CN106008151A - Methyl chloride synthesis method - Google Patents
Methyl chloride synthesis method Download PDFInfo
- Publication number
- CN106008151A CN106008151A CN201610589621.7A CN201610589621A CN106008151A CN 106008151 A CN106008151 A CN 106008151A CN 201610589621 A CN201610589621 A CN 201610589621A CN 106008151 A CN106008151 A CN 106008151A
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- methanol
- chloromethanes
- hydrochloric acid
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- rectifying column
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a methyl chloride synthesis method, which is characterized in that hydrochloric acid and methanol are directly mixed; hydrochloric acid is directly synthesized under a certain condition; the product of methyl chloride is obtained through condensing, drying and compressing; synthesized condensing liquid is rectified to recover unreacted methanol for reaction again.
Description
Technical field
The present invention relates to the preparation method of chloromethanes.
Background technology
Organochlorosilane is the pillar of whole organosilicon chemistry, most organosilicon product (such as silicone oil, silicone rubber, silicones)
It is the polymethyl siloxane (base polymer) prepared by methylchlorosilane hydrolysis, then processes with regulator, cross-linking agent, closure agent etc.
Make it is considered to be the regular product of organosilicon.Polysiloxanes has a lot of excellent physics, chemical property, such as resistant of high or low temperature
Energy, radiation resistance, oxidative resistance, highly-breathable, weatherability, release property, hydrophobicity and physiological inertia etc..Its application throughout
Space flight, aviation, chemical industry, metallurgy or even people's daily life, health care every field.
Current methylchlorosilane industrialized preparing process only one, Rochow method.This is by GE company of U.S. E.G.Rochow
The method being directly synthesized methylchlorosilane of invention, i.e. under copper catalyst and 300 DEG C of high temperature, chloromethanes directly react with silica flour and
?.Primary response formula is as follows:
2MeCl+Si→Me2SiCl2
So the production capacity of chloromethanes is the most closely bound up with the production capacity of methylchlorosilane, chloromethanes more than 90% in the market is used for
Organic silicon monomer synthesizes, and chloromethanes synthesis technique becomes one of key technology of organosilicon synthesis.
The synthesis technique of chloromethanes mainly has three kinds of liquid catalytics, gas-phase catalysis and liquid phase on-catalytic method at present.
US202613 discloses the method for a kind of liquid-phase catalysis synthesis chloromethanes, with methanol and hydrogen chloride gas as raw material, ZnCl2
Solution is catalyst, and reaction temperature is 120～130 DEG C.Pressure is without particular/special requirement, and catalyst will not inactivate, but hydrogen chloride needs
Want excessive to suppress the generation of methyl ether, thus produce a large amount of by-product hydrochloric acid containing methanol, processing cost height.
CN1347862 discloses a kind of method of gas phase catalytic synthesis chloromethanes, and wherein methanol with the mol ratio of hydrogen chloride is
1:1.02～1.1, reaction temperature is 240～300 DEG C, and pressure is 0～0.5MPa, and by-product is the hydrochloric acid of concentration 25%, use γ-
Aluminium oxide is as catalyst, and catalyst life is 7500～8400 hours.
US6111153 disclose a kind of liquid phase on-catalytic synthesis chloromethanes method, during wherein methanol respectively enters two-stage reactor with
Hydrogen chloride reacts, and reaction temperature is 100～170 DEG C, and pressure is 0.24～0.5MPa.Methanol excess and hcl reaction, meeting
Produce acid methanol solution, the methanol that can be reused by rectification isolated and the acid waste water of low concentration.
The hydrogen chloride that organosilicon industry uses generates after mostly being methylchlorosilane hydrolysis, and its pressure is 30～200kPa, wherein contains few
Amount methylchlorosilane, methylsiloxane ring body and water.
Catalysis method synthesis is incremented by along with reaction system methanol partial pressure because of methyl ether selectivity, therefore uses hydrogen chloride excess to suppress the choosing of methyl ether
Selecting property, but substantial amounts of containing alcohol dilute hydrochloric acid can be produced.And the silane carried secretly in hydrogen chloride can cross-link under catalytic condition, the structure of generation
Body blocking condenser.
The synthesis of on-catalytic method is then higher because of pressure, uses hydrogen chloride compressor to carry out supercharging, increase after needing to be dehydrated hydrogen chloride
Substantial amounts of equipment investment and operating cost.
Summary of the invention
The purpose of the present invention provides the synthetic method of a kind of chloromethanes for the problems referred to above, and the present invention directly uses hydrochloric acid to close as raw material
Become chloromethanes, eliminate hydrochloric acid and take off the analysis cost for hydrogen chloride, and methanol excess participates in reaction, will not again produce by-product hydrochloric acid.
The synthetic method of a kind of chloromethanes, the steps include: that hydrochloric acid and methanol are sufficiently mixed in entrance reactor, in mixture methanol with
The mol ratio of hydrogen chloride is 1～1.7:1；Mixture 0.15～1.0Mpa and without catalyst under conditions of, be warming up to 100～150 DEG C,
The reactor liquid phase bed being made up of methanol, hydrogen chloride and water reacts, maintains the height of liquid phase bed, obtain reactant
Chloromethanes, by heating by the way of by product vaporize, enter rectifying column, reactant chloromethanes rectifying column through condensation, be dried,
Product chloromethanes is obtained after compression.
Described chloromethanes is dried through persulfuric acid, the water in removing chloromethanes and dimethyl ether, and the content of the methyl ether in product chloromethanes≤
50ppm。
The gas phase mixture that reactor head vaporization produces enters rectifying column after being directly entered rectifying column, or condensation in liquid form,
The chloromethanes of rectifying column tower top is dried through persulfuric acid.
Chloromethanes and the methanol of vaporization cool down in rectifying column overhead condenser, and methanol condensed is that liquid enters recovery in return tank, not
The methanol of reaction reacts again.Methanol condensed liquid is processed by reflux type, with guarantee the content of methanol condensed liquid methanol >=
90w.t.%
Reactor bottom is provided with the first reboiler, and rectifier bottoms is provided with the second reboiler, and the second reboiler connects heat exchanger,
The height of reactor liquid phase bed is controlled by the first reboiler, the tower bottoms of rectifier bottoms under the heating of the second reboiler,
After removing the methanol wherein carried, it is ensured that the wherein content≤0.1w.t.% of methanol, the content≤3w.t.% of hydrogen chloride, then contain
The tower bottoms of a small amount of hydrogen chloride is discharged after cooling down with heat exchange of methanol in heat exchanger as waste water, delivers to sewage-treatment plant and processes.
The tower bottoms of rectifier bottoms, under the heating of the second reboiler, removes the methanol wherein carried.Described hydrochloric acid is catalysis method synthesis
The containing alcohol dilute hydrochloric acid of chloromethanes by-product, concentration is 10-40wt.%, and containing the hydrochloric acid that methanol is 0-10wt.% or preparation, concentration is
10-40wt.%.
Compared with prior art, advantages of the present invention is as follows:
1, in the inventive method, employing hydrochloric acid is raw material, has skipped over hydrochloric acid and has taken off analysis and produce the process of hydrogen chloride gas, has been greatly reduced
Production cost.
2, in the inventive method, using without catalyst, the selectivity that methanol side reaction generates dimethyl ether is relatively low, improves methanol
Conversion ratio, reduces and is dried the amount using concentrated sulphuric acid.
3, in the inventive method, methanol excess, it is effectively increased the conversion ratio of hydrogen chloride, and will not additionally produce by-product hydrochloric acid.
Accompanying drawing explanation
Fig. 1 is reacting flow chart of the present invention.
Fig. 2 is the analysis result of various embodiments of the present invention.
Detailed description of the invention
In conjunction with the drawings and specific embodiments, the invention will be further described.
The synthetic method of a kind of chloromethanes, the steps include: that hydrochloric acid 1 and methanol 14 are sufficiently mixed in entrance reactor 4, mixture
Middle methanol 14 is 1～1.7:1 with the mol ratio of hydrogen chloride；Mixture 0.15～1.0Mpa and without catalyst under conditions of, heat up
To 100～150 DEG C, react in the reactor liquid phase bed 3 being made up of methanol, hydrogen chloride and water, maintain liquid phase bed 3
Height, obtain reactant chloromethanes, by heating by the way of by product vaporize, enter rectifying column 7 (methanol distillation column), instead
Thing chloromethanes is answered to obtain product chloromethanes 9 at rectifying column 7 after condensing, be dried, compressing.
Described chloromethanes is dried through persulfuric acid, the water in removing chloromethanes and dimethyl ether, and the content of the methyl ether in product chloromethanes≤
50ppm。
The gas phase mixture that the vaporization of reactor 4 top produces enters rectification after being directly entered rectifying column 7, or condensation in liquid form
Tower 7, the chloromethanes of rectifying column 7 tower top is dried through persulfuric acid.
Chloromethanes and the methanol of vaporization cool down in rectifying column 7 overhead condenser 8, and methanol condensed is that liquid enters in return tank 10
Reclaiming, unreacted methanol reacts again.Methanol condensed liquid is processed by reflux type, to guarantee methanol condensed liquid methanol
Content >=90w.t.%.Fresh methanol 2 fills in return tank to meet the consumption of methanol.
It is provided with the first reboiler 5 bottom reactor 4, is provided with the second reboiler 11 bottom rectifying column 7, the second reboiler 11 connects
Being connected to heat exchanger 12, the height of reactor liquid phase bed 3 is controlled by the first reboiler 5.Tower bottoms bottom rectifying column 7
Under the heating of the second reboiler 11, remove the methanol wherein carried, it is ensured that the wherein content≤0.1w.t.% of methanol, hydrogen chloride
Content≤3w.t.%, then contain the tower bottoms of a small amount of hydrogen chloride and cool down heel row with heat exchange of methanol in heat exchanger 12 as waste water
Go out, deliver to sewage-treatment plant and process.
Described hydrochloric acid 1 is the containing alcohol dilute hydrochloric acid of catalysis method synthesis chloromethanes by-product, and concentration is 10-40wt.%, containing methanol is
0-10wt.% or the hydrochloric acid of preparation, concentration is 10-40wt.%.
Embodiments of the invention one are:
Hydrochloric acid 2 is passed through after mixing with methanol 14 in reactor 4, at the reactor liquid phase bed being made up of methanol, hydrogen chloride and water
Reacting in 3, the height of reactor liquid phase bed 3 is controlled by the first reboiler 5, and the thick methyl chloride gas 6 of generation is entered
Entering in rectifying column 7 (methanol distillation column), chloromethanes and methanol cool down in overhead condenser 8, and methanol condensed is that liquid enters back
In stream tank 10, methyl chloride gas 9 then obtains product chloromethanes through dry, compression.Tower reactor liquid phase is then at the second reboiler 11
Heating under, remove the methanol that wherein carries, the waste water 13 containing a small amount of hydrogen chloride is cold with methanol 14 heat exchange in heat exchanger 12
Discharging the most afterwards, fresh methanol 2 fills in return tank 10 to meet the consumption of methanol.
The hydrochloric acid (1000kg/h) of 10%, is passed through in reactor 4 with methanol (114kg/h), and reaction temperature is 100 DEG C, pressure
For 180kpa, product uses gas chromatograph to be analyzed.
Embodiments of the invention two are:
Course of reaction is with embodiment one.The hydrochloric acid (1000kg/h) of 10%, is passed through in reactor with methanol (119kg/h), reaction
Temperature is 110 DEG C, and pressure is 210kpa, and product uses gas chromatograph to be analyzed.
Embodiments of the invention three are:
Course of reaction is with embodiment one.The hydrochloric acid (1000kg/h) of 20%, is passed through in reactor with methanol (249kg/h), reaction
Temperature is 120 DEG C, and pressure is 260kpa, and product uses gas chromatograph to be analyzed.
Embodiments of the invention four are:
Course of reaction is with embodiment one.The hydrochloric acid (1000kg/h) of 20%, is passed through in reactor with methanol (270kg/h), reaction
Temperature is 130 DEG C, and pressure is 350kpa, and product uses gas chromatograph to be analyzed.
Embodiments of the invention five are:
Course of reaction is with embodiment one.The hydrochloric acid (1000kg/h) of 30%, is passed through in reactor with methanol (479kg/h), reaction
Temperature is 135 DEG C, and pressure is 500kpa, and product uses gas chromatograph to be analyzed.
Embodiments of the invention six are:
Course of reaction is with embodiment one.The hydrochloric acid (1000kg/h) of 30%, is passed through in reactor with methanol (513kg/h), reaction
Temperature is 140 DEG C, and pressure is 600kpa, and product uses gas chromatograph to be analyzed.
The analysis result of embodiment arranges in fig. 2, methanol and the molar ratio of hydrogen chloride during wherein mol ratio indicates entry into reactor 4,
Methyl ether is the quality of dimethyl ether in 1000kg chloromethanes；Units/kg.Fig. 2 illustrates that this technique uses hydrochloric acid as raw material, synthesizes chlorine
During methane, the conversion ratio of hydrogen chloride is high, can effectively process all kinds of by-product hydrochloric acids produced in commercial production, and due to dimethyl ether
Selectivity, the utilization rate of methanol is high, can effectively reduce the consumption of concentrated sulphuric acid.
Claims (5)
1. the synthetic method of a chloromethanes, it is characterised in that hydrochloric acid and methanol are sufficiently mixed in entrance reactor, in mixture methanol with
The mol ratio of hydrogen chloride is 1～1.7:1；Mixture 0.15～1.0Mpa and without catalyst under conditions of, be warming up to
100～150 DEG C, react in the reactor liquid phase bed being made up of methanol, hydrogen chloride and water, maintain liquid phase bed
Highly, obtaining reactant chloromethanes, vaporized by product by the way of heating, enter rectifying column, reactant chloromethanes is in essence
Evaporate tower and obtain product chloromethanes after condensing, be dried, compressing.
2. according to the synthetic method of the chloromethanes described in claim 1, it is characterised in that the gas phase mixture that reactor head vaporization produces
Entering rectifying column in liquid form after being directly entered rectifying column, or condensation, the chloromethanes of rectifying column tower top is dried through persulfuric acid.
3. according to the synthetic method of the chloromethanes described in claim 1, it is characterised in that the chloromethanes of vaporization and methanol are at rectifying column tower top
Cooling down in condenser, methanol condensed is that liquid enters recovery in return tank, and unreacted methanol reacts again.
4. according to the synthetic method of the chloromethanes described in claim 1, it is characterised in that reactor bottom is provided with the first reboiler, rectification
Tower bottom is provided with the second reboiler, and the second reboiler connects has heat exchanger, the height of reactor liquid phase bed to be boiled by first again
Device is controlled, and the tower bottoms of rectifier bottoms is under the heating of the second reboiler, and after removing the methanol wherein carried, it contains
The tower bottoms having a small amount of hydrogen chloride is discharged after cooling down with heat exchange of methanol in heat exchanger as waste water.
5. according to the synthetic method of the chloromethanes described in claim 1, it is characterised in that described hydrochloric acid is that catalysis method synthesis chloromethanes is secondary
The containing alcohol dilute hydrochloric acid produced, concentration is 10-40wt.%, and containing the hydrochloric acid that methanol is 0-10wt.% or preparation, concentration is
10-40wt.%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610589621.7A CN106008151A (en) | 2016-07-22 | 2016-07-22 | Methyl chloride synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610589621.7A CN106008151A (en) | 2016-07-22 | 2016-07-22 | Methyl chloride synthesis method |
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| Publication Number | Publication Date |
|---|---|
| CN106008151A true CN106008151A (en) | 2016-10-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610589621.7A Pending CN106008151A (en) | 2016-07-22 | 2016-07-22 | Methyl chloride synthesis method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409526A (en) * | 2018-03-09 | 2018-08-17 | 中国化学赛鼎宁波工程有限公司 | A kind of monochloro methane production energy-saving system and method |
| CN108440244A (en) * | 2018-03-01 | 2018-08-24 | 湖北兴发化工集团股份有限公司 | The technique and device that Methanol Recovery utilizes in a kind of production of chloromethanes |
| CN109574790A (en) * | 2019-01-16 | 2019-04-05 | 杭州东日节能技术有限公司 | Chloromethanes is synthesized without by-product hydrochloric acid technique and its equipment |
| CN111606776A (en) * | 2019-02-26 | 2020-09-01 | 四川晨光工程设计院有限公司 | Clean production process for synthesizing methane chloride by liquid-phase catalyst-free synthesis |
| CN111807924A (en) * | 2020-07-21 | 2020-10-23 | 安徽金轩科技有限公司 | Method for recycling galaxolide waste liquid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3983180A (en) * | 1973-10-06 | 1976-09-28 | Shinetsu Chemical Company | Process for preparing methyl chloride |
| EP1057802A2 (en) * | 1999-06-01 | 2000-12-06 | Dow Corning Corporation | Process for manufacturing methyl chloride |
| CN1686983A (en) * | 2005-04-21 | 2005-10-26 | 江苏梅兰化工股份有限公司 | Method fo rproducing high pure methane chloride |
| 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 |
| CN102838629A (en) * | 2012-09-29 | 2012-12-26 | 山东金岭化学有限公司 | Novel process for synthesizing methyl chlorosilane by methane chloride byproduct chloromethane |
-
2016
- 2016-07-22 CN CN201610589621.7A patent/CN106008151A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3983180A (en) * | 1973-10-06 | 1976-09-28 | Shinetsu Chemical Company | Process for preparing methyl chloride |
| EP1057802A2 (en) * | 1999-06-01 | 2000-12-06 | Dow Corning Corporation | Process for manufacturing methyl chloride |
| CN1686983A (en) * | 2005-04-21 | 2005-10-26 | 江苏梅兰化工股份有限公司 | Method fo rproducing high pure methane chloride |
| 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 |
| CN102838629A (en) * | 2012-09-29 | 2012-12-26 | 山东金岭化学有限公司 | Novel process for synthesizing methyl chlorosilane by methane chloride byproduct chloromethane |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440244A (en) * | 2018-03-01 | 2018-08-24 | 湖北兴发化工集团股份有限公司 | The technique and device that Methanol Recovery utilizes in a kind of production of chloromethanes |
| CN108409526A (en) * | 2018-03-09 | 2018-08-17 | 中国化学赛鼎宁波工程有限公司 | A kind of monochloro methane production energy-saving system and method |
| CN108409526B (en) * | 2018-03-09 | 2020-11-20 | 中国化学赛鼎宁波工程有限公司 | Methane chloride energy-saving production system and method |
| CN109574790A (en) * | 2019-01-16 | 2019-04-05 | 杭州东日节能技术有限公司 | Chloromethanes is synthesized without by-product hydrochloric acid technique and its equipment |
| CN111606776A (en) * | 2019-02-26 | 2020-09-01 | 四川晨光工程设计院有限公司 | Clean production process for synthesizing methane chloride by liquid-phase catalyst-free synthesis |
| CN111807924A (en) * | 2020-07-21 | 2020-10-23 | 安徽金轩科技有限公司 | Method for recycling galaxolide waste liquid |
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Application publication date: 20161012 |