JPH068168B2 - Zeolite molding manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a zeolite molded article using as a starting material a solid substance of an inorganic component such as silicon, aluminum, sodium, calcium and iron recovered from geothermal water. The zeolite molded article obtained by the present invention can be used as an adsorbent, a dehydrating agent, a deoiling agent, a heat storage agent, various catalysts and a catalyst carrier.

In a geothermal power plant that uses geothermal water, inorganic components contained in the geothermal water are deposited as a large amount of sludge in the heat exchanger section. Since these inorganic components impede the plant operation greatly, it is necessary to remove and recover them, and it is desired to develop an effective recycling method of the recovered inorganic components.

As a result of various studies on the effective use of such an inorganic component, the present inventors have found that this is extremely excellent as a starting material for zeolite synthesis,
It was found that the zeolite molded product obtained by molding a mixture of the zeolite obtained from the inorganic component and the inorganic component has various excellent properties as various industrial materials, particularly as a hydrotreating catalyst, and completed the present invention. I have arrived.

Separation and recovery of inorganic components from geothermal water is carried out by a conventionally known method. For example, there is a method in which a foaming agent and a collector are added to geothermal water to float and separate. In this case, the foaming agent is mainly composed of anion (olefin alcohol sulfone of higher alcohol sulfide) and nonionic surfactant (polyethylene glycol nonyl phenyl ether), and is mixed with phosphate or polyethylene glycol nonyl sulfonate. Known substances such as phenyl ether or polypropylene glycol ether are adopted, and known substances such as tallow diamine, tallow diamine acetate, coconut primary amine acetate, etc. are adopted as the collector. In this floating separation method, a pH of around ₅ is usually adopted, but the method is not particularly limited to this. If necessary, cations such as aluminum ions, iron ions, amines and ammonium ions can be added to the geothermal water.

The dried and calcined solid matter of the inorganic component separated and recovered from the geothermal water generally has the following properties.

Composition: Silica (SiO ₂ ) is the main component, and silica is in the form of polymerized silica. Depending on the type of geothermal water, converted to oxide, SiO ₂ ; 20-99.9% by weight Al ₂ O ₃ ; 0.1-20% by weight Na
₂ O; 0.01-5% by weight, CaO; 0.01-1% by weight, Fe
₂ O ₃ ; 0.01 to 3% by weight.

Specific surface area: 30 to 300 m ² / g Specific pore volume: 0.2 to 2.5 ml / g Pore distribution: Radius (Å)% to pore volume 〜 50 5.3 50 〜 100 13.2 100 〜 150 17.2 150-200 7.5 200-400 11.5 400-800 15.0 800-2000 18.1 2000 or more 12.3 The characteristics of these inorganic solids are that the specific surface area is extremely large compared to ordinary inorganic substances, In addition, the distribution of pore radii extends over a wide range of tens to thousands of angstroms.

In addition, when aluminum ions or iron ions are added as cations when recovering inorganic components from geothermal water, the concentration of aluminum or iron in the separated and recovered inorganic components is relatively improved, and in terms of oxides. Al ₂ O ₃ : 20
95 wt%, Fe ₂ O _3: is about 10 to 95 wt%.

In the present invention, in order to obtain a zeolite from the solid inorganic component recovered from geothermal water, the solid of the inorganic component is suspended in 10 times by weight or more of the alkaline aqueous solution, if necessary, water-soluble aluminum A salt, a water-soluble silicate, and / or an organic crystallization agent (for example, an organic ammonium salt) is added, and this is added in the temperature range of 80 to 500 ° C, preferably 90 to 250 ° C for 1 hour or more, preferably 1 hour to several React the day. By such a hydrothermal treatment, the solid matter of the inorganic component from the geothermal water can be crystallized (zeolite). Depending on the type of zeolite of interest, the general synthesis conditions will differ somewhat. For example, silicalite, ZSM-5, ZSM-11 having a high SiO ₂ / Al ₂ O ₃ ratio.
In synthesizing high-silica-type zeolite, such as the above, a solid material of an inorganic component recovered from geothermal water as it is or a material to which a silica component is added can be used as a starting material. In the synthesis of zeolite with a low SiO ₂ / Al ₂ O ₃ ratio such as natural zeolite analogue or Y-type zeolite, solids of inorganic components recovered from geothermal water or aluminum ions were added or recovered. The inorganic component solid and the aluminum ion-added solid may be mixed at an appropriate ratio as needed to prepare a starting material.

Further, aluminum ions in the form of aluminum salt may be appropriately added to the inorganic component recovered from the geothermal water to use as a starting material. Depending on the type of the desired zeolite, an organic crystallization agent may be added, for example, a quaternary alkylammonium salt such as tetra- (n-propyl) ammonium bromide, a cyclic amine such as pyrrolidine, Examples include various diamines such as hexamethylenediamine, choline, and the like.

The crystallized product obtained as described above is a zeolite synthesized by using a solid material of an inorganic component from geothermal water as a starting material, which contains silica and alumina as main components, and additionally, sodium, iron, and titanium. Etc. are included.

In the present invention, a zeolite molded article is produced by using the zeolite obtained as described above and a solid substance of an inorganic component recovered from geothermal water or a fired product thereof as a raw material. Calcination of inorganic components obtained from geothermal water is 300-1200 ℃
By the firing treatment as shown in FIG. 1, the physical properties such as pore size distribution pore volume and surface area of the solid inorganic component can be changed. The zeolite and the inorganic component solid or the fired product thereof are mixed, for example, by using both powders and mixing them in a preferable ratio as an industrial material. Next, various methods can be used to form these mixtures, for example, an organic binder, clay,
Water, etc. are added and mixed, kneaded, and molded by an extrusion molding machine or the like. Thereafter, drying, processing and firing are performed in the same manner as in other general industrial material preparation methods. The industrial material obtained by such a method has regular small pores due to zeolite, large pores and large pore volume of the solid inorganic component, and the like. Therefore, a catalyst system having various pore size distributions can be prepared, and as a material having a binary or ternary function, it is effective for various uses such as a hydrogenolysis reaction or a catalyst for hydrogenation reaction.

Examples of the use of the novel material obtained by the present invention as a catalyst are hydrorefining catalysts for heavy oil, coal, coal liquefied oil, etc. as shown in the examples, and various hydrogenation catalysts for carbon monoxide, methanol, etc. It is used as the subject of. That is, in the present invention, the zeolite molded product is used as it is or as a catalyst by supporting a hydrogenation active metal component thereon.
The hydrogenation-active metal in this case is conventionally known, and examples thereof include manganese, iron, cobalt, nickel, chromium, copper, molypden, tungsten, rhodium, platinum, palladium ruthenium, and iridium. The supported amount of the hydrogenation-active metal component is generally 0.01 to 50% by weight, preferably 0.1 to 20% by weight. As a supporting method,
The soaking method and the kneading method are effective. The catalyst of the present invention is usually 50 to 700 ° C, preferably 100 to 500 ° C.
It is used after being calcined and optionally subjected to hydrogen reduction or sulfurization treatment.

The catalyst of the present invention has crystallinity due to zeolite as its property, and has a regular pore structure,
In addition, since it contains a solid substance of an inorganic component, its specific surface area is extremely larger than that of an ordinary inorganic substance, and the distribution of the pore radius extends over a wide range of several tens to several thousand angstroms and the specific surface area. The feature is that the pore size distribution can be controlled.

The catalyst for hydrorefining heavy hydrocarbons and hydrotreating various raw materials of the present invention has high catalytic activity and selectivity, and is also excellent in catalyst life. When the catalyst of the present invention is used for hydrorefining heavy hydrocarbons, the reaction temperature is 100.
To 600 ° C, preferably 300 to 450 ° C, the hydrogen partial pressure is 10 to 500 Kg / cm ² , preferably 70 to 300 K.
It is g / cm ² . In the case of the present invention, the catalyst is presulfurized with sulfur or a sulfur-containing compound such as H ₂ S, or if necessary, sulfur or a sulfur-containing compound is added in an amount of 0.1 to 300 with respect to the catalyst. The catalytic activity and selectivity can be further improved by adding the weight%, preferably 10 to 150% by weight. The heavy hydrocarbons of the present invention include, as heavy oil, crude oil, atmospheric distillation residual oil, vacuum distillation residual oil, coal, coal liquefied oil, oil sand, oil shell extracted oil, etc. Included.

Further, the catalyst of the present invention can be used for hydrogenation reaction of various raw materials such as carbon monoxide and methanol. In this case, the reaction temperature is room temperature to 500 ° C., preferably 40 to 3
The temperature is 00 ° C. and the hydrogen partial pressure is 1 to 300 kg / cm ² , preferably 10 to 200 kg / cm ² .

Next, the present invention will be described in more detail with reference to Examples.

Example 1 Inorganic solid NO. Recovered from a geothermal power plant.
1 (SiO ₂ : 93.3%, Al ₂ O ₃ : 3.0%, Na ₂ O: 3.4%, Fe ₂ O ₃ : 0.
2%, CaO: 0.1%) was used as a starting material, and a zeolite was synthesized using a 500 ml autoclave. Zeolite synthesis was carried out by mixing the organic salt tetranormalpropylammonium bromide: 10 g, starting material: 15 g, water: 150 ml, putting it in a beaker, adding NaOH (20%): 20 ml, and adjusting the pH to 14. Then autoclave (5
00 ml) and the mixture was heated and stirred at 150 ° C. for 24 hours. The pressure in the autoclave at this time was 5 kg / cm ² . The extracted main product was washed with water and dried at 110 ° C.
The composition thus obtained was ZSM-5 as a result of measurement by X-ray diffraction and a scanning electron microscope.

Example 2 Using the same inorganic solid material No. 1 as in Example 1, synthesis was carried out from an autoclave. The reaction conditions are: organic salt: tetramethylammonium 10% solution 25 ml, raw material: solids NO. 1, 15 g and aluminum sulfate solution 7
0 ml (3.4 g as Al ₂ O ₃ ), NaOH: 10 g, water: 150 ml, reaction temperature: 150 ° C., reaction time: 22 hours, and the pressure during the reaction was 5 kg / cm ² .

After washing with water and drying in the same manner as in Example 1, it was found from the results of X-ray diffraction and the like that ZSM-4 was produced.

Example 3 Various zeolites were synthesized in the same manner as in Examples 1 and 2. The one used for zeolite synthesis is various inorganic components (NO.1 to NO.3) recovered from a geothermal power plant and a mixture thereof, or an alumina salt if necessary,
A silica salt is added. The reaction conditions used for the synthesis are reaction temperature: 100 to 250 ° C., reaction time: 1 hour to 10
0 hours, reaction pressure: 1 atm to 30 atm. The added organic salts are tetrapropylammonium salt, tetramethylammonium salt, benzyltrimethylammonium chloride chloride and tetrabutylammonium salt. Table 1 shows the products obtained.

The compositions of the inorganic components NO.1 to NO.3 are as shown in Table 2 below.

As described above, it has been found that various zeolites can be prepared by using the inorganic component recovered from geothermal water as a starting material.

Example 4 The zeolite prepared in Example 3 is mixed with an inorganic component recovered from a geothermal power plant or a solid product obtained by calcining the same, an organic binder and clay are added, and the mixture is molded by an extruder and calcined at 500 ° C. Then, a catalyst carrier was manufactured. Next, a catalyst was prepared by impregnating and supporting 10 wt% of M ₀ O ₃ as an active component. 400 using 10vol% H ₂ S / H ₂ mixed gas
After pre-sulfurization at 1 ° C for 1 hour, a coal liquefied oil reforming reaction was carried out in a 500 ml autoclave. The reaction conditions are
Reaction temperature: 380 ° C., initial hydrogen pressure: 80 kg / cm ² , reaction time: 100 minutes, coal liquefied oil: 150 g, catalyst: 6 g. The results obtained are shown in Table 3.

[Brief description of drawings]

FIG. 1 shows the change in the pore size distribution due to the baking treatment of the solid inorganic component.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yuji Shimura 1-1-1 Higashitabe-cho, Tsukuba-gun, Ibaraki Prefectural Chemical Research Institute (72) Hiromichi Shimada 1-1-chome, Yatabe-cho, Tsukuba-gun, Ibaraki Chemical Technology Inside the research institute (72) Totaro Goto, 1st east, Yatabe-cho, Tsukuba-gun, Ibaraki 1st in the Chemical Research Laboratory (72) Inventor Shin Shigemitsu, 1st east in Yatabe-cho, Tsukuba-gun, Ibaraki (56) Reference Document JP-A-52-123999 (JP, A)

Claims (1)

[Claims] 1. A zeolite obtained by suspending a solid matter of an inorganic component recovered from geothermal water in an alkaline aqueous solution and hydrothermally synthesizing it, and a solid matter of an inorganic component recovered from geothermal water. Alternatively, a method for producing a zeolite molded product, which comprises mixing the calcined product with the product and molding the product into a desired shape.