JPS60251932A - Catalyst for preparing formaldehyde by oxidation of methylal - Google Patents
Catalyst for preparing formaldehyde by oxidation of methylalInfo
- Publication number
- JPS60251932A JPS60251932A JP59107442A JP10744284A JPS60251932A JP S60251932 A JPS60251932 A JP S60251932A JP 59107442 A JP59107442 A JP 59107442A JP 10744284 A JP10744284 A JP 10744284A JP S60251932 A JPS60251932 A JP S60251932A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- methylal
- oxidation
- formaldehyde
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
発明の目的
（産業上の利用分野）
本発明はメチラール酸化反応によるホルムアルデヒド製
造用触媒に関するものである。さらに詳しくは、メチラ
ールを気相において酸素を含有するガスによって酸化す
ることによりホルムアルデヒドを得るための触媒に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION Object of the Invention (Field of Industrial Application) The present invention relates to a catalyst for producing formaldehyde by methylal oxidation reaction. More specifically, it relates to a catalyst for obtaining formaldehyde by oxidizing methylal in the gas phase with an oxygen-containing gas.
（従来の技術）
従来、ホルムアルデヒドの製造は、銀又は鉄−モリブデ
ン触媒の存在下にメタノールを酸化することにより行な
われている。しかしこの方法により得られるホルマリン
の濃度は量論的に反応したとしても、たかだか６３重量
％である。それに対してメチラール酸化反応により得ら
れるホルマリンの濃度は量論的に反応すれば８３重量％
であシ、メタノールの酸化に比べて生成ガス中の水の量
が非常に少ないという特徴を有する。メチラールの酸化
反応に有効な触媒としては銀、酸化銅及びモリブデンを
基本として、それに鉄、マンガン、マグネシウム、カド
ミウム、カルシウム等を加えた触媒が知られている。し
かしながらこれらの触媒では、−酸化炭素、ジメチルエ
ーテル及びギ酸メチルの副生が多く、高選択性でホルム
アルデヒドを得ることは困難であシ、酸化活性が低いた
め高温での運転を必要とする。本発明者らは、先に鉄、
モリブデン及びアルカリ金属、ビスマス、クロムタング
ステン、ニッケル、コノ々ルトから選ばれた１種又はそ
れ以上の金属元素を不動成分とする触媒が、上記の副生
成物が少なく高選択性を有することを見い出し特許出願
した（特開昭５７−１３４４３２号公報）。(Prior Art) Formaldehyde has traditionally been produced by oxidizing methanol in the presence of silver or iron-molybdenum catalysts. However, the concentration of formalin obtained by this method is at most 63% by weight even if the reaction is stoichiometric. On the other hand, the concentration of formalin obtained by methylal oxidation reaction is 83% by weight if the reaction is carried out stoichiometrically.
However, compared to methanol oxidation, the amount of water in the produced gas is very small. Catalysts based on silver, copper oxide, and molybdenum, to which iron, manganese, magnesium, cadmium, calcium, etc. are added are known as effective catalysts for the oxidation reaction of methylal. However, these catalysts produce many by-products of carbon oxide, dimethyl ether, and methyl formate, making it difficult to obtain formaldehyde with high selectivity, and requiring operation at high temperatures due to low oxidation activity. The inventors first discovered iron,
It has been discovered that a catalyst containing molybdenum and one or more metal elements selected from alkali metals, bismuth, chrome-tungsten, nickel, and conort as an immobile component has high selectivity with few by-products. A patent application was filed (Japanese Unexamined Patent Publication No. 134432/1983).
（発明が解決しようとする問題点）
本発明者等は、メチラールの酸化によるホルムアルデヒ
ドの製造用触媒について、更に鋭意研究をｉねた結果、
ホルムアルデヒドの生成活性が高い上に、その活性が安
定に維持される触媒を見い出し、本発明を完成するに到
った。すなわち、本発明は、メチラールの酸化によるホ
ルムアルデヒドの製造に際して、反応初期の活性が高い
ばかりでなく、長期に反応を行った場合にも、メチラー
ルの転化率及びホルムアルデヒドの選択率が共に制い触
媒を提供するものである。(Problems to be Solved by the Invention) As a result of further intensive research into catalysts for producing formaldehyde by oxidation of methylal, the present inventors have found that:
The present invention was completed by discovering a catalyst that not only has a high formaldehyde production activity but also maintains that activity stably. That is, in the production of formaldehyde by oxidation of methylal, the present invention not only has a high activity at the initial stage of the reaction, but also has a catalyst that controls both the conversion rate of methylal and the selectivity of formaldehyde even when the reaction is carried out for a long period of time. This is what we provide.
発明の目的
（問題点を解決するだめの手段及び作用）本発明は、鉄
及びモリブデンに加えてアルカリ金属、ビスマス、クロ
ム、タングステン、コノＺルト及びニッケルから選ばれ
た１褌またはそれ以上の金属元素を有効成分とし、これ
らの金属元素の割合が金属原子比で、鉄１に対しモリブ
デン１．５〜３．０１アルカリ金属、ビスマス、クロム
、タングステン、コバルト及びニッケルの合計が０．０
０１〜０．１であることを特徴とするメチラールの酸化
によるホルムアルデヒドの製造用触媒に関するものであ
る。触媒組成比が、金属原子比で鉄１に対しモリブデン
が３．０より大きい場合、ホルムアルデヒドの収率が低
くなる。（この傾向は、反応系中に水がよシ多童に存在
する場合には、より顕著になる。）
また、金属原子比で鉄１に対しモリブデンが１．５より
小さい場合には、ホルムアルデヒドの選択率が低下する
だけでなく活性の経時低下があられれてくる。Purpose of the Invention (Means and Effects for Solving the Problems) The present invention is directed to the use of one or more metals selected from iron and molybdenum, as well as alkali metals, bismuth, chromium, tungsten, co-metallic metals, and nickel. Elements are used as active ingredients, and the ratio of these metal elements is a metal atomic ratio of 1.5 to 3.01 molybdenum to 1 iron, and the total of alkali metals, bismuth, chromium, tungsten, cobalt and nickel is 0.0.
The present invention relates to a catalyst for producing formaldehyde by oxidizing methylal, characterized in that the oxidation ratio is 01 to 0.1. If the catalyst composition ratio is greater than 3.0 molybdenum to 1 iron in metal atomic ratio, the yield of formaldehyde will be low. (This tendency becomes more pronounced when there is a large amount of water in the reaction system.) Also, if the metal atomic ratio of molybdenum to iron is less than 1.5, formaldehyde Not only does the selectivity of the compound decrease, but also the activity decreases over time.
一方、触媒組成として、アルカリ金属、ビスマス、クロ
ム、タングステン、コノ々ルト及びニッケルの合計含量
が金属原子比で鉄１に対しｏ、ｏｏｉより小さい場合に
は、ホルムアルデヒドの選択率が低下するたけでなく、
活性の経時低下が顕著にあられれてくる。On the other hand, if the total content of alkali metals, bismuth, chromium, tungsten, conalt, and nickel in the catalyst composition is smaller than o or ooi to 1 iron in terms of metal atomic ratio, the formaldehyde selectivity will simply decrease. Without,
There is a noticeable decrease in activity over time.
また、これらの金橋元累の合計が金属原子比で鉄１に対
し０．１より大きい場合は、ホルムアルデヒドの収率が
低くなる。Furthermore, if the total metal atomic ratio of these metals is greater than 0.1 to 1 iron, the yield of formaldehyde will be low.
これらの触媒を用いた場合、３００℃以下の温度におい
ても、メチラールからホルムアルデヒドの収率は９０％
以上であり、選択率も９５％以上である。また、−酸化
炭素、ジメチルエーテル、ギ酸メチルの生成は少ない。When these catalysts are used, the yield of formaldehyde from methylal is 90% even at temperatures below 300°C.
This is the above, and the selectivity is also 95% or more. Furthermore, the production of -carbon oxide, dimethyl ether, and methyl formate is small.
モリブデンの飛散量が少なく安定性が増すことが示され
た。It was shown that the amount of molybdenum scattered is small and the stability is increased.
本発明の触媒の好ましい例としては、鉄及びモリブデン
にクロムを含むもの、或はクロムとナトリウム、或はク
ロムとカリウムを含むものなどがある。Preferred examples of the catalyst of the present invention include those containing chromium in addition to iron and molybdenum, or those containing chromium and sodium, or chromium and potassium.
本発明における触媒の調製は、通常、含浸法、共演法な
どで行われるが、その他の方法で行っても構わない。好
ましい触媒調製法の一例を示せば、鉄供給物質、モリブ
デン供給物質、アルカリ金属、クロム、ビスマス、タン
グステン、コノ々ルト、マたはニッケルから選ばれたＩ
Ｎまたはそれ以上の元素の供給物質を所定の原子比で混
合（〜、沈澱物を洗浄、乾燥、焼成を経て調製される。The preparation of the catalyst in the present invention is usually carried out by an impregnation method, a co-oxidation method, etc., but other methods may also be used. In one preferred method of catalyst preparation, an iron donor, a molybdenum donor, an alkali metal, I selected from chromium, bismuth, tungsten, conort, aluminum, or nickel.
It is prepared by mixing supply materials containing N or more elements at a predetermined atomic ratio (~, washing the precipitate, drying, and calcination).
混合の割合は、原子比で鉄１に対してモリブデン０．５
〜３．０、アルカリ金属、クロム、ビスマス、タングス
テン、コノζルトまたはニッケルから選ばれた１種また
はそれ以上の元素の合計がｏ、ｏｏｓ〜０．２であるこ
とが好ましい。The mixing ratio is 1 part iron to 0.5 part molybdenum in atomic ratio.
It is preferable that the sum of one or more elements selected from alkali metals, chromium, bismuth, tungsten, conort or nickel is o, oos - 0.2.
各金属の供給物質は、特に限定はなく、塩化物硝酸塩、
酢酸塩など、どの様な形でも良いが、モリブデン及びタ
ングステン供給物質としてはアンモニウム塩が、その他
の金属の供給物質としては、硝酸塩が好ましい。かかる
方法により調製された触媒は、組成が金属原子比で鉄１
に対してモリブデン１．５〜３．０であり、Ｘ線回折に
より結晶性の遊離の三酸化モリブデンの回折線はほとん
ど認められなかった。There are no particular limitations on the materials to be supplied for each metal, including chloride, nitrate,
Any form such as acetate may be used, but ammonium salts are preferred as molybdenum and tungsten supply materials, and nitrates are preferred as other metal supply materials. The catalyst prepared by this method has a composition of 1 iron in terms of metal atomic ratio.
molybdenum was 1.5 to 3.0, and almost no diffraction line of crystalline free molybdenum trioxide was observed by X-ray diffraction.
本発明の触媒を使用するメチラールの酸化に際し用いら
れる温度は通常２００℃から４００℃の範囲である。２
００℃未満ではホルムアルデヒドの収率が低く実際的で
なく、４００℃をこえる温度では一酸化炭素の副生が原
しく、ホルムアルデヒＰの収率、選択率が低下するので
好寸しくない。The temperatures used in the oxidation of methylal using the catalyst of the present invention are generally in the range of 200°C to 400°C. 2
If the temperature is lower than 00°C, the yield of formaldehyde will be low and it is not practical, and if the temperature exceeds 400°C, carbon monoxide will be produced as a by-product, and the yield and selectivity of formaldehyde P will decrease, which is not suitable.
本発明の触媒を使用するメチラールの酪化に際し供給す
るメチラール：酸素の組成比（モル比）はｔ：Ｏ，Ｓ〜
１：３が好ましく、爆発範囲を避けるために、窒素等の
不活性ガスを共存させることが好ましい。The composition ratio (molar ratio) of methylal to oxygen to be supplied during butylation of methylal using the catalyst of the present invention is t:O,S~
The ratio is preferably 1:3, and in order to avoid an explosive range, it is preferable to coexist with an inert gas such as nitrogen.
また、供給ガスの梁間速度（ＳＶ）は２０００ないし５
００００ ｈｒ−１の範囲が好ましい。In addition, the beam velocity (SV) of the supplied gas is between 2000 and 5.
A range of 0000 hr-1 is preferred.
本反応は常圧、加圧、減圧いずれによっても良い。次に
本発明を実施例によりさらに詳細に説明する。This reaction may be carried out under normal pressure, increased pressure, or reduced pressure. Next, the present invention will be explained in more detail with reference to Examples.
実施例１
（ＮＨ４）ｓＭｏ７０ｚ４・４Ｈ２０２６５ｆ／を水３
０００ ｄに溶かした溶液と、Ｆｅ （ＮＯｓ）ｓ ・
９Ｈ２０ｓｏｓ ？ ｆ水ｉｏｏｏｍｌに溶かした溶液
と、０ｒ（ＮＯ３）３ ・９ Ｈ２Ｏ１０？を水ｉ ｏ
Ｏｒｒｔｌに溶かした溶液を混合し清拌した後、生成
ゲルを水３０００ｍにて３回洗浄し、濾過後、１００℃
で２４時間乾燥し、４００℃で４時間空気焼成して生成
物を得た。この生成物のモリブデン：鉄ニクロムの原子
比は２．７ ： ｌ ： ｏ、ｏｚであった。この生成
物を錠剤成型して触媒として使用した。Example 1 (NH4)sMo70z4・4H20265f/3 water
000 d solution and Fe (NOs)s ・
9H20sos? A solution dissolved in f water ioooml and 0r(NO3)3 ・9 H2O10? water io
After mixing and stirring the solution dissolved in Orrtl, the resulting gel was washed three times with 3000 m of water, filtered, and heated at 100°C.
The product was dried for 24 hours and air-calcined at 400° C. for 4 hours to obtain a product. The molybdenum:iron nichrome atomic ratio of this product was 2.7:1:o, oz. This product was tableted and used as a catalyst.
メチラールの酸化反応は、メチラール：Ｎ、：０２モル
比２：３０：３の混合ガスを石英ガラス製反応管中の触
媒層に８Ｖ １００００ ｈｒ ’反応温度２９０℃で
通過させて行なった。The oxidation reaction of methylal was carried out by passing a mixed gas of methylal:N, :02 in a molar ratio of 2:30:3 through a catalyst layer in a quartz glass reaction tube at 8V 10,000 hr' at a reaction temperature of 290°C.
その結果、メチラールの転化率は１００％、ホルムアル
デヒドへの選択率は９８％であった。その際、−酸化炭
素１％、ジメチルエーテル１％が副生した。１００時間
後におけるメチラールの転化率は９８％であった。As a result, the conversion rate of methylal was 100%, and the selectivity to formaldehyde was 98%. At that time, 1% of -carbon oxide and 1% of dimethyl ether were produced as by-products. The conversion rate of methylal after 100 hours was 98%.
実施例２
実施例１において０ｒ（ＮＯ３）３４９Ｈ１０１０Ｓｉ
’ （７）代わシに０ｒ（ＮＯ３）３・９Ｈ２０１０？
及びＫＮＯ３２，５Ｓ’を用いる他は全く同様に触媒を
調製し反応に供した。 ｊ１実施例３
実施例１においてＯｒ （ＮＯ３）３ ・９ Ｈ２Ｏ１
０Ｙ （７）代わりに０ｒ（ＮＯ３）ｓ ・９Ｈ２０１
０？及びＮａＮＯ３２？を用いる他は全く同様に触媒を
調製し反応に供した。Example 2 In Example 1, 0r(NO3)349H1010Si
'(7) 0r(NO3)3・9H2010 instead?
A catalyst was prepared in exactly the same manner except that KNO32,5S' was used and subjected to the reaction. j1 Example 3 In Example 1, Or (NO3)3 ・9 H2O1
0Y (7) Instead 0r(NO3)s ・9H201
0? and NaNO32? A catalyst was prepared and subjected to the reaction in exactly the same manner except that .
実施例４
実施例１においてＣｒ（ＮＯ３）ｓ ・９Ｈ２０１ＯＳ
’の代わシにＢ ｉ （ＮＯり３・５Ｈ２０１２Ｆを用
いる他は全く同様に触媒を調製し反応に供した。Example 4 In Example 1, Cr(NO3)s 9H201OS
A catalyst was prepared in exactly the same manner except that B i (NO 3.5H2012F was used instead of ') and subjected to the reaction.
実施例５
実施例１において０ｒ（Ｎｏｔ）ｓ −９Ｈｚ０１０
ｙの代わシに（ＮＨ４）ｘｏＷ＋ｚＯｎ ・５ＨｚＯ６
ｔを用いる他は全く同様に触媒を調製し反応に供した。Example 5 0r(Not)s -9Hz010 in Example 1
In place of y (NH4)xoW+zOn ・5HzO6
A catalyst was prepared and subjected to the reaction in exactly the same manner except that t was used.
実施例６
実施例１においてＣｒ（ＮＯ３）３ ・９Ｈ２０１０ｆ
’の代わシに００（ＮＯ３）２ ・６Ｈ２０７，３ｔ
ヲ用イル他１ｄ、全＜ Ｐｌ 様に触媒を調製し反応に
供した。Example 6 Cr(NO3)3 ・9H2010f in Example 1
' instead of 00 (NO3)2 ・6H207,3t
A catalyst was prepared and subjected to the reaction.
実施例７
実施例１においてＯｒ （ＮＯ３）３ ・９Ｈ２０１０
？の代わシにＮ ｉ （ＮＯｓ）２・６Ｈ２０７，３Ｆ
を用いる他は全く同様に触媒を調製し反応に供した。Example 7 In Example 1, Or (NO3)3 ・9H2010
? Instead of Ni (NOs) 2・6H207,3F
A catalyst was prepared and subjected to the reaction in exactly the same manner except that .
比較例１
（ＮＨ４）６ＭＯ７０２４・４Ｈ２０８９５Ｙを使う他
は実施例１と同じ転化率を借るには３３０℃の温度が必
要であった。Comparative Example 1 A temperature of 330°C was required to obtain the same conversion as in Example 1, except that (NH4)6MO7024.4H20895Y was used.
比較例２
Ｏｒ （ＮＯ３）３ ・９ Ｈ２Ｏを用いない他は、実
施例１と全く同じ方法で触媒を調製し反応に供した。こ
の触媒を用いて実施例１と同じ条件でメチラールの酸化
反応を行なった。その結果、メチラールの転化率は９９
％であったが１００時間後の転化率は９０％に低下した
。Comparative Example 2 Or (NO3)3 .9 A catalyst was prepared and subjected to reaction in exactly the same manner as in Example 1, except that H2O was not used. Using this catalyst, methylal oxidation reaction was carried out under the same conditions as in Example 1. As a result, the conversion rate of methylal was 99
%, but the conversion rate decreased to 90% after 100 hours.
実施例８
実施例１において０ｒ（ＮＯ３）３・９Ｈ２０の代わシ
にＫＮｏ、 ５．０ ？を用いる他は全く同様に触媒を
調製し反応に供した。Example 8 In Example 1, instead of 0r(NO3)3.9H20, KNo, 5.0? A catalyst was prepared and subjected to the reaction in exactly the same manner except that .
実施例９
実施例１において０ｒ（ＮＯ３）３・９Ｈ２ｏの代わり
にＮａＮＯ３４，０１を用いる他は全く同様に触媒を調
製し、反応に供した。Example 9 A catalyst was prepared in exactly the same manner as in Example 1 except that NaNO34,01 was used instead of Or(NO3)3.9H2o, and subjected to reaction.
実施例１〜９及び比較例１．２の結果を表に示す。The results of Examples 1 to 9 and Comparative Example 1.2 are shown in the table.
発明の効果
以上述べた様に、本発明の触媒はメチラールの酸化によ
シホルムアルデヒドを製造する場合に、反応初期はもち
ろん、長期反応においても、メチラールの転化率及びホ
ルムアルデヒドの選択率の高い活性な触媒であって工業
上極めて有用な触媒である。Effects of the Invention As mentioned above, the catalyst of the present invention is an active catalyst with high methylal conversion and formaldehyde selectivity not only at the initial stage of the reaction but also during long-term reactions when producing cyformaldehyde by oxidizing methylal. It is a catalyst that is extremely useful industrially.
特許出願人 旭化成工業株式会社Patent applicant: Asahi Kasei Industries, Ltd.
Claims (1)
ロム、タングステン、コノモルト、ニッケルから選ばれ
た１種またはそれ以上の金属元素を有効成分とし、これ
らの金属元素の含有割合が金ｌＩ４原子比で鉄１に対し
、モリブデン１．５〜３．０、アルカリ金属、ビスマス
、クロム、タングステン、コバルト、ニッケルの合計が
０．００１〜０．１であることを特徴とするメチラール
の酸化によるホルムアルデヒド製造用触媒In addition to iron and molybdenum, the active ingredient is one or more metal elements selected from alkali metals, bismuth, chromium, tungsten, conomolt, and nickel, and the content ratio of these metal elements is gold lI4 atomic ratio iron 1 A catalyst for formaldehyde production by oxidation of methylal, characterized in that the total of molybdenum is 1.5 to 3.0, alkali metals, bismuth, chromium, tungsten, cobalt, and nickel is 0.001 to 0.1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59107442A JPS60251932A (en) | 1984-05-29 | 1984-05-29 | Catalyst for preparing formaldehyde by oxidation of methylal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59107442A JPS60251932A (en) | 1984-05-29 | 1984-05-29 | Catalyst for preparing formaldehyde by oxidation of methylal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60251932A true JPS60251932A (en) | 1985-12-12 |
| JPH0376179B2 JPH0376179B2 (en) | 1991-12-04 |
Family
ID=14459252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59107442A Granted JPS60251932A (en) | 1984-05-29 | 1984-05-29 | Catalyst for preparing formaldehyde by oxidation of methylal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60251932A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0327343A2 (en) * | 1988-02-03 | 1989-08-09 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for producing formaldehyde and derivatives thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57134432A (en) * | 1981-02-13 | 1982-08-19 | Asahi Chem Ind Co Ltd | Production of formaldehyde |
-
1984
- 1984-05-29 JP JP59107442A patent/JPS60251932A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57134432A (en) * | 1981-02-13 | 1982-08-19 | Asahi Chem Ind Co Ltd | Production of formaldehyde |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0327343A2 (en) * | 1988-02-03 | 1989-08-09 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for producing formaldehyde and derivatives thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0376179B2 (en) | 1991-12-04 |
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