3 Calcium hydroxide 2 in 3 liters of ion-exchanged water
Add 00 g and stir. An aqueous solution of phosphoric acid is added to this solution to prepare hydroxyapatite by a conventional method. After stirring for 3 days, dehydration, washing, and drying at 200 ° C. yielded a hydroxyapatite powder.

[0021]

Example 7 Using 1.0 g of each sample prepared in Examples 1 to 6 and Comparative Examples 1 to 3, a reaction temperature of 420 ° C. and a nitrogen flow rate of 3 g were used.
The reaction was carried out at normal pressure under the conditions of ¹ / hr, a flow rate of the supplied alcohol of 2.0 g / hr, and a supply rate of the raw material alcohol per unit weight of the catalyst WHSV of 2 hr ^-1 . The reaction was carried out using a microreactor, and the reaction was carried out in Example 1, Examples 3 to 6 and Comparative Examples 1 to 3.
Tables 1 and 2 show the results after 8 hours of alcohol supply for the sample prepared in the above, and the results of 8 hours after the alcohol supply (2-1) and after 80 hours (2-2) for the sample prepared in Example 2. Indicated. The same reaction was carried out using silver powder, and the results after 8 hours of alcohol supply are shown in Table 2 as Comparative Example 4.

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

The catalyst used in the present invention is easy to prepare.
By using such a catalyst at a low cost, a gasoline-based hydrocarbon can be obtained from a lower aliphatic alcohol in high yield. It is also possible to obtain hydrocarbons other than the gasoline base material by supporting various metals on a calcium phosphate compound.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Hideo Mitsuyama 2-11-10 Tsukiji, Chuo-ku, Tokyo (Tsukiji Chuo Building) Sanginai Co., Ltd. (56) References JP-A-63-216830 (JP, A) JP-A-61-15848 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B01J 21/00-38/74 C07C 31/02 JICST file (JOIS) WPI (DIALOG)

Claims (5)

(57) [Claims] 1. A method according to claim 1, wherein the calcium phosphate compound comprises titanium,
A transition metal selected from manganese, iron, cobalt, copper, platinum and silver, an alkali metal, an alkaline earth metal, and at least one metal and / or metal ion selected from aluminum and tin are supported. A catalytic composition for catalytic cracking of lower alcohols. 2. The catalyst composition according to claim 1, wherein the content of metal and / or metal ion is 0.1 to 30% by weight based on the calcium phosphate compound. 3. The catalyst composition according to claim 1, wherein the calcium phosphate compound is hydroxyapatite. 4. The catalyst composition according to claim 1, wherein the calcium phosphate compound is tricalcium phosphate. 5. A process for producing a gasoline-based hydrocarbon, comprising contacting an aliphatic lower alcohol having 1 to 4 carbon atoms with the catalyst composition according to any one of claims 1 to 4.