CN102179136A - Recovery method of methyl bromide gas - Google Patents
Recovery method of methyl bromide gas Download PDFInfo
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- CN102179136A CN102179136A CN2011101073576A CN201110107357A CN102179136A CN 102179136 A CN102179136 A CN 102179136A CN 2011101073576 A CN2011101073576 A CN 2011101073576A CN 201110107357 A CN201110107357 A CN 201110107357A CN 102179136 A CN102179136 A CN 102179136A
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- celfume
- methyl bromide
- rectifying column
- absorption
- recovery method
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- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 title claims abstract description 152
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- 238000011084 recovery Methods 0.000 title claims abstract description 36
- 229940102396 methyl bromide Drugs 0.000 title claims abstract description 23
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000167854 Bourreria succulenta Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010009192 Circulatory collapse Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- Gas Separation By Absorption (AREA)
Abstract
The invention discloses a recovery method of methyl bromide gas, comprising the following steps of: 1) leading a gas containing methyl bromide to be fully contacted with an absorbing agent (glycol) at the temperature of 2-10 DEG C in an absorbing tower, dissolving methyl bromide in the absorbing agent (glycol) and obtaining an absorbing liquid discharged from the absorbing tower bottom; and 2) leading the absorbing liquid to enter a rectifying tower for pressurized separation, and after rectifying, obtaining the methyl bromide gas from the top of the rectifying tower. In the recovery method, the glycol is adopted as the absorbing agent to carry out normal-pressure absorption on the methyl bromide, the rectifying tower is adopted to carry out pressurized separation on the absorbing liquid, then the methyl bromide is recovered, the high-purity glycol is obtained for circular use, the operating conditions are easy to realize, and PLC (programmable logical controller) control is conveniently adopted; the recovery rate of the methyl bromide is high, the production cost is low, and environmental protection is achieved; further the high-temperature glycol liquid discharged from the bottom of the rectifying tower is adopted to carry out heat exchange with the absorbing liquid before entering the rectifying tower, so that the energy in the device is reasonably coupled, the scale of the device is reduced, and the energy consumption of the device is reduced.
Description
Technical field
The present invention relates to a kind of Gas recovering method, particularly relate to a kind of methyl bromide gas recovery method.
Background technology
In international trade, various countries carry out compulsory quarantine system for the resource of protection this country to the import that has.Wooden package stifling (sterilization) is exactly to endanger a kind of compulsory measure that importer's forest reserves are taked for the worm that prevents to fall ill.Therefore, contain the export goods of Wooden package, just must carry out disinfection to the Wooden package thing before going out fortune, stifling (sterilization) is a kind of mode in the disinfection.
Present log generally all uses Celfume as fumigant.Celfume is poisonous to the people.After the people poisons, mainly show as slow nerve anesthesia.The methyl bromide gas of high concentration can damage people's lung and cause relevant circulatory failure.So in the reality of Celfume is stifling, should be specifically noted that the methyl bromide gas that does not suck any concentration.So the Celfume to log after stifling must reclaim, and could guarantee to reach environmental requirement.
The chemical property of Celfume is stable, be difficult for being decomposed by acid-base material, but it can be dissolved in the organic solvents such as alcohol, acetone, ether, carbon disulfide in a large number; Solubility in materials such as oils, fat, dyestuff and vinegar is also higher.
The recovery present situation of existing Celfume
One) proposes and studied some reclaim Celfumes in stifling process technology abroad
The so-called recovery is that the Celfume in the stifling process is collected and preserved.Because technology and economically has only the commercial application of three kinds of recovery methods: active carbon adsorption, condensation method and reactive fluid absorption process etc. at present.In addition, also has certain methods just among active research.If, determine that sealing (being to guarantee to fumigate the place can not leak in the stifling processing procedure of reality) and recovery are as reducing the method that Celfume is distributed to atmosphere, what need the regulation Celfume distributes maximum magnitude or concentration, so just must consider effective specification that reclaimer should possess.
May in the specific occasion, still be discharged into atmosphere by the Celfume that reclaims, also can in device for fumigation, recycle or be destroyed.
1) active carbon adsorption:
Activated carbon can adsorb more Celfume.According to the model and the adsorption conditions of active carbon, adsorption rate can reach 10～30% (content).
When stifling operation, the container of filling activated carbon is installed in the outlet conduit of methyl bromide gas discharging.When the stifling final stage of handling, contain Celfume and Air mixing gas by activated carbon layer, Celfume is adsorbed.Adsorption rate depends mainly on free activated carbon amount.The rate of adsorption then with gas in Celfume concentration, gas flow rate, activated carbon performance relevant with temperature.Under underload, the rate of recovery can reach or near 100%.After active carbon reaches the absorption limit, need carry out the regeneration of adsorbent and handle.Processing method can be taken off active carbon and be inhaled the resolution process of handling or removing to carry out in the special installation 600～900 ℃ of high temperature with thermal current (superheated steam, hot nitrogen or flue gas).In the above-mentioned processing procedure, must pay close attention to any dissipation of avoiding the Celfume toxic gas.
Though, the charcoal absorption method of Celfume has been carried out many researchs,, the whole world has only seldom and has adopted this method to reclaim Celfume in the device for fumigation.At first, there is 30 cubic metres fumatorium to adopt this method, do not re-used now in Belgium.There are 5 30 cubic metres of device for fumigation to adopt active carbon adsorption to reclaim Celfume in Holland.70 kilograms of active carbons of filling in each adsorbent bed.The Celfume use amount is 30 gram/cubic meters in the stifling operation, and the rate of recovery reaches 40～50%, active carbon life cycle 40 times.At last, the waste active carbon calcination resolution process of absorption Celfume.Also have one 30 cubic metres to be used for the stifling asparagus fumatorium that exports to Japan in Thailand, its 72 kilograms of active carbons of Celfume adsorption bed filling can will be fumigated Celfume concentration and reduce to 5ppm in 30 minutes.The active carbon that will adsorb Celfume is at last handled with the health phosphorite.Britain Rentokil has developed a charcoal absorption system and has been used for stifling bubble, seal that tight plastics are fluffy to can be used to fumigate little structures.10 kilograms active carbon layer can adsorb 1.5 kilograms of Celfumes (being equivalent to stifling use amount 5 times).The charcoal absorption bed adopts the method for blowing hot-air.The Celfume of last desorb directly is dispersed into atmosphere.Making is in order to guarantee stifling personnel's safety operation in this way, rather than as the recovery method of avoiding Celfume to distribute.Though, the possibility that the charcoal treatment system provides the rapidest minimizing Celfume to distribute, the common dingus of only considering to be used for stifling article or structures.In order to protect operating personnel's safety, only allow to handle the Celfume of low concentration simultaneously.Stifling to big enveloping fields such as big structures such as flour mill and plantation cereal soil then requires to be filled with the charcoal absorption bed of ton magnitude.1994, carried out reclaiming and recycling the test of Celfume in a German flour mill with active carbon.When last active carbon reaches the absorption limit, spent sorbents is removed, so that handle or regenerate with proper method.If do not have if possible this, necessary by carrying out about the rules and regulations of transportation and storage poisonous substance.
2) condensation/active carbon adsorption:
In the treatment system of U.S. California, at first use condensation method to reclaim Celfume, and then remove residual micro-Celfume with active carbon, the Celfume of recovery can directly recycle use.
3) reactive fluid absorption method:
Amine is typical reactive fluid, and it and Celfume reaction obtain nonvolatile methyl compound.Nineteen eighty-two, the former Soviet Union had once reported employing organic amine and alkali, handled the remaining Celfume of 28 cubic metres of casks when stifling.But MBTOC does not grasp the recent developments of this device now.People such as Mord-kovich also reported the use sodium sulfite aqueous solution as nertralizer in 1985, with ethylenediamine and sodium carbonate mixture as the Celfume adsorbent, but do not know whether this method has reached actual use yet.
4) Activated Zeolite Adsorption:
Use zeolite adsorbents to remove commercial application of CFC in the air stream, this method is used for Celfume reclaims and the development of recirculation has also obtained progress.Though zeolite specific activity charcoal is expensive, it has higher adsorption capacity, particularly under the low concentration situation.In some special applications, zeolite can be processed into very narrow aperture size and distribute.Because specific range of aperture size just might be carried out selective absorption, avoid any potential problems that in the Celfume that reclaims, polluted by other volatile compound.This technology had been carried out pilot scale in 1994, so that the feasibility of technology to be discussed.Experimental result shows that the Celfume rate of recovery reaches more than 90%.Reclaim the Celfume of recirculation after the stifling cherry, do not find other volatile compound that cherry discharges by analysis.Yet test also needs to carry out the circulation checking in a large amount of adsorption-desorption cycles.The Port of San Diego authorities apparatus for establishing at the beginning of nineteen ninety-five of handing down its decision uses zeolite adsorbents in 2100 cubic metres quarantine chamber, to reduce the Celfume emission.
Two) recovery technology in the exploitation
1) novel solid adsorbent
Japan has developed a kind of new adsorbent MBAC, and it is the mixture of active carbon and predetermined substance (amine), than simple active carbon higher adsorption capacity is arranged.This mixture can be processed into powdery, in joining packaging material, can reclaim the Celfume that slowly desorbs in the stifling article.Japan Celfume TIA is carrying out evaluation test, but does not also have the concrete processing method of spent sorbents so far.
2) adopt separation method freezing and condensation
Can in the device of the pure Celfume of packing, reclaim the Celfume that can directly use in this way.But, because the Celfume concentration that fumatorium is discharged in the gas is low, add that boiling point is low again, adopt method recovery Celfume in stifling process of freezing and condensation to seem too complicated, cost is also very high.
3) ozone treatment/active carbon adsorption
U.S. California has developed the Celfume recovery and treatment method that a kind of ozone treatment combines with charcoal absorption.The gas stream that at first fumatorium is come out directly destroys Celfume with ozone oxidation, further removes unreacted Celfume by active carbon layer then.This method is tested in middle experimental rig, and has very certainly set up commercial treating apparatus, and the Celfume rate of recovery requires to reach 90%.This method can produce the Celfume fragment of ozone oxidation and pollute active carbon, and whether present not clear processing they have difficulties.
Three) regeneration and recirculation
1. condensation/active carbon adsorption:
The device that is positioned at LOS Angeles uses condensation/active carbon adsorption Celfume is regenerated and to recycle.This installs original two vacuum chambers, has carried out renewal and reform with recovery and EGR.Remaining Celfume after stifling operation is finished is used the air dilution through washing, purifying.The gaseous mixture of dilution is got rid of by container cooling back, adopts cooled with liquid nitrogen in container, most of Celfume recovery that is condensed in the mixture.Remaining Celfume in the gaseous mixture of discharging is adsorbed by active carbon layer the time.The Celfume of the matching requirements 98% of design is recovered and recycles.Computerized control in the process.Be installed on and build up for the year ends 1993.But because fumatorium does not have stable operation to use, only carry out about 30 return periods, also do not obtain cost of investment and running cost, calculate operating efficiency.
2. active carbon adsorption:
By heating, the Celfume that is adsorbed on the active carbon is recycled, be possible technically.Traditional method is hot-air to be passed through active carbon layer or change pressure (temperature and pressure is absorption alternately), proposes the Celfume that is adsorbed from active carbon with circulating air.It obtains regeneration with the air mixture of high concentration, can be used as fumigant and directly use.Because system loss needs to replenish Celfume to reach suitable fumigating concentration.Pilot scale research has been verified technical feasibility.Can reach 95% for the Celfume rate of recovery of directly recirculation use.Because there is other gaseous impurity in the Celfume that recycles in this method,, also do not carry out demonstration test to agricultural product are stifling based on the consideration of product quality and rules and regulations two aspects.
In Germany, a flour mill has equipped the recirculation system of alternately adsorbing based on the active carbon temperature.This circulating system can be added Celfume to improve concentration, and plant bulk has been dwindled in all right condensation.In some technology, use nitrogen as desorption gas, to avoid the explosion potential of Celfume and air mixture.
With the alternately desorb recirculation of absorption of temperature/pressure, can heat with resistor, avoid using too much diluent air.Above-mentioned two kinds of technologies successfully are applied to reclaim CFC-11.From the stifling operation of flour mill, reclaim the template unit of Celfume, come into operation in September, 1994.The stifling space of flour mill reaches 35000 cubic metres.The stifling back residue Celfume rate of recovery reaches 97%, wherein 93.5% recirculation.
3. zeolite process:
The method that adopts the zeolite process adsorbent to reclaim Celfume has been previously described.Preliminary test shows that recirculation rate can reach more than 96%.In fact, method for recycling is very complicated, and the plant construction expense is very high, can equate with the construction cost of device for fumigation, even higher.Energy resource consumption is very big in the recirculation operation, and operating cost is very expensive.And recirculation operation also has a lot of technical problems, and difficulty is bigger, implements often to be difficult to solve.Therefore, Celfume recirculation is not also generally adopted in many stifling facilities.
Summary of the invention
The present invention provides the recovery method of the methyl bromide gas of a kind of environmental protection, economy for solving the technical problem that exists in the known technology.
The technical scheme that the present invention takes for the technical problem that exists in the solution known technology is: a kind of recovery method of methyl bromide gas, may further comprise the steps: the gas that contains Celfume is fully contacted in the absorption tower with 2～10 ℃ absorbent ethylene glycol, Celfume is dissolved in the absorbent ethylene glycol, obtains out the absorption liquid at the bottom of the absorption Tata; 2) absorption liquid enters the rectifying column separation of pressurizeing, and the gaseous bromine methane after the rectifying is obtained by the extraction of rectifying column cat head.
Described step 2) in, the inlet temperature of stabilizer of absorption liquid is 200～210 ℃, and the part temperature rise of absorption liquid is passed through the coupling preheater and obtained from the ethylene glycol heat exchange at the bottom of the rectifying Tata.
Absolute pressure in the described rectifying column is 2～4atm.
Distillation operation reflux ratio in the described rectifying column is controlled at 2～5.
Described absorption tower and described rectifying column are packed tower.
Advantage and good effect that the present invention has are: adopt ethylene glycol as absorbent Celfume to be carried out normal pressure and absorb, adopt rectifying column to absorption liquid separations of pressurizeing, reclaim Celfume, obtain highly purified glycol circulation use, operating condition is easy to realize, is convenient to adopt PLC control; Absorbent ethylene glycol is good to the dissolubility of Celfume, to the Celfume good absorbing effect, and low price, can recycle, Celfume rate of recovery height, production cost is low; Stable, the difficult decomposition of absorbent ethylene glycol chemical property, non-secondary pollution, environmental protection; Further adopt out the ethylene glycol high-temp liquid at the bottom of the rectifying column to carry out heat exchange with the absorption liquid that advances before the rectifying column, the energy in the device that reasonably has been coupled has reduced the scale of device, has reduced the energy consumption of device.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Among the figure: 1, the pump of unloading, 2, the raw sorbent jar, 3, the absorbent feed pump, 4, absorbent storage tank, 5, the absorbent cooler, 6, the absorbent forecooler, 7, absorption tower, 8, surge tank, 9, the rectifying column feed pump, 10, rectifying column coupling preheater, 11, the absorption liquid preheater, 12, rectifying column, 13, rectifying column reboiler, 14, condenser, 15, return tank, 16, reflux pump, 17, the tail gas air-introduced machine.
The specific embodiment
For further understanding summary of the invention of the present invention, characteristics and effect, exemplify following examples now, and conjunction with figs. is described in detail as follows:
See also Fig. 1.
Embodiment 1:
A kind of recovery method of methyl bromide gas,
The unstrpped gas that contains Celfume enters absorption tower 7 at the bottom of tower;
Unload pump 1 with absorbent ethylene glycol raw material suction raw sorbent jar 2,
Absorbent ethylene glycol is delivered to the cat head that absorbent cooler 5 is cooled to 2 ℃ of laggard absorption towers 7 from raw sorbent jar 2 usefulness absorbent feed pumps 3, and the operating temperature that is to say the absorption tower is 2 ℃.Because the boiling point of Celfume is low, therefore need the absorption tower will be sent into after the absorbent glycol-cooled again.
The absorption that contains the ascending air process absorbent ethylene glycol of Celfume is dissolved in Celfume in the absorbent ethylene glycol.Celfume content allow compliance with emission standards is after tail gas air-introduced machine 17 directly discharges in the absorption tower 7 cats head discharge gas, and Celfume concentration is in the emptying tail gas: 0.02g/m
3
The ethylene glycol absorption liquid that has absorbed Celfume is kept in to a certain amount of via surge tank 87 bottoms from the absorption tower, enters rectifying column 12 through rectifying column feed pump 9 again, is forced into absolute pressure 4atm in rectifying column 12, and the pressurization of carrying out absorption liquid separates, and reclaims Celfume.The ethylene glycol absorption liquid that has absorbed Celfume advances before the rectifying column 12, is preheated to 200 ℃ of laggard rectifying columns 12 through rectifying column coupling preheater 10 and absorption liquid preheater 11, and rectifying column 12 bottoms are connected with rectifying column reboiler 13.Absorption liquid before having adopted the ethylene glycol high-temp liquid that goes out at the bottom of the rectifying column in the technical process and having advanced rectifying column carries out heat exchange, and the energy in the device reasonably has been coupled.
The gaseous bromine methane that goes out cat head after rectifying is condensed into liquid state through condenser 14 and enters return tank 15, send through reflux pump 16 again, distribute backflow and extraction ratio by the flowmeter on the pipeline, make the distillation operation reflux ratio in the rectifying column be controlled at 2, it is standby that extraction partly enters the fumigant storage tank, sends into canned district to a certain amount of back by the Celfume delivery pump and carry out canned.
The fixed gas that goes out condenser 14 enters absorbent charcoal adsorption tank, absorbs wherein uncooled methyl bromide gas, guarantees qualified discharge.
Go out ethylene glycol at the bottom of the rectifying Tata through 10 coolings of rectifying column coupling preheater, be cooled to normal temperature through absorbent forecooler 6 again and enter absorbent storage tank 4 in order to recycling.
Above-mentioned absorption tower is used for absorbing the Celfume of mixed gas, and rectifying column is used for reclaiming the Celfume of absorbent.
What need explanation a bit is: in order to guarantee can to carry out processed to ethylene glycol carrying out not having moisture when Celfume absorbs with rectifying column before operating.
In the present embodiment, the unstrpped gas that contains Celfume is formed: Celfume content is 0.6%, and the content of air is 99.4%, and tolerance is 25000m
3/ hr, continued operation can be finished 5000m in two hours
3The absorption of the Celfume in stifling workshop need absorb with the ethylene glycol of 189t/hr, and the rate of recovery that enters the Celfume in the retracting device is more than 98%.
The reaction principle of present embodiment:
Celfume dissolves each other in ethylene glycol substantially, so select for use ethylene glycol as absorbent the Celfume in the tail gas to be absorbed, the gas up to standard that will reach discharge standard is discharged.Different according to the boiling point of ethylene glycol and Celfume then, the method that adopts pressurization to separate reclaims the Celfume in the absorption liquid.Thereby obtain highly purified Celfume and highly purified ethylene glycol, ethylene glycol can be got back to absorption portion and carry out recycling.
Above-mentioned absorption tower and rectifying column are packed tower.
Embodiment 2:
Be with the difference of embodiment 1: 1) operating temperature on absorption tower is 5 ℃; 2) absorption liquid enter rectifying column the time temperature be 205; 3) absolute pressure in the rectifying column is 3atm; 4) reflux ratio in the rectifying column is 5; 5) unstrpped gas that contains Celfume is formed: Celfume content is 20%, and the content of air is 80%, and tolerance is 25000m
3/ hr, continued operation can be finished 5000m in two hours
3The absorption of Celfume in stifling workshop, need absorb with the ethylene glycol of 203t/hr, the rate of recovery that enters the Celfume in the retracting device is 98%.All the other process routes are all identical with embodiment 1.
Embodiment 3:
Be with the difference of embodiment 1: 1) operating temperature on absorption tower is 10 ℃; 2) absorption liquid enter rectifying column the time temperature be 210; 3) absolute pressure in the rectifying column is 2atm; 4) reflux ratio in the rectifying column is 4; 5) unstrpped gas that contains Celfume is formed: Celfume content is 10%, and the content of air is 90%, and tolerance is 25000m
3/ hr, continued operation can be finished 5000m in two hours
3The absorption of Celfume in stifling workshop, need absorb with the ethylene glycol of 195t/hr, the rate of recovery that enters the Celfume in the retracting device is 98%.All the other process routes are all identical with embodiment 1.
Above-mentioned three embodiment show: the content that contains Celfume in the gas of Celfume can be 0.6～20%, that is to say that the present invention can be used for the recovery to the pettiness methyl bromide gas.
Although in conjunction with the accompanying drawings the preferred embodiments of the present invention are described above; but the present invention is not limited to the above-mentioned specific embodiment; the above-mentioned specific embodiment only is schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not breaking away under the scope situation that aim of the present invention and claim protect, can also make a lot of forms, these all belong within protection scope of the present invention.
Claims (5)
1. the recovery method of a methyl bromide gas is characterized in that, may further comprise the steps:
1) gas that contains Celfume is fully contacted with 2～10 ℃ absorbent ethylene glycol in the absorption tower, Celfume is dissolved in the absorbent ethylene glycol, obtain out the absorption liquid at the bottom of the absorption Tata;
2) absorption liquid enters the rectifying column separation of pressurizeing, and the gaseous bromine methane after the rectifying is obtained by the extraction of rectifying column cat head.
2. the recovery method of methyl bromide gas according to claim 1 is characterized in that, described step 2) in, the inlet temperature of stabilizer of absorption liquid is 200～210 ℃, the part temperature rise of absorption liquid is passed through the coupling preheater and is obtained from the ethylene glycol heat exchange at the bottom of the rectifying Tata.
3. the recovery method of methyl bromide gas according to claim 1 is characterized in that, the absolute pressure in the described rectifying column is 2～4atm.
4. the recovery method of methyl bromide gas according to claim 1 is characterized in that, the distillation operation reflux ratio in the described rectifying column is controlled at 2～5.
5. the recovery method of methyl bromide gas according to claim 1 is characterized in that, described absorption tower and described rectifying column are packed tower.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101073576A CN102179136A (en) | 2011-04-27 | 2011-04-27 | Recovery method of methyl bromide gas |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011101073576A CN102179136A (en) | 2011-04-27 | 2011-04-27 | Recovery method of methyl bromide gas |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103638799A (en) * | 2013-12-07 | 2014-03-19 | 中华人民共和国德州出入境检验检疫局 | Recycling method and recycling device of fumigation agent methyl bromide |
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| CN1446782A (en) * | 2002-07-23 | 2003-10-08 | 浙江新安化工集团股份有限公司 | Clean Recovery Process of Glyphosate Acid by-product Methyl Chloride |
| US20100172807A1 (en) * | 2004-10-25 | 2010-07-08 | Value Recovery, Inc. | System for scrubbing alkyl halides from gases |
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- 2011-04-27 CN CN2011101073576A patent/CN102179136A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1446782A (en) * | 2002-07-23 | 2003-10-08 | 浙江新安化工集团股份有限公司 | Clean Recovery Process of Glyphosate Acid by-product Methyl Chloride |
| US20100172807A1 (en) * | 2004-10-25 | 2010-07-08 | Value Recovery, Inc. | System for scrubbing alkyl halides from gases |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103638799A (en) * | 2013-12-07 | 2014-03-19 | 中华人民共和国德州出入境检验检疫局 | Recycling method and recycling device of fumigation agent methyl bromide |
| CN103638799B (en) * | 2013-12-07 | 2016-04-06 | 中华人民共和国德州出入境检验检疫局 | A kind of recovery method of fumigant methyl bromide and retracting device |
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Application publication date: 20110914 |