JPS6140809A - Refreshing method of phosgene manufacturing catalyst - Google Patents
Refreshing method of phosgene manufacturing catalystInfo
- Publication number
- JPS6140809A JPS6140809A JP59161624A JP16162484A JPS6140809A JP S6140809 A JPS6140809 A JP S6140809A JP 59161624 A JP59161624 A JP 59161624A JP 16162484 A JP16162484 A JP 16162484A JP S6140809 A JPS6140809 A JP S6140809A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- catalyst
- phosgene
- reaction
- temperature
- 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.)
- Pending
Links
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- NHYCGSASNAIGLD-UHFFFAOYSA-N chlorine monoxide Inorganic materials Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000007796 conventional method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 2
- 238000012856 packing Methods 0.000 abstract 1
- 230000001186 cumulative effect Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000009529 body temperature measurement Methods 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910001902 chlorine oxide Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はホスゲン製造触媒の更新方法に関し、更に詳し
くは塩素と一酸化炭素を触媒反応させてホスゲンを連続
的に製造するのに使用した反応管中の活性炭触媒を合理
的、経済的に更新する方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for renewing a catalyst for producing phosgene, and more particularly, it relates to a method for renewing a catalyst for producing phosgene, and more specifically, for renewing a catalyst for producing phosgene in a reaction tube used to continuously produce phosgene by catalytically reacting chlorine and carbon monoxide. This invention relates to a method for rationally and economically renewing activated carbon catalysts.
従来技術
ホスゲンの工業的製造方法の一つに、反応管に充填され
た活性炭層に塩素と一酸化炭素の混合ガスを連続的に通
す方法がある。この方法においては、原料混合ガス中に
含まれる不純物等により活性炭の触媒活性が徐々に低下
、失活するので、適当な時期に活性炭を更新する必要が
ある。BACKGROUND OF THE INVENTION One of the industrial methods for producing phosgene is a method in which a mixed gas of chlorine and carbon monoxide is continuously passed through an activated carbon bed filled in a reaction tube. In this method, the catalytic activity of the activated carbon gradually decreases and is deactivated due to impurities contained in the raw material mixed gas, so it is necessary to renew the activated carbon at an appropriate time.
従来、この判断基準としてホスゲンの累積生産量や反応
管の出口側温度が用いられている。しかしながら、原料
ガス中の不純物は該ガスの製造方法、製造原料等によっ
て質、量ともに変化し、また活性、炭の触媒性能も必ず
しも一定しないため、ホスゲンの累積生産量を基準とす
る方法は合理的とは言えず、出口側温度による方法も必
ずしも合理的とは言えない。いずれの方法によるも触媒
の失活状態を正確に把握することが困難なことから、触
媒は未だ触媒能を有する活性炭をも含めて全量を更新す
ることになっていた。Conventionally, the cumulative production amount of phosgene and the temperature on the outlet side of the reaction tube have been used as criteria for this judgment. However, the quality and quantity of impurities in the raw gas vary depending on the gas production method, production raw materials, etc., and the activation and catalytic performance of charcoal are not necessarily constant, so it is reasonable to use the cumulative production amount of phosgene as the standard. It cannot be said that the method based on the outlet side temperature is necessarily rational. Since it is difficult to accurately grasp the deactivated state of the catalyst using either method, the entire amount of catalyst, including activated carbon that still has catalytic ability, was to be renewed.
発明の目的
本発明者らは、真に失活した活性炭を検出しその部分の
みを更新することの合理性、経済性に肴目し、新しい更
新方法を開発すべく鋭意研究した結果、次の事実を見出
した。Purpose of the Invention The present inventors were interested in the rationality and economics of detecting truly deactivated activated carbon and renewing only that part, and as a result of intensive research to develop a new renewal method, they discovered the following. I found out the truth.
すなわち、活性炭の更新直後においては活性炭層の温度
は混合ガス供給側から急傾斜で上昇して最高温度に達し
、それから排出側に向かって緩い傾斜で低下する。そし
てホスゲンの累積生産量の増大につれて、活性炭層の温
度分布はその形を殆ど維持したまま全体として排出側に
移動する。また混合ガスの供給速度を増すと、最高温度
の位置は僅かに排出側に移動し、それから排出側に向か
う温度低下の傾斜が緩くなる。かかる現象の生ずる理由
としては、混合ガスの大部分は供給側の有効な活性炭の
薄い層で反応し、その反応熱が排出側に伝えられており
、混合ガスの供給速度を増すと反応熱量が増加するため
に排出側に向かう温度の傾斜が緩くなること、また混合
ガス中の不純物は供給側から順に活性炭を失活すること
、このため最高温度の位置より排出側の活性炭はほとん
ど失活しないことが推定される。That is, immediately after the activated carbon is renewed, the temperature of the activated carbon layer rises at a steep slope from the mixed gas supply side, reaches the maximum temperature, and then decreases at a gentle slope toward the discharge side. As the cumulative production of phosgene increases, the temperature distribution of the activated carbon layer as a whole moves toward the discharge side while maintaining most of its shape. Furthermore, when the supply speed of the mixed gas is increased, the position of the highest temperature moves slightly toward the discharge side, and the slope of temperature decrease toward the discharge side becomes gentler. The reason for this phenomenon is that most of the mixed gas reacts in a thin layer of effective activated carbon on the supply side, and the heat of reaction is transferred to the discharge side, and as the supply speed of the mixed gas increases, the amount of reaction heat increases. As the temperature increases, the gradient of temperature toward the discharge side becomes gentler, and impurities in the mixed gas deactivate the activated carbon sequentially from the supply side, so activated carbon on the discharge side is hardly deactivated from the position of the highest temperature. It is estimated that
本発明の目的は、真に触媒能の低下乃至失活した活性炭
を検出し、それのみを更新する合理的な更新方法を提供
することにある。An object of the present invention is to provide a rational renewal method that detects activated carbon whose catalytic ability has truly decreased or has been deactivated, and renews only that activated carbon.
発明の構成
本発明の目的は、本発明によれば、触媒として活性炭を
充填した反応管中での、塩素と一酸化炭素の混合ガスの
接触反応でホスゲンを連続的に製造する方法に使用した
該反応管中の触媒を更新するにあたり、活性炭層の反応
時の温度分布で最高温度を示した位置より混合ガス供給
側の活性炭を更新することを特徴とするホスゲン製造触
媒の更新方法によって達成される。According to the present invention, an object of the present invention is to provide a method for continuously producing phosgene by a catalytic reaction of a mixed gas of chlorine and carbon monoxide in a reaction tube filled with activated carbon as a catalyst. In renewing the catalyst in the reaction tube, the activated carbon on the mixed gas supply side is renewed from the position where the highest temperature is shown in the temperature distribution during the reaction of the activated carbon layer. Ru.
塩素と一酸化炭素とからホスゲンを生成する反応は可逆
反応であり、平衡は高温では反応系（混合ガス）側に、
低温では生成系（ホスゲン）側にある。このため生成ホ
スゲンは出来るだけ低温に保つことが好ましい。本発明
者らの知見によれば、活性炭層の排出側温度を１００℃
以下に保つと、９９．５％以上の反応率が得られる。し
かして、触媒更新時期は、活性炭層の排出側温度を測定
しておき、この温度が１００℃以下であることを基準に
して判断すると良い。この場合、９９．５％以上の反応
率を得ることができる。The reaction that produces phosgene from chlorine and carbon monoxide is a reversible reaction, and the equilibrium is on the side of the reaction system (mixed gas) at high temperatures.
At low temperatures, it is on the generation system (phosgene) side. For this reason, it is preferable to keep the generated phosgene at as low a temperature as possible. According to the findings of the present inventors, the discharge side temperature of the activated carbon layer is set at 100°C.
If it is kept below, a reaction rate of 99.5% or more can be obtained. Therefore, it is preferable to measure the temperature on the discharge side of the activated carbon layer and determine when to update the catalyst based on the fact that this temperature is 100° C. or less. In this case, a reaction rate of 99.5% or more can be obtained.
活性炭層の温度分布は、反応管の寸法、冷却方法、混合
ガスの供給速度などによって変化するが、例えば混合ガ
スの供給速度を大きくした場合排出側温度が１００℃を
超えても最高温度を示す位置が活性炭層全長の中央より
供給側にあることがある。The temperature distribution of the activated carbon layer changes depending on the dimensions of the reaction tube, the cooling method, the supply rate of the mixed gas, etc., but for example, when the supply rate of the mixed gas is increased, the maximum temperature will be reached even if the discharge side temperature exceeds 100°C. The position may be on the supply side from the center of the entire length of the activated carbon bed.
このような場合、本発明によれば触媒更新の（５）は従
来法に比して、１／２以下で済むようになる。In such a case, according to the present invention, catalyst renewal (5) can be reduced to 1/2 or less compared to the conventional method.
本発明において用いる活性炭は従来から用いられている
活性炭で良い。またホスゲン製造に供した塩素及び−酸
化炭素も従来から用いられているもので良い。−これら
については特に制限はない。The activated carbon used in the present invention may be any conventionally used activated carbon. Furthermore, the chlorine and carbon oxide used in the production of phosgene may be those conventionally used. - There are no particular restrictions on these.
本発明における活性炭層の温度分布は反応時の活性炭層
の温度分布であり、これは活性炭層中或はその外側に所
定の間隔で温度検出計を置くことによって求やることが
できる。The temperature distribution of the activated carbon layer in the present invention is the temperature distribution of the activated carbon layer during the reaction, and can be determined by placing temperature detectors at predetermined intervals in or outside the activated carbon layer.
発明の効果
本発明によれば失活した乃至活性の低下した活性炭の部
分のみを更新することができ、従って触媒の更新量を低
減することができる。ホスゲンの製造条件によっては触
媒の更新量を、従来法に比して、約１／２以下に低減す
ることができる。Effects of the Invention According to the present invention, it is possible to renew only the portion of the activated carbon that has been deactivated or whose activity has decreased, and therefore the amount of catalyst renewal can be reduced. Depending on the phosgene production conditions, the amount of catalyst renewal can be reduced to about 1/2 or less compared to the conventional method.
実施例 以下に実施例を挙げて本発明を更に説明する。Example The present invention will be further explained with reference to Examples below.
参考例
直径が１０００ａｍと１ｉｏｏ、の同軸二重円筒状の反
応筒の輪状部に温度測定用金属管を挿入し、輪状部に活
性炭を充填し、かつ二重円筒の内側と外側に冷却水を通
した。次に一酸化炭素と塩素の混合ガスを輪状部の上方
から供給した。温度測定用金属管内に熱雷対を挿入し、
ホスゲンの累積生産量に対応して活性炭層の各部の温度
を測定した。また混合ガスの供給速度を変えて同様に温
度を測定した。それらの結果を第１図に示す。Reference example: A metal tube for temperature measurement is inserted into the annular part of a coaxial double cylindrical reaction cylinder with diameters of 1000 am and 1 ioo, the annular part is filled with activated carbon, and cooling water is poured inside and outside of the double cylinder. I passed it. Next, a mixed gas of carbon monoxide and chlorine was supplied from above the ring. Insert a thermal lightning pair into the metal tube for temperature measurement,
The temperature of each part of the activated carbon layer was measured in accordance with the cumulative production amount of phosgene. Furthermore, the temperature was measured in the same manner while changing the supply rate of the mixed gas. The results are shown in FIG.
曲線Ａは累積生産量５００Ｔｏｎ、曲線Ｂは累積生産量
１０００Ｔ ｏｎのときの温度分布であり、曲線Ｂ′は
、混合ガスの供給速度を３０％増加したときの温度分布
である。Curve A is the temperature distribution when the cumulative production amount is 500 tons, curve B is the temperature distribution when the cumulative production amount is 1000 tons, and curve B' is the temperature distribution when the mixed gas supply rate is increased by 30%.
上述の反応を行った後の反応筒から活性炭の表面部分（
着色物何着）のみを採取し、直径４０ｍのガラス管に充
填して、−酸化炭素と塩素の混合ガスを通した。温度は
上らず、排出ガスは微量のホスゲンを含むだけであった
。After performing the above reaction, remove the surface part of activated carbon from the reaction tube (
The colored material was collected and filled into a glass tube with a diameter of 40 m, and a mixed gas of carbon oxide and chlorine was passed through it. The temperature did not rise and the exhaust gas contained only trace amounts of phosgene.
実施例１
参考例による反応を行った後の反応筒から減圧パイプを
使用して最高温度位置から上部の活性炭を抜き取り、そ
れだけを新しい活性炭で補充した。Example 1 After carrying out the reaction according to Reference Example, the activated carbon at the top from the highest temperature position was extracted from the reaction tube using a vacuum pipe, and only that part was replenished with fresh activated carbon.
次いで参考例と同じ条件で反応を行なったところ、はぼ
第１図と同じ温度分布の曲線が得られた。Next, a reaction was carried out under the same conditions as in the reference example, and a curve with the same temperature distribution as in FIG. 1 was obtained.
第１図はホスゲン製造時の触媒活性炭層の温度分布を示
す図である。
特許出願人 帝 人 株 式 会 社
四 −FIG. 1 is a diagram showing the temperature distribution of a catalytic activated carbon layer during phosgene production. Patent applicant Teijin Ltd. Company 4 -
Claims (1)
化炭素の混合ガスの接触反応でホスゲンを連続的に製造
する方法に使用した該反応管中の触媒を更新するにあた
り、活性炭層の反応時の温度分布で最高温度を示した位
置より混合ガス供給側の活性炭を更新することを特徴と
するホスゲン製造触媒の更新方法。When renewing the catalyst in a reaction tube used in a method for continuously producing phosgene through a catalytic reaction of a mixed gas of chlorine and carbon monoxide in a reaction tube filled with activated carbon as a catalyst, the reaction of the activated carbon layer was carried out. A method for renewing a phosgene production catalyst characterized by renewing activated carbon on the mixed gas supply side from the position where the highest temperature is shown in the temperature distribution at the time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59161624A JPS6140809A (en) | 1984-08-02 | 1984-08-02 | Refreshing method of phosgene manufacturing catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59161624A JPS6140809A (en) | 1984-08-02 | 1984-08-02 | Refreshing method of phosgene manufacturing catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6140809A true JPS6140809A (en) | 1986-02-27 |
Family
ID=15738716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59161624A Pending JPS6140809A (en) | 1984-08-02 | 1984-08-02 | Refreshing method of phosgene manufacturing catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6140809A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020216648A1 (en) * | 2019-04-25 | 2020-10-29 | Basf Se | Method for producing phosgene |
-
1984
- 1984-08-02 JP JP59161624A patent/JPS6140809A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020216648A1 (en) * | 2019-04-25 | 2020-10-29 | Basf Se | Method for producing phosgene |
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