CN101318875A - Process for producing chloromethane - Google Patents
Process for producing chloromethane Download PDFInfo
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- CN101318875A CN101318875A CNA2008100712890A CN200810071289A CN101318875A CN 101318875 A CN101318875 A CN 101318875A CN A2008100712890 A CNA2008100712890 A CN A2008100712890A CN 200810071289 A CN200810071289 A CN 200810071289A CN 101318875 A CN101318875 A CN 101318875A
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Abstract
The present invention discloses a method for preparing chloromethane, and relates to a method for preparing hydrochloric ether, in particular to a method for preparing chloromethane. The chloromethane preparation method is provided, which is characterized in that the reaction heat is low, the reaction process is easy to control, the output proportion of each chloro-product is easy to adjust and the manufacturing cost is largely reduced. The method comprises the following steps that nickelous chloride and cuprous chloride are ground into powders; the powders are put into a reactor to react after mixed, wherein, by weight percentage, the addition of the cuprous chloride is 0.5 to 5 percent against that of the nickelous chloride; the temperature of the reaction is controlled between 350 and 430 DEG C; the mixed gases of methane and oxygen pass through the reactor to react; the produced gaseous product flow after the reaction is pressurized to at least 0.5 MPa, and then is cooled to below 30 DEG C to obtain a chloromethane mixed solution; the mixed solution is subject to dehydration and rectifying, and thus the chloromethane product is obtained.
Description
Technical field
The present invention relates to a kind of preparation method of hydrochloric ether, especially relate to a kind of preparation method of methyl chloride.
Background technology
At present, the method for production methyl chloride mainly contains methane direct chlorination method and methyl alcohol method.Because the chlorine of methane direct chlorination method consumption is high, the difficult control of reaction, side reaction is serious, so the methyl alcohol method is occupied an leading position on the market.
In application number was 02813796.5 Chinese patent application, disclosing a kind of was catalyzer with the rare earth chloride, adopted the methane process for oxychlorination to prepare the method for methyl chloride.Comprise and make a kind of methane, halo C of being selected from
1The reactant hydrocarbon of hydrocarbon or its mixture and halogen source and preferred oxygen source in the presence of rare earth halide or rare earth oxyhalide oxide catalyst, contact, thereby form a kind of halo C
1Hydrocarbon product, its more described reactant hydrocarbon has the more halogenic substituent of more number.Preferably, described product is single methyl halide, more preferably methyl chloride.The oxidative halogenation method of described formation methyl halide can combine with downstream process, with preparation valuable commodity chemicals, for example methyl alcohol and/or dme; Light olefin comprises ethene, propylene and butylene; Higher hydrocarbon comprises gasoline; Halogen vinyl monomer and acetate.The common property thing hydrogen halide of these downstream processes, capable of circulation getting back among the described oxidative halogenation method.
Summary of the invention
The object of the present invention is to provide a kind of reaction heat lower, reaction process is easy to control, is easy to regulate the yield ratio of each chloro-product, the preparation method of the methyl chloride that production cost greatly reduces.
Technical scheme of the present invention is that employing is the process for oxychlorination production methyl chloride in chlorine source with the nickelous chloride.
Reaction formula of the present invention is:
NiCl
2+2CH
4+O
2＝NiO+H
2O+2CH
3Cl
NiCl
2+2CH
3Cl+O
2＝NiO+H
2O+2CH
2Cl
2
NiCl
2+2CH
2Cl
2+O
2＝NiO+H
2O+2CHCl
3
NiCl
2+2CHCl
3+O
2＝NiO+H
2O+2CCl
4
The present invention includes following steps:
1) nickelous chloride and cuprous chloride are crushed into powder, react in the reactor of packing into after mixing, by mass percentage, the add-on of cuprous chloride is 0.5%～5% of a nickelous chloride;
2) control reaction temperature is 350～430 ℃, reacts in the mixed gas feeding reactor with methane and oxygen;
3) gaseous product flow that will react the back output is forced into 0.5MPa at least, be cooled to obtain the methyl chloride mixed solution below 30 ℃, through dewater, rectifying obtains the methyl chloride product.
Described methane and oxygen ratio in molar ratio is 5: (1～10), the time of reacting in the mixed gas feeding reactor with methane and oxygen is preferably 0.5～20min, and adjusting reaction time and control oxygen proportion can obtain the chloromethane mixture of different ratios.
Uncooled gas is mainly unreacted methane, oxygen and part methyl chloride after pressurization and cooling, recyclablely recycles to reactor.
Compare with chlorine direct chlorination method and hydrogenchloride process for oxychlorination, the present invention is because to adopt nickelous chloride be the chlorine source, so reaction heat is lower, and reaction is gas-solid reaction, and reaction process is easy to control, is easy to regulate the yield ratio of each chloro-product.Chinese invention patent application as if in conjunction with application number being 200610135336.4 and 200710009827.9 then can realize the cyclic transformation of nickelous chloride and nickel oxide, obtains chlorine source cheaply, and the production cost of methyl chloride is greatly reduced.
Embodiment
Following examples will the present invention is further illustrated.
Embodiment 1
136g nickelous chloride powder and 1g cuprous chloride powder mixes is even, pack in the reactor, control reaction temperature is 380 ℃, and the mol ratio of logical people's methane and oxygen is 2: 1 mixed gass, controlling reaction time 1min, obtain gaseous product flow and be compressed to 1MPa, be cooled to 0 ℃, isolate liquid, after dewatering, the liquid that obtains contains monochloro methane 75% approximately, methylene dichloride 25%.
Embodiment 2
136g nickelous chloride powder and 0.68g cuprous chloride powder mixes is even, pack in the reactor, control reaction temperature is 430 ℃, and the mol ratio of logical people's methane and oxygen is 5: 1 mixed gass, controlling reaction time 0.5min, obtain gaseous product flow and be compressed to 1MPa, be cooled to 0 ℃, isolate liquid, after dewatering, the liquid that obtains contains monochloro methane 95% approximately, methylene dichloride 5%.
Embodiment 3
136g nickelous chloride powder and 2g cuprous chloride powder mixes is even, pack in the reactor, control reaction temperature is 400 ℃, and the mol ratio of logical people's methane and oxygen is 5: 3 mixed gass, controlling reaction time 3min, obtain gaseous product flow and be compressed to 1MPa, be cooled to 0 ℃, isolate liquid, after dewatering, the liquid that obtains contains monochloro methane 65% approximately, methylene dichloride 33%, trichloromethane 2%.
Embodiment 4
136g nickelous chloride powder and 3g cuprous chloride powder mixes is even, pack in the reactor, control reaction temperature is 390 ℃, and the mol ratio of logical people's methane and oxygen is 5: 5 mixed gass, controlling reaction time 4min, obtain gaseous product flow and be compressed to 0.5MPa, be cooled to 10 ℃, isolate liquid, after dewatering, the liquid that obtains contains monochloro methane 45% approximately, methylene dichloride 50%, trichloromethane 5%.
Embodiment 5
With 136g nickelous chloride powder and 4g cuprous chloride powder mixes is even, in the reactor of packing into, control reaction temperature is 410 ℃, the mol ratio of logical people's methane and oxygen is 5: 7 mixed gass, controlling reaction time 10min obtains gaseous product flow and is compressed to 0.5MPa, is cooled to 30 ℃, isolate liquid,, contain monochloro methane 15% approximately after the liquid that obtains dewaters, methylene dichloride 50%, trichloromethane/28%, tetracol phenixin 7%.
Embodiment 6
136g nickelous chloride powder and 5g cuprous chloride powder mixes is even, and in the reactor of packing into, control reaction temperature is 360 ℃, the mol ratio of logical people's methane and oxygen is 5: 8 mixed gass, controlling reaction time 15min obtains gaseous product flow and is compressed to 0.5MPa, is cooled to 30 ℃, isolate liquid,, contain monochloro methane 12% approximately after the liquid that obtains dewaters, methylene dichloride 36%, trichloromethane/38%, tetracol phenixin 14%.
Embodiment 7
136g nickelous chloride powder and 6.8g cuprous chloride powder mixes is even, and in the reactor of packing into, control reaction temperature is 350 ℃, the mol ratio of logical people's methane and oxygen is 5: 10 mixed gass, controlling reaction time 20min obtains gaseous product flow and is compressed to 0.5MPa, is cooled to 30 ℃, isolate liquid,, contain monochloro methane 10% approximately after the liquid that obtains dewaters, methylene dichloride 28%, trichloromethane/45%, tetracol phenixin 17%.
Claims (5)
1. the preparation method of a methyl chloride is characterized in that its reaction formula is:
NiCl
2+2CH
4+O
2＝NiO+H
2O+2CH
3Cl
NiCl
2+2CH
3Cl+O
2＝NiO+H
2O+2CH
2Cl
2
NiCl
2+2CH
2Cl
2+O
2＝NiO+H
2O+2CHCl
3
NiCl
2+2CHCl
3+O
2＝NiO+H
2O+2CCl
4。
2. the preparation method of a kind of methyl chloride as claimed in claim 1 is characterized in that may further comprise the steps:
1) nickelous chloride and cuprous chloride are crushed into powder, react in the reactor of packing into after mixing, by mass percentage, the add-on of cuprous chloride is 0.5%～5% of a nickelous chloride;
2) control reaction temperature is 350～430 ℃, reacts in the mixed gas feeding reactor with methane and oxygen;
3) gaseous product flow that will react the back output is forced into 0.5MPa at least, be cooled to obtain the methyl chloride mixed solution below 30 ℃, through dewater, rectifying obtains the methyl chloride product.
3. the preparation method of a kind of methyl chloride as claimed in claim 2 is characterized in that described methane and oxygen ratio in molar ratio is 5: 1～10.
4. the preparation method of a kind of methyl chloride as claimed in claim 2 is characterized in that the time of reacting in the mixed gas feeding reactor with methane and oxygen is 0.5～20min.
5. the preparation method of a kind of methyl chloride as claimed in claim 2 is characterized in that uncooled gas recovery recycles after pressurization and cooling to reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100712890A CN101318875B (en) | 2008-06-25 | 2008-06-25 | Process for producing chloromethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100712890A CN101318875B (en) | 2008-06-25 | 2008-06-25 | Process for producing chloromethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101318875A true CN101318875A (en) | 2008-12-10 |
| CN101318875B CN101318875B (en) | 2010-09-08 |
Family
ID=40179183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100712890A Expired - Fee Related CN101318875B (en) | 2008-06-25 | 2008-06-25 | Process for producing chloromethane |
Country Status (1)
| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301836A (en) * | 2013-07-01 | 2013-09-18 | 厦门大学 | Cerium-based catalyst for producing chloromethane by catalyzing oxidization reaction of methane chloride and preparation method thereof |
| CN106631678A (en) * | 2016-12-14 | 2017-05-10 | 厦门中科易工化学科技有限公司 | Chlorinating agent used for preparing chloromethane and application thereof and preparing method of chloromethane |
| CN108144632A (en) * | 2018-01-22 | 2018-06-12 | 西安元创化工科技股份有限公司 | A kind of ruthenic oxide catalyst of methane oxychlorination and preparation method thereof |
-
2008
- 2008-06-25 CN CN2008100712890A patent/CN101318875B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301836A (en) * | 2013-07-01 | 2013-09-18 | 厦门大学 | Cerium-based catalyst for producing chloromethane by catalyzing oxidization reaction of methane chloride and preparation method thereof |
| CN106631678A (en) * | 2016-12-14 | 2017-05-10 | 厦门中科易工化学科技有限公司 | Chlorinating agent used for preparing chloromethane and application thereof and preparing method of chloromethane |
| CN106631678B (en) * | 2016-12-14 | 2020-03-31 | 厦门中科易工化学科技有限公司 | Preparation method of chloromethane |
| CN108144632A (en) * | 2018-01-22 | 2018-06-12 | 西安元创化工科技股份有限公司 | A kind of ruthenic oxide catalyst of methane oxychlorination and preparation method thereof |
| CN108144632B (en) * | 2018-01-22 | 2020-11-03 | 西安元创化工科技股份有限公司 | Ruthenium dioxide catalyst for methane oxychlorination and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101318875B (en) | 2010-09-08 |
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Owner name: ZHONGKE YIGONG (SHANGHAI) CHEMICAL TECHNOLOGY CO., Free format text: FORMER NAME: ZHONGKE YIGONG (XIAMEN) CHEMICAL TECHNOLOGY CO., LTD. |
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Address after: 200030 room 6, building 829, No. 558, Xuhui District, Shanghai, Yishan Road Patentee after: ZHONGKE YIGONG (SHANGHAI) CHEMICAL TECHNOLOGY CO.,LTD. Address before: Haicang District of Xiamen City, Fujian province 361026 Weng Kok Road No. 289 Chong Building 422 unit Patentee before: Zhongke Yigong (Xiamen) Chemical Technology Co.,Ltd. |
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