阅读说明：本技术 用于卤代烷熏蒸剂回收和转化的方法和设备 (Method and apparatus for haloalkane fumigant recovery and conversion ) 是由 A·拉瓦尔 L·周 于 2018-09-27 设计创作，主要内容包括：公开了用于通过在吸收器/洗涤器(12)中将臭氧消耗卤代烷熏蒸剂吸收入金属氢氧化物-醇缓冲溶液(26)来从熏蒸剂/空气混合流(14)捕集和转化臭氧消耗卤代烷熏蒸剂以产生无熏蒸剂的空气流(28)的方法和设备(10)。在含水醇溶液中捕集的卤代烷可以与醇溶液中的金属氢氧化物有活性地反应以产生附加值产物(比如沉淀金属卤化物)和进一步增强吸收的另一种醇。将吸收溶液与补充醇和碱流充分混合以将金属氢氧化物的浓度维持在所需的缓冲溶液范围内。将固体沉淀金属卤化物(52)与液体流分离,并且将含金属氢氧化物的混合醇流(26)再循环至吸收器/洗涤器(12)。(A method and apparatus (10) for capturing and converting an ozone-depleting alkyl halide fumigant from a fumigant/air mixed stream (14) by absorbing the ozone-depleting alkyl halide fumigant into a metal hydroxide-alcohol buffer solution (26) in an absorber/scrubber (12) to produce a fumigant-free air stream (28) is disclosed. The alkyl halide trapped in the aqueous alcohol solution can actively react with the metal hydroxide in the alcohol solution to produce a value added product (such as a precipitated metal halide) and another alcohol that further enhances absorption. The absorption solution is thoroughly mixed with make-up alcohol and base stream to maintain the concentration of metal hydroxide within the desired buffer solution range. The solid precipitated metal halide (52) is separated from the liquid stream and the mixed alcohol stream containing metal hydroxide (26) is recycled to the absorber/scrubber (12).)

1. A method of capturing and converting fumigant using an absorber/scrubber apparatus, the method comprising the steps of:

a) feeding an aqueous alcohol and a metal hydroxide buffer solution into said absorber/scrubber unit;

b) feeding a haloalkane fumigant/air mixture into the absorber/scrubber apparatus such that the fumigant/air mixture contacts the buffer solution, wherein a fumigant component of the fumigant/air mixture is transferred from the fumigant/air mixture to the buffer solution, the fumigant component reacting with a metal hydroxide component of the buffer solution to produce a second mixture comprising at least one alcohol, unreacted metal hydroxide and metal halide;

c) discharging the second mixture from the absorber/scrubber apparatus; and

d) separating the metal halide from the second mixture to produce a solid metal halide and a third mixture comprising an aqueous alcohol and a metal hydroxide solution.

2. The method of claim 1, further comprising the step of discharging the treated lean air stream to a process after-treatment device and a measurement instrument for discharge to the atmosphere.

3. The method of claim 1, wherein the at least one alcohol comprises two alcohols.

4. The method of claim 1, wherein the alkyl halide is methyl bromide.

5. The method of claim 1 wherein the fumigant/air mixture is fed into the absorber/scrubber apparatus in a first direction and the buffer solution is fed into the absorber/scrubber apparatus in a second direction opposite the first direction.

6. The method of claim 1 wherein the fumigant/air mixture is fed into the absorber/scrubber apparatus in a first direction and the buffer solution is fed into the absorber/scrubber apparatus in a second direction that is the same as the first direction.

7. The method of claim 1, wherein the metal hydroxide composition comprises sodium hydroxide.

8. The method of claim 1, wherein the metal hydroxide composition comprises potassium hydroxide.

9. The method of claim 1, wherein the buffer solution comprises an alcohol selected from the group consisting of: methanol, ethanol, butanol and isopropanol.

10. The method of claim 1, further comprising the step of feeding the second mixture through a reservoir containing an absorption solution.

11. The method of claim 10, wherein the absorption solution comprises an aqueous alcohol and a metal hydroxide that is the same as the metal hydroxide component of the buffer solution.

12. The method of claim 10, wherein the aqueous alcohol of the absorption solution is the same as the aqueous alcohol of the buffer solution.

13. The method of claim 1, further comprising the step of providing at least one supplemental stream to be mixed with the second mixture.

14. The method of claim 13, wherein the at least one make-up stream comprises an alcohol-absorbing stream.

15. The method of claim 14, wherein the at least one make-up stream comprises a stream of a solution comprising an alcohol and a metal hydroxide.

16. The method of claim 1 wherein the fumigant component of the fumigant/air mixture is derived from a process other than a fumigation process.

17. The method of claim 1, wherein steps a) -d) are repeated using the third mixture as the buffer solution.

18. The method of claim 1, wherein the buffer solution has a mass fraction of the alcoholic component of about 0 to about 1.

19. The method of claim 1, wherein the buffer solution has a mass fraction of aqueous components from about 0 to about 1.

20. The method of claim 1, wherein the concentration of the metal hydroxide component is in the range of about 0g/100ml of the buffer solution to about 50g/100ml of the buffer solution.

21. The method of claim 1 wherein the concentration of the fumigant component is in the range of about 0g fumigant/air mixture to about 0.25g fumigant/air mixture.

22. An apparatus for capturing and converting fumigant, comprising:

a first feeding means for feeding an aqueous alcohol and a metal hydroxide buffer solution into the absorber/scrubber;

a second feed means for feeding a haloalkane fumigant/air mixture into the absorber/scrubber such that the fumigant/air mixture contacts the buffer solution, wherein a fumigant component of the fumigant/air mixture is transferred from the fumigant/air mixture to the buffer solution, the fumigant component reacting with a metal hydroxide component of the buffer solution to produce a second mixture comprising an alcohol and a metal halide;

a discharge means for discharging the second mixture from the absorber/scrubber; and

a separation device for separating the metal halide from the second mixture to produce a solid metal halide and a third mixture comprising an aqueous alcohol and a metal hydroxide solution.

23. The apparatus of claim 22, further comprising: a process aftertreatment device for treating a lean air stream discharged from the absorber/scrubber prior to discharge of the lean air stream to atmosphere, the process aftertreatment device comprising instrumentation adapted to measure a fumigant component of the lean air stream.

24. The apparatus of claim 22, wherein the absorber/scrubber comprises a metal cylindrical column.

25. The apparatus of claim 22, wherein the absorber/scrubber comprises a tray column.

26. The apparatus of claim 22, wherein the absorber/scrubber comprises a packed column.

27. The apparatus of claim 22, wherein the absorber/scrubber is maintained at a temperature of about 20 ℃ to about 50 ℃.

28. The apparatus of claim 22, wherein the absorber/scrubber is maintained at an operating pressure of at least about one atmosphere.

29. The apparatus of claim 22 wherein the fumigant/air mixture is treated in a continuous mode and the buffer solution is treated in a continuous but recirculating mode.

30. The apparatus of claim 22 wherein the fumigant/air mixture is treated in a continuous mode and the buffer solution is treated in a batch mode.

Technical Field

The present invention relates to cost-effective (cost-effective) methods and apparatus for treating fumigated waste/off-gases, and more particularly to the recovery of alkyl halides from an air stream containing them with concomitant conversion of the recovered alkyl halides into useful compounds.

Background

Fumigants (fumigants) are used to treat agricultural products such as fruits, grains or logs (logs) in an enclosure (enclosure) before allowing such products to be exported overseas, imported to local or sold locally. After fumigation, sufficient time has passed for the fumigant to be absorbed by the product. Subsequently, the enclosure is aerated (aerate) so that residual fumigant is released into the atmosphere, which may be up to 50% of the initial amount applied. Alkyl halides, especially methyl bromide (MeBr), are common fumigants.

Because of its toxicity, methyl bromide is considered an effective quarantine/plant hygiene (phyto-sanitary) fumigant for the control of insects and other pests. However, studies in humans have demonstrated acute and chronic health effects associated with methyl bromide, and EPA has classified methyl bromide as a group D compound. In addition to its toxicity, another serious problem with the use of methyl bromide is the damage it causes to the stratospheric ozone layer. In fact, methyl bromide is considered an ozone depleting chemical and has thus been classified as a class I ozone depleting substance by the montreal protocol, while also being regulated by the clean air act due to the ozone depletion potential value (ozone depletion potential) of 0.2%. Thus, international, federal and state regulations require strict control of methyl bromide emissions due to the harmful effects of methyl bromide on the environment.

The use of methyl bromide as a fumigant has not been completely stopped due to the lack of an effective alternative, but such use is only permitted if its emissions can be sufficiently reduced. This has a detrimental economic impact on, for example, lumbering companies, which are limited by federal and state regulations regarding the amount of fumigant they can release into the atmosphere, thereby limiting their operation.

Currently, there are methods for capturing fumigants that are implemented on a large scale; however, they often destroy the fumigant, producing byproducts and concomitant disposal (disposal) problems. In addition, they are also expensive. Most existing methods rely on the use of activated carbon beds and the absorption solution is not recyclable. Other disadvantages associated with these prior art techniques include, for example, the following. They involve complex systems comprising multiple stages and therefore require high capital investment and operating expenses. These techniques often require changes to existing fumigation methods, which can affect the effectiveness and reliability of those methods, e.g., requiring longer treatment times per vessel. Existing emission control methods/processes focus primarily on capturing halogenated fumigants using different sorbents/absorbents, thus typically requiring further treatment methods to safely dispose of the halogen-containing agent/absorbent, which adds additional cost to the process and makes it economically less advantageous. Current processing systems are typically large, which makes their transportation for on-site gas processing difficult. Existing processes also typically involve extreme processing conditions of high temperature or energy input.

Disclosure of Invention

The present invention relates to a method and apparatus for capturing and converting fumigants using a reactive absorber/scrubber equipped to recycle an aqueous buffer solution of an alcohol and a metal hydroxide. The air containing the alkyl halide fumigant (i.e. the fumigant/air mixture) is then passed through an absorber/scrubber apparatus, the fumigant/air mixture is contacted with a buffer solution, causing the fumigant to be absorbed by the alcohol, and thereby cleaning the fumigant's air. The captured alkyl halide is then reacted with a metal hydroxide to produce a metal halide. A purge stream containing a concentrated metal halide solution or metal halide slurry (slurry) is continuously withdrawn to avoid the build up of solids and contaminants in the system. Upon discharge from the absorber/scrubber unit, solid metal halides will precipitate and separate from the residual aqueous alcohol and metal hydroxide solution. After the salt (e.g., metal halide) recovery process, the solution is fed back to the absorber as an absorption solution feed. In embodiments, the fumigant/air mixture is treated in a continuous mode, and the buffer solution is treated in a continuous mode while in a recirculation mode. In embodiments, the fumigant/air mixture is treated in a continuous mode and the buffer solution is treated in a batch mode.

Drawings

For a more complete understanding of the present invention, reference is made to the following detailed description of exemplary embodiments, which is to be considered in connection with the accompanying drawings, wherein:

FIG. 1 is a schematic diagram of a process/apparatus for recovering and converting an alkyl halide according to the present invention, which may be operated in a batch or recycle mode;

FIG. 2 is a schematic diagram of a batch process/apparatus for recovering and converting an alkyl halide according to the present invention;

FIG. 3 is a schematic diagram of a recycle process/apparatus for recovering and converting an alkyl halide according to the present invention;

fig. 4 is a graph showing the results of the following study: for the scenarios with (packing) and without packing, the effect of packing on halide absorption in batch mode is depicted in fig. 2, where the x-axis corresponds to the run time (time-on-stream) and the y-axis represents the MeBr concentration in the liquid product;

FIG. 5 is a graph depicting the results of a study of the absorption capacity of various solvents, plotting MeBr concentration (see y-axis) of the liquid product of various alcohol solvents as a function of time (see x-axis);

FIG. 6 is a graph illustrating the effect of the concentration of two commonly used metal hydroxides on the absorption capacity of various solvents, plotting the resultant MeBr concentration in the gaseous product (see y-axis) as a function of time (see x-axis) for various hydroxides and concentrations;

figure 7 is a graph depicting the steady-state values (in percent) of the removal of MeBr from the gas phase (see left y-axis) and the MeBr concentration in the MeBr-depleted gas (MeBr-depleted gas) (see right y-axis) for the numbers associated with the solutions specified in table 2 below (see x-axis);

FIG. 8 is a graph showing the results of a study of the effect of gas-liquid (G-L) contact time on MeBr absorption in the recirculation mode depicted in FIG. 3, plotting the MeBr concentration in the gas product (see y-axis) as a function of time (see x-axis) for different gas-liquid contact times;

FIG. 9 is a graph illustrating the effect of surface (super) gas velocity (or residence time) on absorption in the recirculation mode depicted in FIG. 3, plotting MeBr concentration in the gas product (see y-axis) as a function of time (see x-axis) for a plurality of flow rates;

FIG. 10 is a graph showing the effect of different gas/liquid ratios and flow rates on absorption for 10g NaOH/100ml ethanol solution, which plots MeBr concentration of the gas product (see y-axis) against time (see x-axis) for different gas/liquid ratios and flow rates; and

FIG. 11 is a graph depicting the effect of different gas/liquid ratios and flow rates on absorption for a 10g KOH/100ml ethanol solution, and the MeBr concentration of the gas product (see y-axis) is plotted against time (see x-axis) for different gas/liquid ratios and flow rates.

Detailed Description

The exemplary embodiment disclosed below, which is but one of many exemplary embodiments of the present invention, was developed to recover significant amounts of methyl bromide (which is used as a fumigant gas to fumigate wood logs) which is then converted into value added products. The fumigated exhaust gas treated according to the present invention better complies with emission regulations. Although the methods and apparatus described below relate to the recovery and conversion of methyl bromide, it will be understood by those of ordinary skill in the art that they are also effective for the recovery and conversion of other alkyl halide fumigants.

In the process of the present invention, the scrubbing solution is an alcohol-based buffer solution that is not discarded, but separated from the suspended solids (i.e., metal halides) produced and recycled, thereby further improving the economics and feasibility of the process. All reactants for the proposed process are inexpensive compared to existing processes, and metal halides (such as sodium bromide) can be high value commodities. Another byproduct of the methods disclosed herein is methanol, a solvent that is also recycled in the absorption solution to aid in further absorption of the fumigant.

The one-step (one-step) highly integrated wet reactive absorption process as developed herein requires reduced capital and operating costs and mild process conditions compared to currently available processes. By means of the enhanced mass transfer properties, an efficient exhaust gas treatment can be achieved with a reduced size of the plant, which makes it feasible for on-site treatment. In addition, the added value by-products from the process increase its cost effectiveness and make fumigant treatment economically near self-sustaining (self-sustaining).

With the foregoing introductory comments in mind, reference is made to FIG. 1 wherein apparatus 10 comprises an absorber/scrubber 12, such as a model PPS-24 steam scrubber from Vapor Tech, equipped to contact and thereby react fumigant gas and dissolved metal hydroxide. It should be understood that any absorber or scrubber apparatus known to those of ordinary skill in the art is suitable for use as the absorber/scrubber 12 of the apparatus 10. For example, in embodiments, the absorber may be a metal cylindrical column or tower. In some embodiments, the column may be a packed column, while in other embodiments, it may be a tray column (traytower). Various fillings and discs are available and known and their selection is well within the knowledge of a person skilled in the art.

With continued reference to fig. 1, a mixed air stream 14 comprising air and an alkyl halide, such as methyl bromide, originates from a fumigation process 16 in which an alkyl halide stream 18 has been used to fumigate produce, such as logs 20 or fruit or grain (not shown), that has been stored in a fumigation container 22. Air 24 is continuously pumped through the fumigation container 22 to aerate the fumigated produce (i.e., the logs 20) as well as the container 22 itself. In other embodiments, mixed air stream 14 may originate from sources and processes other than a fumigation process. The mixed air stream 14 leaving the vessel 22 carries with it the removed alkyl halide fumigant (e.g., methyl bromide) as it enters the absorber/scrubber 12 from the bottom. During its upward travel, mixed air stream 14 contacts a counter-current flow stream of absorption solution 26 fed from the top of absorber/scrubber 12 and traveling downward through absorber/scrubber 12. In another embodiment, the combined air stream 14 and the stream of absorption solution 26 may flow through the absorber/scrubber in the same direction.

The flow of absorption solution 26 is a metal hydroxide-alcohol buffer solution that serves to enhance external mass transfer of the alkyl halide from mixed air stream 14 to the absorption solution, as well as to provide a stable alkyl halide conversion medium. The alkyl halide (e.g., methyl bromide) is highly soluble in the absorbing alcohol, thereby facilitating its transfer from the mixed air stream 14 to the absorbing solution. A lean air stream 28 comprising air and a reduced amount of alkyl halide is withdrawn from the top of the absorber/scrubber 12 and passed through an optional de-entrainment/demisting device 30 and an on-line alkyl halide detection/quantification (i.e., measurement) instrument 32 before being discharged to atmosphere a.

Since the alkyl halide is super-active for reaction with the metal hydroxide in the absorbing solution, the bimolecular nucleophilic substitution reaction (SN2) produces two reaction products, where the metal is an alkali metal (i.e., sodium, potassium, or any of the elements of group 1A (1) of the periodic table). One reaction product is the product alcohol, which corresponds to the alkyl group of the alkyl halide and is a liquid that is miscible with the absorbing alcohol. Another reaction product is a metal halide, which corresponds to the halide of the metal hydroxide and the alkyl halide, and which subsequently precipitates as a solid. The following reaction is a general reaction that occurs:

more specifically, for example, when the alkyl halide is methyl bromide and the metal hydroxide is sodium hydroxide, the reaction will proceed as follows to produce methanol as the product alcohol and sodium bromide as the metal halide:

still referring to fig. 1, a stream 34 containing metal halide and alcohol is supplied from the absorber/scrubber 12 to an absorption solution tank (drum) 36. A small make-up (make-up) stream 38 containing the absorption alcohol is also supplied to the absorption solution tank 36 to compensate for any absorption alcohol that may be lost due to reaction with the product alcohol or evaporation into the air stream or other losses. Similarly, a make-up caustic stream 40 containing a concentration of metal hydroxide and alcohol is supplied to the absorption solution tank 36. The discharge stream 42 exits the absorption solution tank 36 via a pump 44. After leaving pump 44, stream 42 is divided into an absorbing solution stream 26 and a purge stream 46. The purge stream 46 passes through a solid-liquid separation device 48, such as a Russell Eco separator, which produces (i) a stream 50 containing negligible amounts of dissolved salts (e.g., metal halides), which stream 50 is returned to the absorption solution tank 36, and (ii) a collected solid 52, i.e., metal halides, which may be packaged for sale.

The transfer of the alkyl halide fumigant from the mixed air stream 14 to the liquid absorption solution in the absorber/scrubber 12 occurs primarily on the column packing or trays (not shown) of the absorber/scrubber 12. The absorption solution typically comprises an alkali-alcohol solution and may be, for example, methanol, ethanol, butanol, isopropanol, or a combination thereof. Generally, the mass fraction of alcohol in the absorption solvent will vary, but in some embodiments, the mass fraction will be from about 0 to about 1. Thus, the water content (i.e., the aqueous component) of the absorption solvent ranges from about 0 to about 1. Typically, the concentration of metal hydroxide in the absorbing solution will vary, but in some embodiments, the concentration will be from about 0g/100ml of solvent to about 50g/100ml of solvent. The flow rate of the absorption solution stream 26 into the absorber/scrubber 12 will vary depending on: (i) concentration of fumigant in the gas stream, (ii) gas stream flow rate, (iii) desired fumigant concentration in the outlet gas stream, and (iv) solubility of fumigant in the absorption solution, among others.

The flow rate can be determined by one of ordinary skill in the art and is typically determined as part of the process design. It is expected that the concentration of fumigant in the lean air stream 28 will range from trace amounts (i.e., in the parts per billion range) to undetectable amounts. The temperature of the absorber column within the absorber/scrubber 12 will be maintained at a selected value to increase the solubility of the fumigant in the alcohol and also to inhibit evaporation of the solvent into the gas stream. In some embodiments, the temperature will be maintained at a value of about room temperature (e.g., about 20 ℃ to about 26 ℃) to about 50 ℃. The operating pressure in the absorber column will depend on the pressure of the mixed air stream 14 and may be above atmospheric pressure. In some embodiments, the operating pressure may be at least about atmospheric pressure (e.g., 1 atmosphere, or 14.7 psig).

The product alcohol formed will generally be miscible with the absorbing solution and the metal halide will precipitate, thereby facilitating its separation from the product stream of the reactor. For any absorbing solution stream, the concentration of metal hydroxide should be controlled to meet any TSS and TDS and any associated tubing design specifications specified by the manufacturer of the pump 44.

As noted above, the method of the present invention may be practiced in conjunction with the fumigation of produce in a variety of containers or envelopes. In some embodiments, the container may be a sealed container (shipping container), trailer, rail vehicle, mill, and warehouse. The fumigated product may be agricultural products, including wood products such as logs and fruits or grains. The concentration of fumigant in the mixed air stream 14 exiting the container 22 during aeration will vary over time. In certain embodiments, the concentration will vary from about 0.25g fumigant/g mixture to about 0.0g fumigant/g mixture. The flow rate of the air stream 24 will vary depending on the size of the alkyl halide fumigant and the container 22. In fumigation of wood products in containers, the air flow 24 may have an air flow rate of up to 1200ft at room temperature³/min。

After the liquid level in the absorber/scrubber 12 has remained constant for a period of time, the gas flow is turned on and the run time is started to be measured. The counter-current flow of absorption solution 26 and the gas stream to be cleaned provides a large contact area and produces a relatively high concentration difference between the two phases, which is the driving force for mass transfer.

FIG. 2 depicts a batch process and apparatus 110 for recovering and converting alkyl halides according to the present invention, hereinafter this apparatus (setup) will be referred to as a batch mode apparatus Raschig rings (Raschig rings) (PTFE, 3mm × 3mm × 1mm L× O.D. × thickness) are filled into the height of the absorber 112 to 6'. after such filling, 50ml of absorption/reaction solution is first transferred into the reservoir of the batch mode apparatus and the run time is measured from the time the gas flow is turned on, MeBr-rich gas stream 114 flowing from gas source 116 is regulated by mass flow controller 118(MFC) and passes through check valve 120 and control valve 122 en route to the inlet 124 of the absorber 112. MeBr-rich gas stream 114 is supplied to the bottom 126 of the packed bed and generates gas bubbles through the overflow (flooded) packed bed before exiting through outlet 128 and then through gas chromatography apparatus 130 or vent 132 via valve 134.

FIG. 3 depicts a schematic diagram of an apparatus 210 for recovery and conversion of alkyl halides in accordance with the present invention, which apparatus 210 may be operated as a batch or recycle process, hereinafter, the device will be referred to as a recycle mode device, as shown in FIG. 3, the effective flow path of the absorber/reactor section 212 of the recycle mode device has an ID of 1/4 ", a height of 21.26" (54cm), and is filled with 3mm Raschig rings (PTFE, 3mm × 3mm × 1mm L× O.D. × thickness). after such filling, first 20ml of solution is transferred into the recycle mode device and then circulated at a selected flow rate for the absorption process. after the flow of MeBr-rich gas 214 out of the gas source 216 is regulated by Mass Flow Controller (MFC)218 and through check valve 220 and control valve 222 to the inlet 224 of the absorber 212. high pressure liquid chromatography pump 226 drives the fluid flow. after the liquid level at the bottom of the absorber 212 is held constant for 10min, the gas flow is opened and the run time is measured 228 and the gas flow is passed through a check valve 222 to the inlet 224 of the absorber 212. this provides a relatively high gas flow difference between the gas flow to be produced by the gas outlet port 230 and the gas flow outlet 234, which is a relatively high gas flow of the gas flow produced by the gas outlet port 230.

To describe the invention in more detail, the following examples are given: