CN102408300B - Method for preparing chloromethane and ammonia by liquid phase method - Google Patents
Method for preparing chloromethane and ammonia by liquid phase method Download PDFInfo
- Publication number
- CN102408300B CN102408300B CN201110355648.7A CN201110355648A CN102408300B CN 102408300 B CN102408300 B CN 102408300B CN 201110355648 A CN201110355648 A CN 201110355648A CN 102408300 B CN102408300 B CN 102408300B
- Authority
- CN
- China
- Prior art keywords
- ammonia
- chloride
- reaction
- ammonium chloride
- methyl
- 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.)
- Expired - Fee Related
Links
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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the chemical industry technical field, and concretely relates to a method for preparing chloromethane and ammonia by a liquid phase method. The method comprises the following steps: taking a mixture of methanol, ammonium chloride and water as a raw material and placing in a high pressure reaction vessel, adding a catalyst to prepare methyl chloride and ammonia, wherein the catalyst is a mixed solution of zinc-containing chloride and nickel-containing chloride. The Method for preparing chloromethane and ammonia has the advantages of short process flow, cheap and easily available raw material, high selectivity, less by-product, short reaction time, low reaction temperature, low energy consumption, simple equipment, no environmental pollution and the like.
Description
Technical field
The present invention relates to a kind of method of Liquid preparation methods methyl chloride and ammonia, belong to chemical technology field.
Background technology
Methyl chloride is mainly for the production of methyl chlorosilane, and then the synthesizing organo-silicon polymkeric substance.Due to developing rapidly of national economy, China's silicone industry in China demand sharply increases, and supply falls short of demand, and methyl chloride production and trade still are zooming trend.The production method of methyl chloride mainly contains methane chlorination method and methyl alcohol hydrogen chloride, the product composition complexity of methane chlorination method wherein, and the product composition of methyl alcohol hydrogen chloride is single, be mainly monochloro methane, the method for current industrial employing is all generally the methyl alcohol hydrogen chloride.
Take soda ash byproduct ammonium chloride as raw material production high added value methyl chloride, react with methyl alcohol by ammonium chloride, the chlorine in the ammonium chloride molecule is introduced in organic molecule and generated methyl chloride, the ammonia simultaneously discharged is capable of circulation produces sodium carbonate for the ammonia alkali process.As far back as twentieth century beginning of the fifties, U.S. Olin Mathieson chemical company, at publication US2755311, in US2755316, has proposed to prepare with ammonium chloride and methyl alcohol reaction the production method of methyl chloride and ammonia.This technique is pointed out: gaseous state ammonium chloride is passed in the fixed bed that aluminium oxide catalyst is housed and reacted together with gaseous state alcohol.In order to prevent that ammonium chloride from decomposing hydrogenchloride and the ammonia crystallization again generated, temperature of reaction must maintain on 350 ℃, and this just needs to consume more energy.
Twentieth century eighties, Mitsubishi gas chemical company has further improved the reaction process that ammonium chloride and methyl alcohol reaction prepare methyl chloride and ammonia.In its disclosed patent JP57130930, JP58146519 and JP58194823, proposition be take the form of solid by ammonium chloride and is directly joined gac in the fixed bed or fluidized-bed of carrier impregnation Zinc compounds catalyzer, methyl alcohol is passed into bed the inside, both contact reactss after gasification.By further research and the optimization to this technique, improved yield and the selectivity of catalyst of methyl chloride.
Recently, Hebei University of Science and Technology has succeeded in developing a kind of novel process that is the raw material production methyl chloride by ammonium chloride and methyl alcohol, and wherein fluidized-bed process and catalyst development have been applied for patent of invention (CN101574657, CN101579611, CN102019157A).This novel process be take activated alumina as carrier, take the efficient catalyst that silicon oxide and transition metal be active ingredient, employing has the fluidized-bed reactor of raising section and conversion zone, realizes that ammonium chloride decomposes and the methyl chloride building-up process is coupled in a reaction zone.Reaction process adopts a minute step separation, at high temperature isolates ammonium chloride, then through washing water miscible methyl alcohol, ammonia and methylamine separating substances.
In above-mentioned published patent, adopt fixed bed or fluidized-bed reactor, by the ammonium chloride pyrolytic decomposition, carry out chemical reaction after methanol gasifying again, these processes all need to consume higher energy, and increase necessary equipment for gasification.Above-mentioned gas, solid/liquid/gas reactions or gas, solid reaction, temperature all will, more than 350 ℃, be had relatively high expectations to the heat resistance of equipment material.In addition, hydrogenchloride is also more serious to the etching problem of equipment.If can realize at low temperatures, ammonium chloride reacts with methyl alcohol prepares methyl chloride and ammonia, both can reduce energy consumption, can alleviate again the etching problem of hydrogenchloride.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of Liquid preparation methods methyl chloride and ammonia, the characteristics such as technical process is short, raw material is cheap and easy to get, selectivity is high, by product is few, the reaction times is short, temperature of reaction is low, energy consumption is low, equipment is simple, non-environmental-pollution that it has.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions:
The method of a kind of Liquid preparation methods methyl chloride of the present invention and ammonia, in autoclave, the mixture of methyl alcohol, ammonium chloride and water of take is raw material, adds catalyzer, makes methyl chloride and ammonia.
Described catalyzer is the muriate containing zinc and nickeliferous muriatic mixing solutions, and the described muriate containing zinc and nickeliferous muriatic mass ratio are: (0.8～1.1): 1.
The mass ratio of described methyl alcohol, ammonium chloride, water and catalyzer is: 1: (1～1.3): (1.2～1.8): (2～3.5).
The method of described a kind of Liquid preparation methods methyl chloride and ammonia, in reactor, temperature of reaction is 150～180 ℃, and reaction pressure is 1～1.4MPa, and the agitator motor rotating speed is 100～200r/min, and the reaction times is 1～2.5 hour.
The beneficial effect that the present invention compared with prior art has is:
1) the present invention carries out in autoclave, and equipment is simple, technical process is short, less investment;
2), under catalyst action, impel ammonium chloride to react with methyl alcohol.Temperature of reaction is low, and the reaction times is short.
3) methyl alcohol, ammonium chloride, water in miscible state, do not need independent gasification after heating, make Energy Intensity Reduction.
4) in product, ammonia is combined with water, with gaseous chlorine methane, easily separates.
5) operate airtight carrying out, without waste liquid, exhaust gas emission, non-environmental-pollution.
In a word, the present invention has the characteristics such as technical process is short, raw material is cheap and easy to get, selectivity is high, by product is few, the reaction times is short, temperature of reaction is low, energy consumption is low, equipment is simple, non-environmental-pollution.Utilize this processing method can make low value-added ammonium chloride be converted into the methyl chloride of high added value and realize the recycling of ammonia.
Embodiment
Below the present invention is described in further detail.
The present invention relates to a kind of method of Liquid preparation methods methyl chloride and ammonia, specific practice is: in autoclave, by 1: (1～1.3): (1.2～1.8): the mass ratio of (2～3.5) adds methyl alcohol, ammonium chloride, water and catalyzer successively, wherein catalyzer is the muriate containing zinc and nickeliferous muriatic mixing solutions, containing the muriate of zinc and nickeliferous muriatic mass ratio, is: (0.8～1.1): 1.In the conditioned reaction still, temperature of reaction is 150～180 ℃, and reaction pressure is 1～1.4MPa, and the agitator motor rotating speed is 100～200r/min, and the reaction times is 1～2.5 hour, makes methyl chloride and ammonia.Methanol conversion can reach 95%～100%, methyl chloride yield 90～98%, ammonia yield 90～95%.Specific embodiment is:
Embodiment 1:
In autoclave, by 1: 1: 1.2: 2 mass ratio added methyl alcohol, ammonium chloride, water and catalyzer successively, wherein catalyzer is the muriate containing zinc and nickeliferous muriatic mixing solutions, and the muriate and the nickeliferous muriatic mass ratio that contain zinc are 0.8: 1.The conditioned reaction temperature is 160 ℃, and reaction pressure is 1.2MPa, and the agitator motor rotating speed is 200r/min, and the reaction times is 1.5 hours, and methanol conversion is 98%, methyl chloride yield 95%, ammonia yield 92%.
Embodiment 2:
In autoclave, by 1: 1: 1.2: 2 mass ratio added methyl alcohol, ammonium chloride, water and catalyzer successively, wherein catalyzer is the muriate containing zinc and nickeliferous muriatic mixing solutions, and the muriate and the nickeliferous muriatic mass ratio that contain zinc are 1: 1.The conditioned reaction temperature is 160 ℃, and reaction pressure is 1.2MPa, and the agitator motor rotating speed is 200r/min, and the reaction times is 1.5 hours, and methanol conversion is 99%, methyl chloride yield 97%, ammonia yield 94%.
Embodiment 3:
In autoclave, by 1: 1.3: 1.8: 3.5 mass ratio added methyl alcohol, ammonium chloride, water and catalyzer successively, wherein catalyzer is the muriate containing zinc and nickeliferous muriatic mixing solutions, and the muriate and the nickeliferous muriatic mass ratio that contain zinc are 0.8: 1.The conditioned reaction temperature is 160 ℃, and reaction pressure is 1.2MPa, and the agitator motor rotating speed is 200r/min, and the reaction times is 1.5 hours, and methanol conversion is 99%, methyl chloride yield 93%, ammonia yield 90%.
Embodiment 4:
In autoclave, by 1: 1.3: 1.8: 3.5 mass ratio added methyl alcohol, ammonium chloride, water and catalyzer successively, wherein catalyzer is the muriate containing zinc and nickeliferous muriatic mixing solutions, and the muriate and the nickeliferous muriatic mass ratio that contain zinc are 0.8: 1.The conditioned reaction temperature is 160 ℃, and reaction pressure is 1.2MPa, and the agitator motor rotating speed is 200r/min, and the reaction times is 2.5 hours, and methanol conversion is 100%, methyl chloride yield 96%, ammonia yield 93%.
Embodiment 5:
In autoclave, by 1: 1.3: 1.8: 3.5 mass ratio added methyl alcohol, ammonium chloride, water and catalyzer successively, wherein catalyzer is the muriate containing zinc and nickeliferous muriatic mixing solutions, and the muriate and the nickeliferous muriatic mass ratio that contain zinc are 0.8: 1.The conditioned reaction temperature is 180 ℃, and reaction pressure is 1.2MPa, and the agitator motor rotating speed is 200r/min, and the reaction times is 2.5 hours, and methanol conversion is 100%, methyl chloride yield 98%, ammonia yield 95%.
Claims (1)
1. the method for a Liquid preparation methods methyl chloride and ammonia, is characterized in that, in autoclave, the mixture of methyl alcohol, ammonium chloride and water of take is raw material, adds catalyzer, makes methyl chloride and ammonia;
Described catalyzer is the muriate containing zinc and nickeliferous muriatic mixing solutions, and the described muriate containing zinc and nickeliferous muriatic mass ratio are: (0.8～1.1): 1;
The mass ratio of described methyl alcohol, ammonium chloride, water and catalyzer is: 1:(1～1.3): (1.2～1.8): (2～3.5);
In reactor, temperature of reaction is 150～180 ℃, and reaction pressure is 1～1.4MPa, and the agitator motor rotating speed is 100～200r/min, and the reaction times is 1～2.5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110355648.7A CN102408300B (en) | 2011-11-11 | 2011-11-11 | Method for preparing chloromethane and ammonia by liquid phase method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110355648.7A CN102408300B (en) | 2011-11-11 | 2011-11-11 | Method for preparing chloromethane and ammonia by liquid phase method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102408300A CN102408300A (en) | 2012-04-11 |
| CN102408300B true CN102408300B (en) | 2014-01-08 |
Family
ID=45910694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110355648.7A Expired - Fee Related CN102408300B (en) | 2011-11-11 | 2011-11-11 | Method for preparing chloromethane and ammonia by liquid phase method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102408300B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816045B (en) * | 2012-09-05 | 2015-06-03 | 河北科技大学 | Method for synthesizing chloromethane by tail gas generated during chloroacetic acid production |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3502733A (en) * | 1967-11-08 | 1970-03-24 | Allied Chem | Production of chloromethanes |
| RO106731B1 (en) * | 1989-08-14 | 1993-06-30 | Carol Trabalka | Methyl chloride synthesis process |
| CN101429093A (en) * | 2008-11-28 | 2009-05-13 | 山东东岳有机硅材料有限公司 | Energy-saving process for producing monochloro methane with liquid phase catalysis method |
-
2011
- 2011-11-11 CN CN201110355648.7A patent/CN102408300B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3502733A (en) * | 1967-11-08 | 1970-03-24 | Allied Chem | Production of chloromethanes |
| RO106731B1 (en) * | 1989-08-14 | 1993-06-30 | Carol Trabalka | Methyl chloride synthesis process |
| CN101429093A (en) * | 2008-11-28 | 2009-05-13 | 山东东岳有机硅材料有限公司 | Energy-saving process for producing monochloro methane with liquid phase catalysis method |
Non-Patent Citations (4)
| Title |
|---|
| 以氯化铵为氯源制备氯代烃;邵玉昌等;《纯碱工业》;20081231(第6期);第3-10页 * |
| 孙玉捧等.甲醇氯化铵法反应催化剂的研究.《化学反应工程与工艺》.2011,第27卷(第5期), |
| 甲醇氯化铵法反应催化剂的研究;孙玉捧等;《化学反应工程与工艺》;20111031;第27卷(第5期);第400-405页 * |
| 邵玉昌等.以氯化铵为氯源制备氯代烃.《纯碱工业》.2008,(第6期), |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102408300A (en) | 2012-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107473183B (en) | Application of molybdenum phosphide in catalytic hydrogen production in alkaline formaldehyde solution | |
| CN113457711B (en) | Graphite-phase carbon nitride-loaded magnesium monoatomic composite material, preparation method thereof and method for preparing hydrogen peroxide through photocatalysis | |
| JP2015514563A (en) | Process for the preparation of solid nitrosyl ruthenium nitrate by using a waste catalyst containing ruthenium | |
| CN111170982B (en) | Method for improving selectivity of cyclohexanone oxidation reaction product epsilon-caprolactone | |
| CN102923716A (en) | Process for producing trichlorosilane through inverse disporportionation of dichlorosilane | |
| CN100497305C (en) | Method for preparing ethylsulfonyl acetonitrile | |
| CN102583239A (en) | Method and device for preparing CO and H2 by thermochemical cycle decomposition of CO2 and H2O | |
| CN108579397B (en) | Fluorine fixing agent with high utilization rate and preparation method thereof | |
| CN102408300B (en) | Method for preparing chloromethane and ammonia by liquid phase method | |
| CN108530318B (en) | Method for synthesizing adiponitrile | |
| CN108610260A (en) | A kind of technique preparing tert-butylamine in raw material dynamic equilibrium | |
| CN108993614A (en) | A kind of preparation method of the CdS photochemical catalyst of flower ball-shaped zinc ion doping | |
| WO2011074524A1 (en) | Process for synthesis of ammonia | |
| CN110372536B (en) | Method for preparing cyclohexanone oxime by cyclohexanone ammoximation | |
| CN105567325B (en) | It is a kind of for the catalytic removal of nox of solar energy thermochemical study and the mixture system of carbonate and its preparation and application | |
| CN102730771A (en) | Production of high purity sodium-free high activity composite nickel carbonate by three-step continuous process | |
| CN105754681A (en) | Chemical chain hydrogen production composite oxygen carrier with anti-carbon property and preparation method of chemical chain hydrogen production composite oxygen carrier | |
| CN103224445B (en) | Technology for preparing resorcinol by direct oxidation of benzene | |
| CN112403505A (en) | CoP-g-C3N4Electronic current collector photocatalyst and preparation method and application thereof | |
| CN102816071B (en) | Synthesis method of N-ethyl ethylene diamine | |
| CN108160085B (en) | Preparation method of silicon-based nano-selenium | |
| CN101774882A (en) | Method for catalytic hydrodechlorination of CFC125 into HFC-125 | |
| CN109796305A (en) | A method of cyclohexanol is prepared using composite catalyst | |
| CN103524541A (en) | Preparation method of 9-boron bicyclo (3,3,1)-nonane (9-BBN) | |
| CN102580768B (en) | Novel catalyst for preparing ethylene by low-temperature oxidative dehydrogenation of ethane and using method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140108 Termination date: 20141111 |
|
| EXPY | Termination of patent right or utility model |