CN101357877B - Method for preparing dibromomethane and methylene chlorobromide by one-pot - Google Patents
Method for preparing dibromomethane and methylene chlorobromide by one-pot Download PDFInfo
- Publication number
- CN101357877B CN101357877B CN2008101394378A CN200810139437A CN101357877B CN 101357877 B CN101357877 B CN 101357877B CN 2008101394378 A CN2008101394378 A CN 2008101394378A CN 200810139437 A CN200810139437 A CN 200810139437A CN 101357877 B CN101357877 B CN 101357877B
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- bromochloromethane
- bromide
- reaction
- methylene
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing dibromomethane and bromochloromethane by a kettle method, which adopts the following processes: hydrogen bromide and dichloromethane react to obtain dibromomethane; methanol is reacted with water to obtain pure hydrogen; the hydrogen is then reacted with bromine to obtain hydrogen bromide gas; the hydrogen bromide gas is then purified until the purity is above 98 percent, thus ensuring that the side effect brought to the reaction by the hydrogen can be reduced to the lowest; the hydrogen bromide gas and the dibromomethane are added into a reaction kettle for reaction; after the operations of washing, distilling, and the like, the dibromomethane and bromochloromethane with high purity can be obtained from reactants; the dichloromethane is used for the combined production of dibromomethane and bromochloromethane, which is the most direct and economical way, and the method is characterized by no introduction of other impurities, no by-products, the high quality of products and no pollution of three-waste.
Description
Technical field
The present invention relates to a kind of one still process and produce the preparation method of methylene bromide, bromochloromethane.
Background technology
Methylene bromide is the raw material of multiple organic compound, as agricultural chemicals synthetic aspect, be used for synthetic nitrile bacterium azoles, dithiocyano-methane, Nialate etc., the former is efficient, the less-persistent pesticide widelyd popularize of country just.
Bromochloromethane is a kind of important fine chemical material as the intermediate of medicine, agricultural chemicals, sterilant, water conditioner.
Methylene bromide English name Dibromomethane is colourless or light yellow transparent liquid, density 2.4970g/cm
3(20 ℃), fusing point-52.7 ℃, 96.5 ℃ of boiling points, specific refractory power 1.542, the solubleness 1.17g/100g in water (15 ℃) is soluble in alcohol, acid, the ester.Methylene bromide is the main raw material of synthesizing new high-effective broad-spectrum fungicide nitrile bacterium azoles, azoles bacterium nitrile, dithiocyano-methane, the acaricidal raw material of large-tonnage especially as pesticide intermediate.Methylene bromide is a kind of good flame agent, and it adds the combustion heat in the time of reducing the plastics burning in the polymkeric substance effectively to.
Bromochloromethane English name Bromine Chloro Methane is colourless liquid, has special sweet taste, is slightly soluble in water, and nonflammable, non-explosive, freezing point is low, can with multiple immiscible organic solvent, 68.1 ℃ of boiling points, density 1.92g/cm
3(20 ℃), freezing point-88 ℃.Bromochloromethane is a kind of important fine chemical product as the intermediate of medicine, agricultural chemicals, sterilant, water conditioner etc.
At present, the main production of methylene bromide has following several:
(1) makes at the chlorine element that replaces on the methylene dichloride by bromo element under the catalyst condition.The main advantage of this production technique is exactly that transformation efficiency is higher relatively, good product quality.But this technology also has many shortcomings, mainly shows: the main source of bromo element is the exsiccant bromize hydrogen gas, but bromize hydrogen gas contains a large amount of hydrogen usually in producing, and just production has brought very big side effect to methylene bromide for this.Hydrogen does not participate in reaction as a kind of rare gas element in reaction process, begin to reacting the whole process that finishes all along with material acutely flows from reaction.This will inevitably cause a part of methylene dichloride also not have enough time to react and just be blown away by hydrogen, so the transformation efficiency of methylene dichloride just greatly reduces.Methylene dichloride is very expensive in addition, and responseless methylene dichloride is discharged very waste with hydrogen, also can bring environmental problem simultaneously, therefore needs methylene dichloride with the Hydrogen Separation recycle.But because of the sepn process complexity, to having relatively high expectations of equipment, this has just increased the production cost of methylene bromide greatly.
This technology principal reaction principle:
(2) another production technique of methylene bromide is to carry out substitution reaction with NaBr and methylene dichloride, and the major advantage of this technology is that technology is comparatively simple, and lower to the requirement of production unit, early investment is less.But this production technique is because of metal Na among the NaBr
+The blunt effect that causes make the selectivity of reaction pair methylene bromide reduce greatly, this has just caused the productive rate very low (30-35%) of methylene bromide, production cost is too high.Along with the exploitation of development of technology and novel process, this production technique will be eliminated gradually.
This technology principal reaction principle:
(3) production technique that also has a kind of methylene bromide is direct methyl bromide at high temperature, and this technology is to be that catalyzer, temperature are under 370 ℃ the condition, to be the direct methyl bromide of raw material with bromine with iron.This production process equipment input is less relatively, and reaction conditions is relatively low, and the quality of product is higher.But this production technique has reverse selectivity, and production capacity is low, and obtainable maximum yield is 44.4%.
This technology principal reaction principle:
At present, the main production of bromochloromethane has following several:
(1) utilizes methylene dichloride and hydrogen bromide under the effect of catalyzer, carried out substitution reaction than 1: 1 by amount of substance and generate bromochloromethane.This production technique is easy and simple to handle, is the main production method of present bromochloromethane.
This technology principal reaction principle:
(2) another production technique of bromochloromethane is to carry out substitution reaction with NaBr and methylene dichloride at 1: 1 by amount of substance, and the major advantage of this technology is that technology is comparatively simple, and lower to the requirement of production unit, early investment is less.But this production technique is because of metal Na among the NaBr
+The blunt effect that causes make the selectivity of reaction pair bromochloromethane reduce greatly, thereby influenced the carrying out of reaction.
Summary of the invention
Problem to be solved by this invention provides the preparation method that a kind of one still process is produced methylene bromide, bromochloromethane, and this method technology is simple, and cost is lower, and productive rate is higher, and quality product can meet the requirements of the standard.Technical scheme of the present invention is as follows:
This invention is adopted by hydrogen bromide and the synthetic methylene bromide of methylene dichloride reaction.Methyl alcohol and water make purified hydrogen, and hydrogen and bromine reaction generate bromize hydrogen gas.Bromize hydrogen gas purified to be obtained purity and reaches gas 98% or more, and assurance brings hydrogen to reaction side effect drops to minimum.Bromize hydrogen gas and methylene bromide are added reaction kettle for reaction, and reactant makes highly purified methylene bromide and bromochloromethane through operations such as washing, distillations.
(1) ultimate principle:
CH
3OH+H
2O→H
2+CO
2
H
2+Br
2→HBr
CH
2Cl
2+HBr→CH
2BrCl+HCl
CH
2BrCl+HBr→CH
2Br
2+HCl
One still process is produced the preparation method of methylene bromide, bromochloromethane, and it is characterized in that: described preparation method may further comprise the steps:
1. hydrogen manufacturing operation
With methyl alcohol and pure water weight ratio wiring solution-forming by 1: 1, squeeze into reactor with volume pump, add mixed, be forced under 280 ℃ of conditions and produce H
2, CO
2, obtaining purity through transformation absorption and purifying treatment is 99.9% hydrogen;
2. hydrogen bromide synthesis procedure
Open quartzy resistance furnace, when furnace temperature is raised to 700 ℃, open exhaust-valve, go out air in the calcinatory towards nitrogen replacement, be in 1: 1 the silica glass synthetic furnace of 700 ℃ of proportioning feeding temperature with the hydrogen that purifies and bromine according to mol ratio, synthesizing hydrogen bromide gas, then through debrominate, it is stand-by to enter storage tank after the molecular sieve drying;
3. reaction
Methylene dichloride metering back is added reactor, add the catalyzer aluminum chloride, open stirrer and open refrigerator, progressively feed the bromize hydrogen gas that measures when temperature reaches-30 ℃, regulate flow, flow control is at 8～10m
3/ h, blow afloat feed liquid, be as the criterion, heat then not fall material, controlled temperature when heating, per hour heat up 1-2 ℃, observe the condenser return velocity, do not become line to be as the criterion to reflux, temperature of reaction is no more than 40 ℃, in 24 hours reaction times, distillation obtained finished product methylene bromide, bromochloromethane after the thick product that reacting finishes generates was handled through washing, and it is synthetic again that low-boiling-point substance returns reactor.
Above-mentioned preparation method's advantage:
1, adopting methylene dichloride coproduction methylene bromide, bromochloromethane is direct, the most most economical production method, and it does not introduce other impurity, no coupling product, quality product height, does not have " three wastes " and pollutes.
2, hydrogen bromide synthesis route aspect
This technical scheme has adopted bromo element to replace the production technique of the chlorine element on the methylene dichloride, and the technical bottleneck in the former technology mainly is to contain hydrogen in the source hydrogen bromide of bromo element, the side effects that hydrogen brings as rare gas element the productive rate of methylene bromide.Therefore, the synthesis technique of hydrogen bromide makes the purity of synthetic bromize hydrogen gas reach more than 98%, has fundamentally solved hydrogen and has given the synthetic influence that brings, and makes production cost reduce greatly.
Original domestic hydrogen bromide synthesis technique is relatively backward, and the hydrogen in the gas hydrogen bromide, free bromine and moisture content are higher, and is difficult to get rid of.This process using High Purity Hydrogen and bromine be high-temp combustion synthesizing hydrogen bromide gas in quartzy roasting kiln, and adsorb a small amount of unreacted bromine through the AL adsorption tower, adsorbing tower with molecular sieve absorption less water wherein, the bromize hydrogen gas of treated mistake reach next step reaction requirement fully.
3, this technology utilization high purity hydrogen bromide gas and technical grade methylene dichloride are raw material, and technology is simplified and stablized to reaction synthesis of high purity methylene bromide and bromochloromethane.
4, methylene bromide, bromochloromethane coproduction, at present domestic also do not have producer to carry out this method.This technology confirms to reach fully design requirements through large-scale production.
5, the synthetic methylene bromide of the one still process of our company's employing, bromochloromethane technology, product yield is largely increased, and as benchmark, total product yield can reach more than 80% with methylene dichloride.
The present invention is further illustrated below by embodiment:
Embodiment
The preparation method that embodiment, one still process are produced methylene bromide, bromochloromethane, described preparation method may further comprise the steps:
1. hydrogen manufacturing operation
With methyl alcohol and pure water weight ratio wiring solution-forming by 1: 1, squeeze into reactor with volume pump, add mixed, be forced under 280 ℃ of conditions and produce H
2, CO
2, obtaining purity through transformation absorption and purifying treatment is 99.9% hydrogen;
2. hydrogen bromide synthesis procedure
Open quartzy resistance furnace, when furnace temperature is raised to 700 ℃, open exhaust-valve, going out air in the calcinatory towards nitrogen replacement, is that mol ratio is in 1: 1 the silica glass synthetic furnace of 700 ℃ of proportioning feeding temperature with hydrogen 3.1kg and the bromine 229.4kg that purifies, synthesizing hydrogen bromide gas, then through debrominate, it is stand-by to enter storage tank after the molecular sieve drying, and this process loss 0.5kg obtains the bromize hydrogen gas of 232kg;
3. reaction
500kg methylene dichloride metering back is added reactor, add the catalyzer aluminum chloride, open stirrer and open refrigerator, progressively feed the bromize hydrogen gas that 232kg measures when temperature reaches-30 ℃, regulate flow, flow control is at 8～10m
3In/h the scope, blow afloat feed liquid, be as the criterion not fall material, heat then, controlled temperature when heating, per hour heat up 1-2 ℃, observe the condenser return velocity, do not become line to be as the criterion to reflux, temperature of reaction is no more than 40 ℃, in 24 hours reaction times, distillation obtained the finished product methylene bromide after the thick product that reacting finishes generates was handled through washing, it is synthetic again that bromochloromethane, low-boiling-point substance return reactor, in the reactor in the reflection process absorbing hydrogen chloride and hydrogen bromide amount to 105kg, residual reactant material 627kg, washing stage loss material 0.6kg, real surplus 626.4kg material enters the distillation stage, entering No. 1 distiller distills, 60 ~ 70 ℃ of distillation condition temperature, pressure 0.2 ~ 0.4Mpa obtains methylene bromide 92kg, entering No. 2 distillers then distills, distillation condition is 90 ~ 100 ℃ of temperature, and pressure 0.2 ~ 0.4Mpa obtains bromochloromethane 312kg.
Quality index, the examination criteria of methylene bromide, bromochloromethane are as follows:
Table 1 is the quality index of the methylene bromide in the standard:
| Title | Index |
| Outward appearance | Colourless liquid |
| Methylene bromide, % | ≥99.90 |
| Bromochloromethane, % | ≤0.09 |
| Methylene dichloride, % | ≤0.01 |
| Acidity, % | ≤0.01 |
The detection method of the every index in the table 1:
Outward appearance: use visual observations.
Methylene bromide, bromochloromethane, methylene dichloride Determination on content, gas chromatograph, glass capillary column or stainless steel are breathed out skin pine filled column, 170 ℃ of temperature of vaporization chamber, 130 ℃ of column temperatures, 180 ℃ of detectors, nitrogen pressure 0.8kg/cm
2' ask percentage composition with area normalization method.
The detection of acidity is measured according to the method for GB/T4120.3 regulation.
Table 2 is the quality index of the methylene bromide in the standard:
| Title | Index |
| Outward appearance | Colourless liquid |
| Bromochloromethane, % | ≥99.90 |
| Methylene bromide, % | ≤0.02 |
| Methylene dichloride, % | ≤0.08 |
| Moisture content, % | ≤0.05 |
The detection method of the every index in the table 2:
Outward appearance: use visual observations.
Methylene bromide, bromochloromethane, methylene dichloride Determination on content, gas chromatograph, glass capillary column, column length 20cm, 170 ℃ of temperature of vaporization chamber, 130 ℃ of column temperatures, 180 ℃ of detectors, nitrogen pressure 0.8kg/cm
2' ask percentage composition with area normalization method.
The detection of moisture is measured according to the regulation of " mensuration of Chemicals moisture content-karl Fischer method (universal method) ".
The finished product methylene bromide of method for preparing, the detected result of bromochloromethane are as follows:
Is that methylene bromide and bromochloromethane all meet every index request through Shandong Province's salt and salt chemical product quality monitoring testing station according to above-mentioned standard detection check conclusion.
The detection conclusion such as the table 3 of methylene bromide
| Test item | Quality index | Detected result | Conclusion |
| Sense organ | Colourless liquid | Colourless liquid | Qualified |
| Methylene bromide, % | ≥99.90 | 99.97 | Qualified |
| Bromochloromethane, % | ≤0.09 | 0.02 | Qualified |
| Methylene dichloride, % | ≤0.01 | 0.002 | Qualified |
| Acidity, % | ≤0.01 | 0.004 | Qualified |
The detection conclusion such as the table 4 of bromochloromethane
| Title | Index | Detected result | Conclusion |
| Sense organ | Colourless liquid | Colourless liquid | ? |
| Bromochloromethane, % | ≥99.90 | 99.95 | ? |
| Methylene bromide, % | ≤0.02 | 0.02 | ? |
| Methylene dichloride, % | ≤0.08 | 0.005 | ? |
| Moisture content, % | ≤0.05 | 0.02 | ? |
, from above-mentioned detection as can be seen, the requirement that the finished product that the method applied in the present invention is produced reaches quality standards fully.
Claims (1)
1. one still process is produced the preparation method of methylene bromide, bromochloromethane, and it is characterized in that: described preparation method may further comprise the steps:
1. hydrogen manufacturing operation
With methyl alcohol and pure water weight ratio wiring solution-forming by 1: 1, squeeze into reactor with volume pump, add mixed, be forced under 280 ℃ of conditions and produce H
2, CO
2, obtaining purity through transformation absorption and purifying treatment is 99.9% hydrogen;
2. hydrogen bromide synthesis procedure
Open quartzy resistance furnace, when furnace temperature is raised to 700.℃ the time, open exhaust-valve, go out air in the calcinatory towards nitrogen replacement, be in 1: 1 the silica glass synthetic furnace of 700 ℃ of proportioning feeding temperature with the hydrogen that purifies and bromine according to mol ratio, synthesizing hydrogen bromide gas, then through debrominate, it is stand-by to enter storage tank after the molecular sieve drying;
3. reaction
Methylene dichloride metering back is added reactor, add the catalyzer aluminum chloride, open stirrer and open refrigerator, progressively feed the bromize hydrogen gas that measures when temperature reaches-30 ℃, regulate flow, flow control is at 8～10m
3/ h, blow afloat feed liquid, be as the criterion, heat then not fall material, controlled temperature when heating, per hour heat up 1-2 ℃, observe the condenser return velocity, do not become line to be as the criterion to reflux, temperature of reaction is no more than 40 ℃, in 24 hours reaction times, distillation obtained finished product methylene bromide, bromochloromethane after the thick product that reacting finishes generates was handled through washing, and it is synthetic again that low-boiling-point substance returns reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101394378A CN101357877B (en) | 2008-09-10 | 2008-09-10 | Method for preparing dibromomethane and methylene chlorobromide by one-pot |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101394378A CN101357877B (en) | 2008-09-10 | 2008-09-10 | Method for preparing dibromomethane and methylene chlorobromide by one-pot |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101357877A CN101357877A (en) | 2009-02-04 |
| CN101357877B true CN101357877B (en) | 2011-06-22 |
Family
ID=40330494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101394378A Expired - Fee Related CN101357877B (en) | 2008-09-10 | 2008-09-10 | Method for preparing dibromomethane and methylene chlorobromide by one-pot |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101357877B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913981A (en) * | 2010-07-30 | 2010-12-15 | 天津长芦海晶集团有限公司 | Method for preparing dibromomethane by continuous distillation |
| CN104492411B (en) * | 2014-12-16 | 2016-06-29 | 华东师范大学 | A kind of ZnO/SiO2-γ-Al2O3Catalyzing hydrolysis Celfume prepares the method for methanol and dimethyl ether |
| CN106594543B (en) * | 2016-12-29 | 2019-03-22 | 常州市福兴电器有限公司 | A kind of LED filament lamp and its lighting device |
| CN106892793A (en) * | 2017-02-22 | 2017-06-27 | 常州大学 | The circulation utilization method of bromine in a kind of bactericide dithiocyano-methane production |
| CN107973692B (en) * | 2017-11-24 | 2021-03-12 | 天津大学 | Preparation method of brominated alkanes |
| CA3162881A1 (en) * | 2019-11-28 | 2021-06-03 | Saltigo Gmbh | Improved process for preparing bromochloromethane |
| CN112158806A (en) * | 2020-09-03 | 2021-01-01 | 潍坊摩根化工有限公司 | Preparation and application method of hydrogen bromide gas |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2226311A (en) * | 1988-11-07 | 1990-06-27 | Bromine Compounds Ltd | Gas-phase process for the production of bromochloromethane and dlbromomethane |
-
2008
- 2008-09-10 CN CN2008101394378A patent/CN101357877B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2226311A (en) * | 1988-11-07 | 1990-06-27 | Bromine Compounds Ltd | Gas-phase process for the production of bromochloromethane and dlbromomethane |
Non-Patent Citations (1)
| Title |
|---|
| Wolfgang Gerhartz.1.4.9.Bromochloromethane and Dibromomethane.《Ullmann"s Encyclopedia of Industrial Chemistry》.VCH,1985,第A4卷(第5版),413. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101357877A (en) | 2009-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101357877B (en) | Method for preparing dibromomethane and methylene chlorobromide by one-pot | |
| JP5339782B2 (en) | Method for producing alkali metal alcoholate | |
| CN106748632B (en) | A kind of clean preparation method synthesizing chloromethanes | |
| CN102816045B (en) | Method for synthesizing chloromethane by tail gas generated during chloroacetic acid production | |
| CN103724155A (en) | Chloropropene production process | |
| CN102976945A (en) | Method for synthetizing ethyl chrysanthemumate compound by microreactor | |
| CN109336746A (en) | A kind of preparation method of methyl eight bromo ether | |
| CN106831315A (en) | A kind of continuous production method of chloroethanes | |
| CN101781164B (en) | Preparation method of difluoromono-chloroethane | |
| CN101747176B (en) | Method for preparation of trifluoro acetyl chloride with trifluoroethane chlorinated mixture | |
| EP1360164B1 (en) | Production of potassium formate | |
| CN108947758A (en) | A method of catalysis dibenzofurans open loop prepares biphenyl | |
| CN101306980B (en) | Method for preparing perchloro cyclopentadiene | |
| CN1330624C (en) | Process for the preparation of monochloroacetic acid | |
| CN115246808B (en) | Preparation method of chloroethylene carbonate | |
| CN1730127A (en) | Process for preparing clean highly effective gas fire-extinguishing medium | |
| CN112142690A (en) | Process for producing epichlorohydrin by using chlorinated paraffin and chlorine-containing tail gas glycerin method | |
| CN208482225U (en) | A kind of hydrogen chloride purification and recovery system | |
| CN206624653U (en) | A kind of device for preparing dichlororosilane eiectronic grade | |
| CN100491238C (en) | Method and device for synthesizing chlorosulfonic acid from liquid sulphur trioxide | |
| CN1915984A (en) | Method for preparing whisky lactone | |
| CN112479858A (en) | Methanol carbonylation enhanced reaction system and process with aldehyde recovery function | |
| CN100376524C (en) | Prepn process of p-bromofluoro benzene | |
| CN112341309B (en) | Preparation method of dichloroalkane | |
| CN220861410U (en) | Methyl chloride synthesis system without byproduct hydrochloric acid |
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 | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wang Chunjie Inventor after: Sun Wenyong Inventor after: Song Yongliang Inventor after: Li Yingtang Inventor after: Yuan Yanming Inventor after: Yuan Yanqiang Inventor before: Wang Chunjie Inventor before: Song Yongliang Inventor before: Li Yingtang Inventor before: Yuan Yanming Inventor before: Yuan Yanqiang |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: WANG CHUNJIE SONG YONGLIANG LI YINGTANG YUAN YANMING YUAN YANQIANG TO: WANG CHUNJIE SUN WENYONG SONG YONGLIANG LI YINGTANG YUAN YANMING YUAN YANQIANG |
|
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110622 Termination date: 20130910 |