JPH03133939A - Production of partially chlorinated methane - Google Patents
Production of partially chlorinated methaneInfo
- Publication number
- JPH03133939A JPH03133939A JP27183289A JP27183289A JPH03133939A JP H03133939 A JPH03133939 A JP H03133939A JP 27183289 A JP27183289 A JP 27183289A JP 27183289 A JP27183289 A JP 27183289A JP H03133939 A JPH03133939 A JP H03133939A
- Authority
- JP
- Japan
- Prior art keywords
- group element
- catalyst
- carbon tetrachloride
- methane
- hydrogen
- 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.)
- Granted
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000005909 Kieselgur Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 33
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 22
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000047 product Substances 0.000 abstract description 11
- 229940050176 methyl chloride Drugs 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 4
- 229910052763 palladium Inorganic materials 0.000 abstract description 3
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 230000001419 dependent effect Effects 0.000 abstract 1
- 239000007792 gaseous phase Substances 0.000 abstract 1
- 229910052703 rhodium Inorganic materials 0.000 abstract 1
- 229910052707 ruthenium Inorganic materials 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 3
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- 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】
［産業上の利用分野］
本発明は部分塩素化メタンであるクロロホルム、塩化メ
チレン、塩化メチルの製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing partially chlorinated methane such as chloroform, methylene chloride, and methyl chloride.
［従来の技術及び発明が解決しようとする課題］クロロ
ホルム、塩化メチレン、塩化メチルの製造方法としては
、従来、メタンを塩素と ４００〜５００℃高温条件下
又は３０００〜５０００人の波長の光照射下で反応させ
る方法が知られている。更に、メタノールを出発原料と
して用い塩酸と反応させることにより、塩化メチルを製
造し、次いでこれを塩素化して高次塩素化メタンを製造
するいわゆるメタノール法が知られている。[Prior art and problems to be solved by the invention] Conventionally, chloroform, methylene chloride, and methyl chloride have been produced by mixing methane with chlorine under high-temperature conditions of 400 to 500°C or under irradiation with light having a wavelength of 3,000 to 5,000 degrees Celsius. A method of reacting is known. Furthermore, a so-called methanol method is known in which methyl chloride is produced by using methanol as a starting material and reacting it with hydrochloric acid, and then chlorinating this to produce highly chlorinated methane.
しかしながら、いずれの方法においても生成する塩素化
メタンの組成比率は反応条件の調整により変化させるこ
とは可能であるが、単一化合物だけを生成させることは
できず、必ず複数の塩素化メタンの混合物が得られる。However, although it is possible to change the composition ratio of chlorinated methane produced by either method by adjusting the reaction conditions, it is not possible to produce only a single compound, and a mixture of multiple chlorinated methane is always produced. is obtained.
より高次に塩素化されたメタンを得たい場合には生成物
をリサイクルすることによりその目的を達成することが
できるが完全に塩素化されてしまった四塩化炭素を部分
的に塩素化されたメタン（クロロホルム、塩化メチレン
、塩化メチル）に転化させることは従来の塩素化プロセ
スでは不可能である。四塩化炭素を部分的に還元する方
法としては、塩酸を鉄と反応させて生ずる発生期の水素
による還元やメタンやエタン等の低級アルカンの共存下
に高温に加熱する方法等が知られている。しかしながら
、前者は多量の鉄を消費するうえ副生ずる多量の塩化鉄
を処理せねばならずコスト的に工業的規模で採用するこ
とは不可能であり、後者は塩素化エチレン等の副生を伴
う等の問題点を有している。If you want to obtain more highly chlorinated methane, you can achieve that goal by recycling the product, but you can replace completely chlorinated carbon tetrachloride with partially chlorinated carbon tetrachloride. Conversion to methane (chloroform, methylene chloride, methyl chloride) is not possible with conventional chlorination processes. Known methods for partially reducing carbon tetrachloride include reducing it with nascent hydrogen produced by reacting hydrochloric acid with iron, and heating it to high temperatures in the coexistence of lower alkanes such as methane and ethane. . However, the former consumes a large amount of iron and must process a large amount of iron chloride produced as a by-product, making it impossible to use on an industrial scale due to cost considerations, and the latter involves producing by-products such as chlorinated ethylene. It has the following problems.
［課題を解決するための手段］
本発明は前述のような従来技術の問題点を解決すべくな
されたものであり、完全に塩素化された四塩化炭素を部
分的に塩素化されたメタン（クロロホルム・塩化メチレ
ン・塩化メチル）に転化させる製造方法を新規に提供す
ることを目的とするものである。[Means for Solving the Problems] The present invention has been made to solve the problems of the prior art as described above. The purpose of this project is to provide a new manufacturing method for converting chloroform, methylene chloride, and methyl chloride.
即ち、本発明は鉄族元素又は白金族元素触媒の存在下に
、四塩化炭素を水素と反応せしめて部分塩素化メタンを
得ることを特徴とする部分塩素化メタンの製造方法に関
するものである。That is, the present invention relates to a method for producing partially chlorinated methane, which is characterized by reacting carbon tetrachloride with hydrogen in the presence of an iron group element or platinum group element catalyst to obtain partially chlorinated methane.
本発明における鉄族元素触媒としては、Ｆｅ。The iron group element catalyst in the present invention is Fe.
Ｃｏ、Ｎｉを、白金族元素触媒としてはＰｄ、 Ｐｔ、
Ｒｕ。Co, Ni, as platinum group element catalysts Pd, Pt,
Ru.
Ｒｈ等を挙げることができる。これらの鉄族元素や白金
族元素触媒は２種以上併用してもよ（、また、活性炭、
ケイソウ土あるいはアルミナ等の担体に担持させること
ができ、これにより触媒活性を高め、触媒寿命をのばす
ことができる。本発明反応においては、塩化水素が副生
ずるため、耐酸性の高い白金族元素触媒が好ましい。Examples include Rh. Two or more of these iron group element and platinum group element catalysts may be used in combination (also, activated carbon,
It can be supported on a carrier such as diatomaceous earth or alumina, thereby increasing the catalyst activity and extending the catalyst life. In the reaction of the present invention, since hydrogen chloride is produced as a by-product, a platinum group element catalyst with high acid resistance is preferred.
本発明における反応温度としては、あまり低い場合には
反応率が充分得られず、高すぎる場合には、反応率は高
いものの副反応による高沸点成分が生成し、選択率を低
下させたり、触媒寿命を短くしたりするので、 １００
〜４００’Ｃ１好ましくは１５０〜３５０℃の範囲から
選択するとよい。反応は、常圧又は加圧下に液相でも気
相でも可能であるが、選択率や触媒寿命の観点から気相
法が好ましい。気相での反応時間はおよそ５〜６００秒
好ましくは１０〜１００秒が適当である。In the present invention, if the reaction temperature is too low, a sufficient reaction rate cannot be obtained, and if it is too high, although the reaction rate is high, high-boiling components are generated due to side reactions, which may reduce the selectivity or catalyze the reaction. 100 as it may shorten the lifespan.
-400'C1, preferably from the range of 150-350°C. Although the reaction can be carried out in a liquid phase or a gas phase under normal pressure or increased pressure, a gas phase method is preferred from the viewpoint of selectivity and catalyst life. The reaction time in the gas phase is approximately 5 to 600 seconds, preferably 10 to 100 seconds.
使用する水素の量は、使用する四塩化炭素の１倍モル未
満では四塩化炭素の反応率を１００％にすることはでき
ず、又、多すぎる場合には、不必要なメタンの生成量を
多くしてしまう結果となる。従って、使用する水素の量
は、最も得たい生成物がクロロホルムであるか、塩化メ
チレンであるか、塩化メチルであるかにより最適屋とす
ればよいが、およそ四塩化炭素の１〜３倍モルとするこ
とが好ましい。If the amount of hydrogen used is less than 1 mole of carbon tetrachloride to be used, the reaction rate of carbon tetrachloride will not be 100%, and if it is too large, the amount of unnecessary methane produced will be reduced. The result is that you end up spending too much. Therefore, the amount of hydrogen to be used can be optimized depending on whether the desired product is chloroform, methylene chloride, or methyl chloride, but it is approximately 1 to 3 times the molar amount of carbon tetrachloride. It is preferable that
［実施例］
実施例１
直径１インチ長さ１ｍの鉄製反応器に活性炭に０．５ｗ
ｔ％のパラジウムを担持した触媒を充填し、これをマン
トルヒーターにより ２５０’Ｃに加熱した。この反応
器に気化させた四塩化炭素１５４ｇ （１モル）／ｈｒ
を水素 ３４Ｎｌ／ｈｒとともに供給した。四塩化炭素
と水素のモル比は１：１．５である。反応器出口からの
ガスを５％ＮａＯＨ除害びん中バブルさせることにより
、その底部に油状生成物が得られ、又凝縮しないガスが
除害びんから出てきた。３０分間のサンプリングにより
油状生成物４５ｇと非凝縮ガス１４Ｉ２を得た。[Example] Example 1 0.5 W of activated carbon was placed in a steel reactor with a diameter of 1 inch and a length of 1 m.
A catalyst supporting t% of palladium was charged and heated to 250'C with a mantle heater. 154g (1 mol)/hr of carbon tetrachloride vaporized in this reactor
was supplied together with 34 Nl/hr of hydrogen. The molar ratio of carbon tetrachloride to hydrogen is 1:1.5. Bubbling the gas from the reactor outlet into a 5% NaOH abatement bottle resulted in an oily product at the bottom, and non-condensable gas came out of the abatement bottle. Sampling for 30 minutes yielded 45 g of oily product and 14 I2 of non-condensable gas.
ガスクロマトグラフィー分析によると油状生成物の組成
は面積比をモル比に補正後四塩化炭素１５％、クロロホ
ルム６８％、塩化メチレン１４％、塩化メチル３％であ
った。According to gas chromatography analysis, the composition of the oily product, after correcting the area ratio to the molar ratio, was 15% carbon tetrachloride, 68% chloroform, 14% methylene chloride, and 3% methyl chloride.
一方、非凝縮ガスの組成は同様にクロロホルム８％、塩
化メチレン２３％、塩化メチル５４％、メタン１５％で
あったが、このガスクロマトグラフィーの分析条件では
水素は検出できないので組成にはカウントされていない
。On the other hand, the composition of the non-condensable gas was similarly 8% chloroform, 23% methylene chloride, 54% methyl chloride, and 15% methane, but hydrogen cannot be detected under these gas chromatography analysis conditions, so it is not counted in the composition. Not yet.
実施例２
実施例１で用いた反応器を２００’Ｃに加熱し、これに
四塩化炭素７０ｇ （０，４５モル） ／ｈｒ、水素２
５Ｎ１／ｈｒを供給した。四塩化炭素と水素のモル比は
１：２．５である。実施例１と同様に３０分間のサンプ
リングにより除害びんの底部に２６ｇの油状生成物を得
た。実施例１と同様なガスクロマドグラフィー分析によ
れば油状生成物の組成は四塩化炭素３８％、クロロホル
ム４３％、塩化メチレン１８％、塩化メチル２％メタン
痕跡であった。また除害びんから出たガスはほとんど水
素であったため捕捉できなかった。Example 2 The reactor used in Example 1 was heated to 200'C, and 70 g (0.45 mol) of carbon tetrachloride/hr and 2 hydrogen were added to it.
5N1/hr was supplied. The molar ratio of carbon tetrachloride to hydrogen is 1:2.5. As in Example 1, 26 g of oily product was obtained at the bottom of the abatement bottle by sampling for 30 minutes. According to the same gas chromatography analysis as in Example 1, the composition of the oily product was 38% carbon tetrachloride, 43% chloroform, 18% methylene chloride, 2% methyl chloride, and traces of methane. Furthermore, the gas that came out of the abatement bottle was mostly hydrogen, so it could not be captured.
実施例３
実施例１で用いた反応器に２ｗｔ％の白金を活性炭に担
持した触媒を充填し、これをマントルヒーターにより
２５０℃に加熱した。この反応器に気化させた四塩化炭
素１５４ｇ （１モル）／ｈｒを水素３４Ｎ１／ｈｒと
ともに供給した。四塩化炭素と水素のモル比はｌ：１．
５である０反応語呂口からの５％ＮａＯＨ除害びん中バ
ブルさせることにより、その底部に油状生成物が得られ
、又凝縮しないガスが除害びんから出てきた。３０分間
のサンプリングにより油状生成物５２ｇを得た非凝縮ガ
スは水素がほとんどであり分析できなかった。ガスクロ
マトグラフィー分析では油状生成物の組成は四塩化炭素
３８％、クロロホルム４８％、塩化メチレン１２％、塩
化メチル２％であった。Example 3 The reactor used in Example 1 was filled with a catalyst in which 2 wt% of platinum was supported on activated carbon, and this was heated using a mantle heater.
It was heated to 250°C. 154 g (1 mol)/hr of vaporized carbon tetrachloride was fed into this reactor together with 34 N1/hr of hydrogen. The molar ratio of carbon tetrachloride and hydrogen is 1:1.
By bubbling 5% NaOH into the abatement bottle from the 0 reaction mouthpiece, an oily product was obtained at its bottom, and non-condensable gas came out of the abatement bottle. The non-condensable gas from which 52 g of oily product was obtained by sampling for 30 minutes was mostly hydrogen and could not be analyzed. Gas chromatography analysis revealed that the composition of the oily product was 38% carbon tetrachloride, 48% chloroform, 12% methylene chloride, and 2% methyl chloride.
［発明の効果］
本発明は実施例にも示されるように四塩化炭素を有効に
クロロホルム、塩化メチレン、塩化メチルに変換するこ
とができろ。本発明に従えば、メタンまたは塩素化反応
によって得られる四塩化炭素を部分的に還元することが
でき、従来の塩素化反応による四塩化炭素の製法と併用
することにより、任意の部分塩素化メタンをメタン又は
メタノールから効率よく製造することが可能である。[Effects of the Invention] As shown in the Examples, the present invention can effectively convert carbon tetrachloride into chloroform, methylene chloride, and methyl chloride. According to the present invention, it is possible to partially reduce methane or carbon tetrachloride obtained by a chlorination reaction, and by using it together with the conventional method for producing carbon tetrachloride by a chlorination reaction, any partially chlorinated methane can be reduced. can be efficiently produced from methane or methanol.
Claims (1)
素を水素と反応せしめて部分塩素化メタンを得ることを
特徴とする部分塩素化メタンの製造方法。 ２、鉄族元素又は白金族元素触媒が活性炭、ケイソウ土
、又はアルミナに担持されている請求項１に記載の製造
方法。 ３、反応温度が１５０℃〜３５０℃の範囲から選ばれる
請求項１に記載の製造方法。 ４、水素を四塩化炭素の１〜３倍モル使用する請求項１
に記載の製造方法。[Claims] 1. A method for producing partially chlorinated methane, which comprises reacting carbon tetrachloride with hydrogen in the presence of an iron group element or platinum group element catalyst to obtain partially chlorinated methane. 2. The manufacturing method according to claim 1, wherein the iron group element or platinum group element catalyst is supported on activated carbon, diatomaceous earth, or alumina. 3. The manufacturing method according to claim 1, wherein the reaction temperature is selected from the range of 150°C to 350°C. 4.Claim 1 in which hydrogen is used in an amount of 1 to 3 times the mole of carbon tetrachloride.
The manufacturing method described in.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1271832A JP2737308B2 (en) | 1989-10-20 | 1989-10-20 | Method for producing partially chlorinated methane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1271832A JP2737308B2 (en) | 1989-10-20 | 1989-10-20 | Method for producing partially chlorinated methane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03133939A true JPH03133939A (en) | 1991-06-07 |
| JP2737308B2 JP2737308B2 (en) | 1998-04-08 |
Family
ID=17505484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1271832A Expired - Lifetime JP2737308B2 (en) | 1989-10-20 | 1989-10-20 | Method for producing partially chlorinated methane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2737308B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992018447A1 (en) * | 1991-04-23 | 1992-10-29 | Ag Technology Co., Ltd. | Process for producing hydrochloromethanes |
| JP2009298772A (en) * | 2008-06-10 | 2009-12-24 | John E Stauffer | Methanol synthesis method |
| CN107876046A (en) * | 2017-10-27 | 2018-04-06 | 江苏理文化工有限公司 | A kind of effective catalyst of preparing chloroform by carbon tetrachloride gaseous phase hydrogenation and dechlorination |
-
1989
- 1989-10-20 JP JP1271832A patent/JP2737308B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992018447A1 (en) * | 1991-04-23 | 1992-10-29 | Ag Technology Co., Ltd. | Process for producing hydrochloromethanes |
| US5334782A (en) * | 1991-04-23 | 1994-08-02 | Ag Technology Co., Ltd. | Method for producing a hydrogen-containing chloromethane |
| JP2009298772A (en) * | 2008-06-10 | 2009-12-24 | John E Stauffer | Methanol synthesis method |
| CN107876046A (en) * | 2017-10-27 | 2018-04-06 | 江苏理文化工有限公司 | A kind of effective catalyst of preparing chloroform by carbon tetrachloride gaseous phase hydrogenation and dechlorination |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2737308B2 (en) | 1998-04-08 |
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