JPS60190240A - Preparation of catalyst - Google Patents

Abstract

PURPOSE:To form and support a hardly soluble compound, by reacting alkali and a metal salt on a carrier. CONSTITUTION:Alkali such as an alkali metal compound, an alkaline earth metal compound, ammonia gas or aqueous ammonia is reacted with chloride of platinum, palladium or rhodium on a powdery or molded carrier comprising alumina, silica, silica-alumina, zirconia or titania. By this method, an insoluble compound can be formed and supported by said carrier.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a catalyst preparation method using an impregnation method, and more particularly to a catalyst preparation method in which an alkali and a gold FiR salt are reacted on a carrier to form an insoluble compound to support an active ingredient.

Conventionally, various methods are known for preparing noble metal catalysts. These conventional preparation methods are described, for example, in the following documents.

a) Catalysis Handbook by Element (Catalysis Society of Japan) (from page 543) b
) Catalytic Chemistry (Nikkan Kogyo) Tatsuo Yamanaka (page 207~) C)
Catalyst Preparation Chemistry (Kodansha) (page 52~) However, the conventional method has the following three drawbacks. Firstly, due to adsorption equilibrium on the carrier, active ingredients remain in the residual impregnating solution after immersion, and secondly, anions that degrade catalyst performance remain on the carrier. However, even if it is washed away, it is difficult to remove it, or even the active ingredients are leaked out. Thirdly, if the anion is removed during use, it will destroy the catalyst. This means that the downstream catalysts and equipment will be adversely affected.

As mentioned above, conventional methods have drawbacks such as large loss of active ingredients during catalyst preparation or failure to obtain sufficient catalytic activity in the prepared catalyst.
When using an X-membered metal, there is an economical problem.

In view of the above-mentioned problems of the prior art, the present invention removes harmful components remaining on the carrier without leaving the active ingredient in the impregnating solution when the active ingredient is supported on the carrier by the impregnation method. It is an object of the present invention to provide a method for preparing a catalyst that allows only harmful components to be easily washed and removed without causing the effective components to flow out.

As a result of intensive research in line with the above objectives, the present inventors found that
The inventors have discovered that the above problems can be solved by the following method and have arrived at the present invention.

That is, the present invention provides a method for preparing a catalyst in which an active ingredient is supported on a carrier by an impregnation method, which is characterized in that an alkali and a metal salt are reacted on the carrier to form an insoluble compound. It is.

In the present invention, it is essential that an alkali and a metal salt are reacted on a carrier to form a metal compound that is sparingly soluble in water. In this case, a method of adsorbing or supporting an alkali on the carrier in advance and then impregnating it with a metal salt solution, and a method of making the carrier support a metal salt in advance by an impregnation method and then impregnating it with an alkali can be considered. Either method may be used.

Note that if the alkali necessary for the reaction has already been mixed in as an impurity during the manufacturing process of the carrier, it is not necessary to add it.

In addition, when supporting an alkali first, NaOH
If a strong alkali such as , KOll, etc. is used, the carrier may change in quality.
After supporting a salt of a strong alkali and a strong acid such as N820, it is baked to form an oxide such as N820.

Supports that can be used in the present invention include alumina, silica,
Examples include silica/alumina, zirconia, titania, activated carbon, etc., but are not particularly limited to these.

Further, the carrier can be applied either in the form of a powder or a molded product.

Examples of the alkali used in the present invention include alkali metals, alkaline earth metal compounds such as hydroxides, carbonates, bicarbonates, nitrates, sulfates, and ammonia gas or aqueous ammonia. Examples of metal salts include chlorides, nitrates, and nitrates of negative metals such as platinum, palladium, rhodium, ruthenium, and silver. I acid 1! There are various acid salts such as i, etc., but those having a certain degree of solubility in water are preferably used.

Furthermore, in the present invention, if alkali and anions are harmful substances that degrade catalyst performance, they are removed by washing. In such cases, it is necessary to change the combination of alkali and metal salt as appropriate to facilitate washing and removal.

The present invention will be specifically explained below based on Examples and Comparative Examples.

Comparative Example 1 Alumina carrier 30 ( ) was impregnated with a ruthenium chloride solution in an amount such that the ruthenium content was o, s wt, %. Thereafter, it was dried at 110°C in a dryer by a conventional method. , catalyst A was obtained.

1iL alumina carrier 30 (] with an atomic ratio of Na/AJ of 6/1
It was impregnated with a sodium nitrate solution to give a concentration of 0.00. After that, dry it in a dryer using the usual method, and dry it in the air at 800℃.
It was baked for 2 hours. For this carrier, ruthenium is o, s
Ruthenium was immobilized by impregnating the carrier with a 0% wt ruthenium chloride solution and reacting with an alkali on the carrier.

Then, chloride ions were washed away with a 0.05 moJ/J sodium carbonate solution, and finally washed with distilled water and dried to obtain catalyst B.

After fixing ruthenium in the same manner as in Example 1, it was washed only with distilled water and dried to obtain catalyst B'.

Example 3 Ruthenium was fixed in the same manner as in Example 1 and then dried to obtain catalyst B''.

30 g of X134 alumina support was impregnated with m ruthenium chloride solution having a ruthenium content of 0.5 wt.%. Thereafter, it was immersed in 0.11110 J/J of sodium carbonate for 5 hours without drying, filtered and washed with water to remove chloride ions, and then dried to obtain catalyst C.

[Catalyst A obtained in Comparative Example 1 was immersed in a 0.1 moj/J sulfur to silium carbonate solution for 5 hours. Thereafter, it was filtered, washed with water, and dried to obtain a catalyst.

1 East 11 Catalyst E was obtained in the same manner as in Example 3, except that the catalyst was immersed in distilled water instead of in the sodium carbonate solution.

Furthermore, when immersed in distilled water, it was observed that rutheni-cum chloride was eluted into the water.

Comparative Example 4 30 g of alumina carrier had a palladium content of 1. A palladium chloride solution was impregnated in an amount of Owt.%. Thereafter, it was dried at 110° C. in a dryer using a conventional method to obtain catalyst F.

111 feet alumina carrier 30 (], the atomic ratio of Na/Ai is 6/1
It was impregnated with sodium nitrate solution to give a concentration of 0.00%. After that, dry it in a dryer using the usual method, and dry it in the air at 800℃.
It was baked for 2 hours. For this carrier, the palladium content is 1. Palladium was immobilized by impregnating the carrier with a palladium chloride solution in an amount of Owt 0% and reacting with an alkali on the carrier.

Then 0.0! Chlorine ions were washed away with a 1-lium carbonate solution of 1 10J/J, and finally washed with distilled water and dried to obtain catalyst G.

Tomo 111 30g of alumina carrier has a 1 Kyoko ratio of Na/AJ of 6/
It was impregnated with sodium nitrate solution to a concentration of 100%.

After that, dry it in a dryer using the usual method, and then dry it in the air at 800℃.
, and baked for 2 hours.

This carrier was immersed in 100 cc of 0,075 moJ/j ruthenium chloride solution for 5 hours, filtered, and 0,0
Catalyst H was obtained by washing with an aqueous sodium carbonate solution of 5IIlOJ/j and distilled water and drying.

1 (PJ 7) Processed in the same manner as in Example 4 except that a palladium nitrate solution was used instead of palladium chloride, and the palladium content was 1.
Owt.% catalyst I was obtained.

Example 8 Alumina carrier 30! Add ammonia gas to 4-J at room temperature.
U is absorbed in minutes. This ammonia-adsorbed alumina carrier was impregnated with a ruthenium chloride solution containing ruthenium-containing jQlO, 5 wt.%, and then washed with distilled water and dried to obtain catalyst J.

Example 9 Similar to Example 8, alumina carrier 30 (l) sufficiently adsorbed ammonia gas, palladium content 1.Owt, %
It was impregnated with a palladium sulfate solution. After that, it was washed with distilled water, dried, and touched to a 1 liter size.

Example 10 In the same manner as in Example 8, 30 g of an alumina carrier that had sufficiently adsorbed ammonia gas was impregnated with a chloroplatinic acid solution having a platinum content of 0.5 wt.%. Thereafter, it was washed with distilled water and dried to obtain a catalyst.

111 First, 30 g of an alumina carrier was impregnated onto the surface of the carrier with a solution prepared by diluting commercially available 28% ammonia water 4 times. This carrier was impregnated with a ruthenium chloride solution containing 110.5 wt % of ruthenium. Thereafter, it was washed with distilled water and dried to obtain catalyst M.

The metal content, anion content, and L1-12 adsorption amount of the catalyst thus obtained were measured, and the results are shown in Table 1.

Incidentally, 1. lfi was identified by the leco method for SOJ, and NO:q- was identified by Δ in chromatography.

From the results shown in Table 1 and above, it is clear that according to the present invention, chlorine, nitrate ions, sulfate ions, etc. can be efficiently removed and metal dispersibility is improved.

As explained above, the catalyst prepared according to the present invention is
It has the following effects.

(2) Since the active ingredient is formed and supported on the carrier as a poorly water-soluble compound, the active ingredient does not remain in the impregnating solution. Therefore, there is less loss of active ingredients.

- Since the active ingredient is supported as a compound that is poorly soluble in water, the effective ingredient will not flow out when washed with water. Further, since harmful components such as chloride ions, sulfate ions, and nitrate ions are easily washed away by alkonori, these can be sufficiently washed away. Therefore,
Loss of active ingredients, poisoning of downstream catalysts during use and corrosion of equipment can be prevented.

■ No need for calcination to decompose the metal salt supported on the carrier.

(2) The dispersibility of the active ingredient on the carrier is improved, and the catalytic properties (1) and (1) are improved.

Patent Attorney Tatsuo Ito Patent Attorney Tetsuya Ito Procedural Amendment (Voluntary) August 1, 1980 Commissioner of the Patent Office Manabu Shiga 1 , Indication of the case 1981 Special Patent Application No. 43981 No. 2, Name of the invention Catalyst preparation method 3, Person making the amendment Relationship to the case Patent applicant Location 2-2-1 Otemachi, Chiyoda-ku, Tokyo Name (4
41) JGC Corporation Representative: Nobuo Yamayama 4, Agent: 105 Address: Toranomon Electric Building, 2-8-1 Toranomon, Minato-ku, Tokyo Phone: (501) 93705.7 Subject of the invention in the specification Detailed Description Column" 6. Contents of Amendment 1, ``Example 4'' on page 9, line 15 for the specification is corrected to ``Example 5."

2. Add the following sentence next to Table 1 on page 11 of the same circle.

[Example 12 B in noflumina hydrate (Al103 ・3l-120)
A barium nitrate solution in an amount such that the atomic ratio of a/AJ was a7 ioo was combined, dried, and fired at 800°C to form an AJ203 carrier of 1 watt.

This carrier was impregnated with a ruthenium chloride solution having a ruthenium content of 0.5 wt%. Thereafter, it was washed with distilled water and dried to obtain catalyst N.

The metal (Ru) content of this catalyst N is 0.5 wt,%
, anion (CJ) content is 0.02 wt,%, H
2 Adsorption volume was 14.5 μmol/(i.) Procedural amendment (voluntary) December 19, 1980 Manabu Shiga, Commissioner of the Patent Office 1, Indication of the case 1982 Patent Application No. 43981 2 , Name of the invention Catalyst preparation method 3, Relationship with the case of the person making the amendment Special V
41) Buki Co., Ltd. Representative: Yama 1) Shin 711 4, Agent: 105 Address: Toranomon Electric Building, 2-8-1 Toranomon, Minato-ku, Tokyo Phone: <501) 93705 6. In addition, ammonia gas or ammonia water, etc." in page 5, line 15 for details of amendments" should be changed to "in addition to ammonia gas, aqueous ammonia, urea, ammonium salts such as mH ammonium, etc." ammonium hydrogen carbonate, organic basic substances such as amines, etc.” ′

Claims (1)

[Claims] 1. A catalyst preparation method in which an active ingredient is supported on a carrier by an impregnation method, characterized in that an alkali and a metal salt are reacted on the carrier to generate a poorly soluble compound and then supported. Catalyst preparation method. 2. The catalyst preparation method according to claim 1, wherein the slightly soluble compound is produced by adsorbing or supporting an alkali on a carrier and then impregnating the carrier with a metal salt solution. 3. After adsorbing or supporting an alkali on a carrier in advance, the alkali is converted into an oxide form by firing the carrier,
2. The catalyst preparation method according to claim 1, wherein the poorly soluble compound is produced by impregnating the catalyst with a metal salt solution. 4. After supporting a metal salt in advance on a carrier by an impregnation method, the above-mentioned M
A method for preparing a catalyst according to claim 1, which produces a soluble compound. 5. After preparing the catalyst by the above method, excess alkali and anion are added.
The method for preparing a catalyst according to any one of Item 4. 6. Claim 1, wherein the metal salt is a salt of a noble metal.
The catalyst preparation method according to any one of Items 7 to 5.