CN105237410A - Method for preparing tetramethyl ammonium bromide - Google Patents
Method for preparing tetramethyl ammonium bromide Download PDFInfo
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- CN105237410A CN105237410A CN201510699341.7A CN201510699341A CN105237410A CN 105237410 A CN105237410 A CN 105237410A CN 201510699341 A CN201510699341 A CN 201510699341A CN 105237410 A CN105237410 A CN 105237410A
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- monobromethane
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Abstract
The invention discloses a method for preparing tetramethyl ammonium bromide. The method includes the steps that methyl aryl ether is subjected to demethylating reaction under the acid condition to generate gas containing methyl bromide, the gas containing methyl bromide is firstly introduced into an alkaline solution for adsorption, overflow gas then sequentially passes a particle activated carbon filler adsorption column and a particle anhydrous calcium chloride filler adsorption column, and pure dried methyl bromide gas is obtained; the methyl bromide gas is introduced into stirred absolute ethyl alcohol to obtain a methyl bromide and ethanol solution; dried trimethylamine gas is introduced into the methyl bromide and ethanol solution, and tetramethyl ammonium bromide precipitate is generated through reaction. The problem about recycle and use of the side product methyl bromide of the demethylating reaction of methyl aryl ether is solved through the simple method, the methyl bromide absorption rate is nearly 100%, the technology is simple and feasible, emission of three wastes meets requirements, methyl bromide recycle cost is low, and competitiveness is extremely good.
Description
Technical field
The present invention relates to a kind of preparation method of 4 bromide, particularly relate to a kind of by product monobromethane utilizing methyl aryl ether to be hydrolyzed demethylation reaction for raw material and prepare the method for 4 bromide.
Background technology
Methyl aryl ether acid demethylating reaction is a classical reaction, for medium with acetic acid and bromine hydracid or boron tribromide, demethylating and carrying out reacts in acid condition, particularly with acetic acid and bromine hydracid for medium, demethylating in backflow situation, the reaction forming byproduct monobromethane is the most general.Reason is that this reaction production cost is minimum, and reaction controls very well.Shortcoming is that side reaction is more, and the monobromethane of generation is difficult to process.
When methyl aryl ethers and Hydrogen bromide carry out demethylating reaction under acidic conditions, six class poisonous substances monobromethanes can be produced.Monobromethane molecular formula CH
3br, molecular weight 94.95, boiling point 3.6 DEG C is gas under normal temperature.Monobromethane severe toxicity, air small mouse lethal concentration is 513ppm, and reaching 10 ~ 20mg/L can causing death.In air, monobromethane maximum allowable concentration is 20ppm.Monobromethane is again a kind of material of depletion, and according to " Montreal Protocol Copenhagen amendment ", developed country eliminated in 2005, and developing country also will eliminate in 2015.A lot of is like this that the chemical of starting raw material synthesis is also faced with and must changes synthetic route and could produce with monobromethane, and this just substantially increases the manufacturing cost of these chemical.
Although the monobromethane that under acidic conditions, methyl aryl ethers and Hydrogen bromide carry out demethylating reaction generation arbitrarily discharges the danger with height, but yet there are no the report producing monobromethane about this reaction of comprehensive reutilization, the monobromethane that reaction generates is recycled great difficulty.
1, the methyl aryl ether demethylating reaction under acidic conditions is rhythmic reaction, and the monobromethane amount produced due to every batch reaction is less, and gas storage cost is too high, and the industrial problem cannot considering to store, the monobromethane that every batch reaction produces must be used up in time.
The reaction times of 2, often criticizing demethylating reaction is approximately 2 ~ 6 hours, and existing monobromethane recycles the technological reaction time all more than 12 hours.To manufacture N-dodecyl methyl secondary amine, dodecyl primary amine and monobromethane are reacted in dimethyl formamide, for up to 14 hours.This just causes the generating rate of monobromethane and the recycling speed severe mismatch of monobromethane, causes this technique to realize industrialization.
3, existing monobromethane is recycled technique to absorb the transformation efficiency of monobromethane all not ideal, that is many residual monobromethanes are still had in emission after treatment, can impact environment, simultaneously because monobromethane concentration in emission is not high, cannot recycle further it again.
4, the facility investment of existing recycling methyl bromide gas technique is large, and the product price of methyl aryl ether demethylating reaction is not too high, and drop into if increase monobromethane recovery process again, whole technique will not have industrial application value.
In sum, existing monobromethane recycling technique cannot be applied in the industrial production of methyl aryl ether demethylating reaction.
Summary of the invention
The object of this invention is to provide a kind of method preparing 4 bromide, the method of the invention utilizes the by product monobromethane of methyl aryl ether demethylating reaction to prepare 4 bromide for raw material, to recycle the methyl bromide gas that methyl aryl ether demethylating reaction produces.
The method utilizing the by product monobromethane of methyl aryl ether demethylating reaction to prepare 4 bromide for raw material of the present invention is: first passed in basic solution by the methyl aryl ether gas containing monobromethane that demethylating reaction produces in acid condition and carry out absorption process; escaping gas is more successively by after granulated active carbon filling adsorption post and particle Calcium Chloride Powder Anhydrous filling adsorption post; pass in the dehydrated alcohol of stirring and obtain monobromethane ethanolic soln; in described monobromethane ethanolic soln, pass into dry Trimethylamine 99 gas, reaction produces 4 bromide precipitation.
Wherein, methyl aryl ether of the present invention demethylating reaction in acid condition refers in acetic aid medium, the demethylating reaction carried out when bromine hydracid exists.
Aryl in methyl aryl ether of the present invention is with substituent phenyl on phenyl or phenyl ring, and wherein, described substituting group is positioned at the ortho position of ether on phenyl ring, contraposition or a position, also can be adjacent, have substituting group to a, position.
Further, described substituting group can be straight chained alkyl, also can be the substituting group containing carbonyl or hydroxyl.
Usually, the monobromethane that demethylating reaction generates is the gas that a kind of purity is not high, has to pass through alkaline solution absorption process and could for the preparation of 4 bromide after charcoal absorption and drying treatment.Wherein, alkaline solution absorption process be will the gas that generates of reaction by the aqueous solution of potassium hydroxide, sodium hydroxide or calcium hydroxide, to remove bromine hydracid wherein and acetic acid, the mass concentration of basic solution can be 2 ~ 50%.Charcoal absorption process is then by the gas through basic solution process by active carbon layer, the reactant of the absorption minute quantity of being taken out of by reactant gases wherein and resultant.Drying treatment is by the gas after charcoal absorption process through anhydrous chlorides of rase Calcium treatment, removes the residual moisture wherein contained.
Clean dry methyl bromide gas after above-mentioned purifying treatment is passed in the dehydrated alcohol of-5 ~ 40 DEG C and obtains monobromethane ethanolic soln.Preferably, the mass concentration of described monobromethane in dehydrated alcohol is 3 ~ 75%.
In the present invention, described Trimethylamine 99 gas can be heated to 30 ~ 70 DEG C by the trimethylamine aqueous solution of mass concentration 30 ~ 40%, the pure Trimethylamine 99 gas of the drying obtained after Calcium Chloride Powder Anhydrous drying, also can be in the potassium hydroxide of mass concentration 4 ~ 50%, sodium hydroxide or calcium hydroxide aqueous solution, be heated to 30 ~ 70 DEG C by trimethylamine hydrochloride, the pure Trimethylamine 99 gas of the drying obtained after Calcium Chloride Powder Anhydrous drying can also be the Trimethylamine 99 gas directly supplied by steel cylinder.
Trimethylamine 99 gas pure for drying passes in the monobromethane ethanol solution of stirring in-5 ~ 40 DEG C by the present invention, till producing without precipitation, reacting liquid filtering is gone out precipitation, and absolute ethanol washing, drying, can obtain the 4 bromide solid that content is greater than 99%.The mother liquid recycle that filtration obtains is in the recovery of next batch monobromethane.
The present invention solves the recycling problem of the methyl aryl ether by product monobromethane of demethylating reaction in acid condition with simple method, methyl bromide gas reaction generated, successively after basic solution process, activated carbon treatment and processed, generates 4 bromide with the Trimethylamine 99 gas reaction of drying in dehydrated alcohol.4 bromide is a kind of broad-spectrum tensio-active agent and sterilant, may be used in oil, chemical industry recirculated water, as preventing the additive generating moss and fouling, also may be used in washing powder, replace phosphoric acid six sodium as calcium ions and magnesium ions complexing agent, also have effect of sterilant simultaneously.
The by product monobromethane of methyl aryl ether demethylating reaction is in acid condition a kind of gas of purity extreme difference, and according to the difference of reactant and the difference of reaction conditions, the ratio generating each component of gas is also each variant.Containing monobromethane, reactant, resultant, acetic acid and hydrogen bromide in the gas produced, other gaseous constituent wherein except monobromethane must be removed, monobromethane just can be made to recycle, otherwise qualified 4 bromide product can not be obtained.The emission gases that the present invention makes reaction produce is first through basic solution process, remove acetic acid wherein and bromine hydracid, again through charcoal absorption process, remove the reactant and resultant that wherein contain, eventually pass Calcium Chloride Powder Anhydrous drying, methyl bromide gas pure for the drying obtained directly is passed in the dehydrated alcohol of-5 ~ 40 DEG C and obtain monobromethane ethanolic soln.
Trimethylamine aqueous solution (also can be trimethylamine hydrochloride or Trimethylamine 99 gas) is heated to 30 ~ 70 DEG C, make Trimethylamine 99 gaseous volatilization out, be passed in above-mentioned monobromethane ethanol solution after Calcium Chloride Powder Anhydrous removing moisture, until produce without precipitation, this reaction approximately needs 1 hour.Treatment process of the present invention makes the monobromethane finishing time of methyl aryl ether demethylating reaction (namely manufacturing the time of 4 bromide) be significantly smaller than the demethylating reaction time, so only need a set of finishing apparatus, just can meet the whole processing requirement of demethylating reaction.
As long as reacting liquid filtering is gone out precipitation by the present invention, absolute ethanol washing, drying, the 4 bromide solid that content is greater than 99% can be obtained, the mother liquor that filtration obtains can also overlap the recovery for next batch monobromethane, the recycling process of monobromethane is discharged without any the three wastes, meets industry and civilian demand.
The monobromethane specific absorption for the treatment of process of the present invention almost reaches 100%, and not only simple for process, three waste discharge meets the requirements, and owing to reclaiming the cost of monobromethane and cheap, commercially has fabulous competitive power.
Embodiment
Embodiment 1
In the three-necked bottle that 1000ml band stirs, add 600ml dehydrated alcohol, be cooled to 20 DEG C.
122g is added methoxy toluene in the acetum of hydrogen bromide and carry out demethylating reaction; the methyl bromide gas that reaction generates first passes in the 200ml20%NaOH aqueous solution; again successively by diameter 1cm, high 5cm; the adsorption column of in-built seed activity carbon filling material and diameter 3cm, high 10cm; the adsorption column of in-built particle Calcium Chloride Powder Anhydrous filler; the clean dry methyl bromide gas of removing residual moisture passes in the dehydrated alcohol in above-mentioned stirring, until demethylating reaction terminates.
30% trimethylamine aqueous solution 500g is placed in 1000ml three-necked bottle, be heated to 50 DEG C, the Trimethylamine 99 gas discharged passes into diameter 3cm, high 10cm, the adsorption column of in-built particulate state Calcium Chloride Powder Anhydrous filler, pass in above-mentioned monobromethane ethanolic soln after moisture in removing gas, reaction produces 4 bromide precipitation, until after can't see precipitation generation, stops passing into Trimethylamine 99 gas.
By reacting liquid filtering, with 8ml absolute ethanol washing filter cake, dry, obtain 4 bromide 142g, yield 92.2%.The mother liquid recycle that filtration obtains is in the recovery of next batch monobromethane.
Embodiment 2
In the three-necked bottle that 1000ml band stirs, add 600ml dehydrated alcohol, be cooled to 10 DEG C.
150g p-methoxy-acetophenone is added in the acetum of hydrogen bromide and carry out demethylating reaction; the methyl bromide gas that reaction generates first passes in the 200ml10%NaOH aqueous solution; again successively by diameter 1cm, high 5cm; the adsorption column of in-built seed activity carbon filling material and diameter 3cm, high 10cm; the adsorption column of in-built particle Calcium Chloride Powder Anhydrous filler; the clean dry methyl bromide gas of removing residual moisture passes in the dehydrated alcohol in above-mentioned stirring, until demethylating reaction terminates.
Be placed in by 200g trimethylamine hydrochloride in 1000ml three-necked bottle, slowly drip the 600ml20%NaOH aqueous solution, in dropping process, control temperature is no more than 50 DEG C.The Trimethylamine 99 gas discharged in dropping process passes into diameter 3cm, high 10cm, the adsorption column of in-built particulate state Calcium Chloride Powder Anhydrous filler, pass in above-mentioned monobromethane ethanolic soln after moisture in removing gas, reaction produces 4 bromide precipitation, until after can't see precipitation generation, stop passing into Trimethylamine 99 gas.
By reacting liquid filtering, with 8ml absolute ethanol washing filter cake, dry, obtain 4 bromide 138g, yield 92%.The mother liquid recycle that filtration obtains is in the recovery of next batch monobromethane.
Claims (9)
1. prepare the method for 4 bromide for one kind, for raw material with the by product monobromethane of methyl aryl ether demethylating reaction, the methyl aryl ether gas containing monobromethane that demethylating reaction produces in acid condition is first passed in basic solution, escaping gas is more successively by after granulated active carbon filling adsorption post and particle Calcium Chloride Powder Anhydrous filling adsorption post, obtain the methyl bromide gas of clean dry, pass in the dehydrated alcohol of stirring and obtain monobromethane ethanolic soln, dry Trimethylamine 99 gas is passed in described monobromethane ethanolic soln, reaction produces 4 bromide precipitation.
2. the method preparing 4 bromide according to claim 1, is characterized in that described methyl aryl ether demethylating reaction in acid condition refers in acetic aid medium, the demethylating reaction carried out when bromine hydracid exists.
3. the method preparing 4 bromide according to claim 1 and 2, the aryl that it is characterized in that in described methyl aryl ether is with substituent phenyl on phenyl or phenyl ring, described substituting group is positioned at the ortho position of ether on phenyl ring, contraposition or a position, or adjacent, have substituting group to a, position.
4. the method preparing 4 bromide according to claim 3, is characterized in that described substituting group is straight chained alkyl, or contains the substituting group of carbonyl or hydroxyl.
5. the method preparing 4 bromide according to claim 1, is characterized in that described basic solution is the aqueous solution of potassium hydroxide, sodium hydroxide or calcium hydroxide, and the mass concentration of described basic solution is 2 ~ 50%.
6. the method preparing 4 bromide according to claim 1, is characterized in that the methyl bromide gas of clean dry to pass in the dehydrated alcohol of-5 ~ 40 DEG C to obtain monobromethane ethanolic soln.
7. the method preparing 4 bromide according to claim 1 or 6, is characterized in that the mass concentration of described monobromethane ethanolic soln is 3 ~ 75%.
8. the method preparing 4 bromide according to claim 1, is characterized in that described Trimethylamine 99 gas is heated to 30 ~ 70 DEG C by the trimethylamine aqueous solution of mass concentration 30 ~ 40%, the pure Trimethylamine 99 gas of the drying obtained after Calcium Chloride Powder Anhydrous drying.
9. the method preparing 4 bromide according to claim 1, it is characterized in that described Trimethylamine 99 gas in the potassium hydroxide of mass concentration 4 ~ 50%, sodium hydroxide or calcium hydroxide aqueous solution, is heated to 30 ~ 70 DEG C, the pure Trimethylamine 99 gas of the drying obtained after Calcium Chloride Powder Anhydrous drying by trimethylamine hydrochloride.
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| CN201510699341.7A CN105237410B (en) | 2015-10-26 | 2015-10-26 | A kind of method for preparing 4 bromide |
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| CN201510699341.7A CN105237410B (en) | 2015-10-26 | 2015-10-26 | A kind of method for preparing 4 bromide |
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| CN105237410B CN105237410B (en) | 2017-08-01 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112047807A (en) * | 2020-08-24 | 2020-12-08 | 临海市建新化工有限公司 | Impurity removal process for methyl bromide by adopting weak base |
| CN112047806A (en) * | 2020-08-24 | 2020-12-08 | 临海市建新化工有限公司 | Process for removing impurities from methyl bromide by using strong alkali |
Citations (5)
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| US4018704A (en) * | 1974-11-14 | 1977-04-19 | Mitsui Toatsu Chemicals, Incorporated | Method for desorption of methyl bromide |
| CN1326933A (en) * | 2001-06-19 | 2001-12-19 | 王世国 | Process for preparing bromo-ortho-piperonaldehyde |
| CN201162937Y (en) * | 2008-03-03 | 2008-12-10 | 天津市检验检疫科学技术研究院 | Bromomethane pressurization and condensation reclaimer |
| CN102020571A (en) * | 2009-09-23 | 2011-04-20 | 天津市化学试剂研究所 | Preparation method of tetramethylammonium bromide |
| JP2013158763A (en) * | 2012-02-09 | 2013-08-19 | Toray Ind Inc | Exhaust gas treatment method |
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2015
- 2015-10-26 CN CN201510699341.7A patent/CN105237410B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4018704A (en) * | 1974-11-14 | 1977-04-19 | Mitsui Toatsu Chemicals, Incorporated | Method for desorption of methyl bromide |
| CN1326933A (en) * | 2001-06-19 | 2001-12-19 | 王世国 | Process for preparing bromo-ortho-piperonaldehyde |
| CN201162937Y (en) * | 2008-03-03 | 2008-12-10 | 天津市检验检疫科学技术研究院 | Bromomethane pressurization and condensation reclaimer |
| CN102020571A (en) * | 2009-09-23 | 2011-04-20 | 天津市化学试剂研究所 | Preparation method of tetramethylammonium bromide |
| JP2013158763A (en) * | 2012-02-09 | 2013-08-19 | Toray Ind Inc | Exhaust gas treatment method |
Non-Patent Citations (1)
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| G. DRIVER，K. E. JOHNSON: "3-Methylimidazolium bromohydrogenates(I): a room-temperature ionic liquid for ether cleavage", 《GREEN CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112047807A (en) * | 2020-08-24 | 2020-12-08 | 临海市建新化工有限公司 | Impurity removal process for methyl bromide by adopting weak base |
| CN112047806A (en) * | 2020-08-24 | 2020-12-08 | 临海市建新化工有限公司 | Process for removing impurities from methyl bromide by using strong alkali |
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| CN105237410B (en) | 2017-08-01 |
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Effective date of registration: 20211105 Address after: 261000 Lingang Industrial Park, Binhai Development Zone, Weifang City, Shandong Province Patentee after: Shandong Yubin New Material Co.,Ltd. Address before: 200435 No. 21, Hyde garden, No. 2488, Yunchuan Road, Baoshan District, Shanghai Patentee before: Cao Yishan |