CN102408300A - Method for preparing chloromethane and ammonia by liquid phase method - Google Patents
Method for preparing chloromethane and ammonia by liquid phase method Download PDFInfo
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- CN102408300A CN102408300A CN2011103556487A CN201110355648A CN102408300A CN 102408300 A CN102408300 A CN 102408300A CN 2011103556487 A CN2011103556487 A CN 2011103556487A CN 201110355648 A CN201110355648 A CN 201110355648A CN 102408300 A CN102408300 A CN 102408300A
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- 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
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- 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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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 the method that a kind of liquid phase method prepares methyl chloride and ammonia, belong to chemical technology field.
Background technology
Methyl chloride is mainly used in the production methyl chlorosilane, and then the synthesizing organo-silicon polymkeric substance.Because rapid development of national economy, the domestic organosilicon demand of China sharply increases, and supply falls short of demand, and methyl chloride production and trade still are zooming trend.The working method of methyl chloride mainly contains methane chlorination method and methyl alcohol hydrogen chloride; Wherein the product composition of methane chlorination method is complicated; And the product composition of methyl alcohol hydrogen chloride is single, mainly is monochloro methane, and it generally all is the methyl alcohol hydrogen chloride that the method that adopts is gone up in industry at present.
With soda ash sub product ammonium chloride is raw material production high added value methyl chloride, and through ammonium chloride and methyl alcohol reaction, with generating methyl chloride in the introducing of the chlorine in the ammonium chloride molecule organic molecule, the ammonia that discharges the simultaneously ammonia alkali process that is used for capable of circulation is produced yellow soda ash.As far back as twentieth century beginning of the fifties, U.S. Olin Mathieson chemical company among the US2755316, has proposed the working method with ammonium chloride and methyl alcohol prepared in reaction methyl chloride and ammonia at publication US2755311.This technology is pointed out: gaseous state ammonium chloride and gaseous state alcohol are fed in the fixed bed that aluminium oxide catalyst is housed together react.In order to prevent that ammonium chloride from decomposing hydrogenchloride and the ammonia crystallization once more that generates, 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 of ammonium chloride and methyl alcohol prepared in reaction methyl chloride and ammonia.In its disclosed patent JP57130930, JP58146519 and JP58194823; Proposition directly joins ammonium chloride in the fixed bed or fluidized-bed that gac is a carrier impregnation Zinc compounds catalyzer with the solid form; Methyl alcohol is passed into bed the inside, both contact reactss after gasification.Through further research and optimization, improved the yield and the selectivity of catalyst of methyl chloride to this technology.
Recently, it is the novel process of raw material production methyl chloride by ammonium chloride and methyl alcohol that Hebei University of Science and Technology has succeeded in developing a kind of, wherein fluidized-bed process and catalyst development applied for patent of invention (CN101574657, CN101579611, CN102019157A).This novel process is carrier with the activated alumina; With silicon oxide and transition metal is the efficient catalyst of active ingredient; Employing has the fluidized-bed reactor of section of promoting and conversion zone, realizes that ammonium chloride decomposes and the methyl chloride building-up process is coupled in a reaction zone.Reaction process adopts divides step separation, at high temperature isolates ammonium chloride, then through washing water miscible methyl alcohol, ammonia and methylamine class separating substances.
In the above-mentioned disclosed patent, adopt fixed bed or fluidized-bed reactor, with the ammonium chloride pyrolytic decomposition, carry out chemical reaction behind the methanol gasifying again, these processes all need consume higher energy, and increase necessary equipment for gasification.Above-mentioned gas, solid/liquid/gas reactions or gas, solid reaction, temperature all will be had relatively high expectations to the heat resistance of equipment material more than 350 ℃.In addition, hydrogenchloride is also relatively more serious to the corrosion on Equipment problem.If can realize ammonium chloride and methyl alcohol prepared in reaction methyl chloride and ammonia at low temperatures, both can cut down the consumption of energy, can alleviate the etching problem of hydrogenchloride again.
Summary of the invention
The technical problem that the present invention will solve provides the method that a kind of liquid phase method prepares methyl chloride and ammonia, 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 adopts following technical scheme to be achieved:
A kind of liquid phase method of the present invention prepares the method for methyl chloride and ammonia, in autoclave, is raw material with the mixture of methyl alcohol, ammonium chloride and water, adds catalyzer, makes methyl chloride and ammonia.
Said catalyzer is zinciferous muriate and nickeliferous muriatic mixing solutions, and said zinciferous muriate and nickeliferous muriatic mass ratio are: (0.8～1.1): 1.
The mass ratio of said methyl alcohol, ammonium chloride, water and catalyzer is: 1: (1～1.3): (1.2～1.8): (2～3.5).
Described a kind of liquid phase method prepares the method for methyl chloride and ammonia, and in reaction kettle, 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 the reaction of ammonium chloride and methyl alcohol.Temperature of reaction is low, and the reaction times is short.
3) methyl alcohol, ammonium chloride, water are in miscible state after heating, do not need independent gasification, and energy consumption is reduced.
4) ammonia combines with water in the product, with gaseous chlorine methane separate easily.
5) airtight the carrying out of operation, no waste liquid, exhaust gas emission, non-environmental-pollution.
In a word, the present invention has 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 process 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
Do further detailed description in the face of the present invention down.
The present invention relates to the method that a kind of liquid phase method prepares 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 zinciferous muriate and nickeliferous muriatic mixing solutions, and zinciferous muriate and nickeliferous muriatic mass ratio are: (0.8～1.1): 1.Temperature of reaction is 150～180 ℃ in the conditioned reaction still, 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 zinciferous muriate and nickeliferous muriatic mixing solutions, and zinciferous muriate and nickeliferous muriatic mass ratio 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 zinciferous muriate and nickeliferous muriatic mixing solutions, and zinciferous muriate and nickeliferous muriatic mass ratio 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 zinciferous muriate and nickeliferous muriatic mixing solutions, and zinciferous muriate and nickeliferous muriatic mass ratio 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 zinciferous muriate and nickeliferous muriatic mixing solutions, and zinciferous muriate and nickeliferous muriatic mass ratio 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 zinciferous muriate and nickeliferous muriatic mixing solutions, and zinciferous muriate and nickeliferous muriatic mass ratio 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 (2)
1. a liquid phase method prepares the method for methyl chloride and ammonia, it is characterized in that, and in autoclave, be raw material with the mixture of methyl alcohol, ammonium chloride and water, add catalyzer, make methyl chloride and ammonia;
Said catalyzer is zinciferous muriate and nickeliferous muriatic mixing solutions, and said zinciferous muriate and nickeliferous muriatic mass ratio are: (0.8～1.1): 1;
The mass ratio of said methyl alcohol, ammonium chloride, water and catalyzer is: 1: (1～1.3): (1.2～1.8): (2～3.5).
2. a kind of liquid phase method as claimed in claim 1 prepares the method for methyl chloride and ammonia, it is characterized in that, in reaction kettle; Temperature of reaction is 150～180 ℃; 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 |
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| 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 |
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| CN102408300A true CN102408300A (en) | 2012-04-11 |
| CN102408300B CN102408300B (en) | 2014-01-08 |
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| CN201110355648.7A Expired - Fee Related CN102408300B (en) | 2011-11-11 | 2011-11-11 | Method for preparing chloromethane and ammonia by liquid phase method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816045A (en) * | 2012-09-05 | 2012-12-12 | 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 (2)
| Title |
|---|
| 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》, vol. 27, no. 5, 31 October 2011 (2011-10-31) * |
| 邵玉昌等: "以氯化铵为氯源制备氯代烃", 《纯碱工业》, no. 6, 31 December 2008 (2008-12-31) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816045A (en) * | 2012-09-05 | 2012-12-12 | 河北科技大学 | Method for synthesizing chloromethane by tail gas generated during chloroacetic acid production |
| 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 |
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| CN102408300B (en) | 2014-01-08 |
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