CN1191770A

CN1191770A - Shear mixing apparatus and use thereof

Info

Publication number: CN1191770A
Application number: CN97109965A
Authority: CN
Inventors: 罗伯特·佩奇·希尔图姆; 戴维·L·特伦特; 谢里尔·A·蒂托维佐约; 保罗·A·吉利斯
Original assignee: Dow Chemical Co
Current assignee: Dow Global Technologies LLC
Priority date: 1997-02-28
Filing date: 1997-02-28
Publication date: 1998-09-02

Abstract

Shear mixing apparatuses and associated methods are disclosed for controllably and economically producing small gas bubbles, for examble, of an average diameter of less than about 0.5 millimeters in a liquid, whereby mass transfer of the gas into the liquid is improved (as compared to the mass transfer achieved by conventional large bubble generators under the same circumstances) in applications benefiting by such improved mass transfer, involving injecting a gas under pressure via one or more orifices into a liquid that is flowing at a velocity sufficient to cause bubbles formed at the orifice(s) to subdivide to the desired small bubble size.

Description

Shear mixing apparatus and application thereof

The present invention relates generally to a kind of shear mixing apparatus that is used for various operations.The present invention be more particularly directed to a kind of shear mixing apparatus, this device produces very little bubble, and this device provides gas to liquid medium.The present invention also is particularly related to a kind of like this device and uses, and this device is used in the mass transfer as chemistry or biological respinse intensified response gas.Oxygen i.e. a kind of in the reacting gas for this reason.

" very little bubble carries out the optimized bubble size of mass transfer-ventilation ", chemical engineering science, the 33rd volume, M.Motarjemi and G.J.Jameson lecture in the 1415-1423 page or leaf (1978), bubble is used for the purpose of mass transfer continually, particularly in the water-soluble system of oxygen.They are 1422 pages of suggestions, need work out a kind of practical new and make " a large amount of, very little, diameter is less than the bubble of 1mm " G.J.Jameson at " bubble motion ", TransIChemE, Vol.71, among the Part A 587-594 (in January, 1993), looked back John Davidson the research bubble gentle-contribution in the gas-liquid two-phase liquid.In the 592nd page, he has discussed by reducing the sprayer average pore size and has produced the existing problem of minute bubbles.Remarkable increase that descends comprising pressure behind sprayer and the problem that may stop up spray orifice as solid matter in the sewage of pond.At the 593rd page, he has discussed the merging of bubble, and mentions: bubble is applied a power, it is removed from nozzle fast, to prevent merging.The method that can apply this power is included in cross-current on the nozzle and crosses a kind of liquid and maybe vibration is applied on the gas on the nozzle or in the nozzle.

First scheme of the present invention has provided a kind of shear mixing apparatus, this device can produce diameter less than 1 millimeter bubble, simultaneously, reduce on traditional bubble generator the sprayer average pore size aspect, those problems that Jameson mentions can not take place, and the inventive system comprises:

At least one pipeline of carrying first fluid to be mixed, first end of this pipeline is opened, and accepts first fluid to be mixed, second end is closed, near its second end place that closes one or more apertures being arranged, by this aperture, the fluid of being received by first termination of opening is discharged from pipeline;

A blender, it is generally round one or more this pipelines, and first end of a sealing is arranged, and this first end defines corresponding one or more aperture, wherein by corresponding one or more pipelines; This blender also has one second end, this second end and each pipeline define a resistance nozzle, a relative space, this space is by the blender sealing and be limited between first end and second end of blender sealing the resistance nozzle place that the aperture on each pipeline is placed in basically and this given pipeline interrelates;

The pipeline that second fluid is provided, this pipeline leads to the space of being sealed by blender, so that provide second fluid to it, this second fluid is by one or more resistance nozzles at blender second end, and with a kind of mode of shearing with mix by the first fluid that aperture was provided that is positioned at each resistance nozzle place.

Alternative plan of the present invention relates to a kind of shear mixing apparatus, and it comprises:

One or more pipelines of first fluid to be mixed are provided, on a segment length of each pipeline, limit one or more apertures;

A blender, it has one first end and one second end, and between its first end and second end, define a space that is generally sealing, lead in fluid supply tube road and this space, each defines a corresponding opening therein first end of blender and second end, so that pipeline with holes is passed therethrough, like this, provide hole and space on the pipeline of first kind of fluid to be mixed to lead to.

Third party's case of the present invention relates to the 3rd, the embodiment relevant with shear mixing apparatus, it comprises hollow gas and liquid receiving-member, a bubble generation part and an optional handle, gas is connected and leads to the bubble generation part with the liquid receiving-member.

The gas of the 3rd embodiment and liquid receiving-member preferably include:

A center tube, it has the arrival end of opening, is used for receiving the liquid that enters wherein, also has a port of export and bubble generation part to lead to;

A gas receiving chamber, it generally separates round center tube and with center tube, thereby define a passage, gas is flow through arrive the bubble generation part, which comprises at least the passage of a receiver gases, so that receive the gas flow through and through passage passage and bubble generation part are led to, an end of gas receiving chamber is connected on the center tube airtightly, its tie point is nearer from the input of center tube, and is far away from output.

Bubble generation part in the 3rd shearing-mixing arrangement preferably includes a substrate, and this substrate is being connected with center tube airtightly near the center tube output; Gas and liquid distributor chamber are used for holding and distributing respectively from the gas and the liquid of gas receiving chamber and center tube, and this distributor chamber is connected on the substrate airtightly; A cover plate, it is connected with the liquid distributor chamber airtightly with gas, and gas and liquid distributor chamber have funnelform fluid pressure chamber, a center, and it and substrate, cover plate are divided into the liquid relief chamber on top and the gas relief chamber of bottom with the bubble generation part; Funnelform fluid pressure chamber has a hollow stem, this hollow stem is fixed on close port of export place and circular extension of stretching out from said hollow stem of center tube usually airtightly outwardly, define one group of aperture and one group of fluid passage of leading to of leading in this hollow stem with the gas relief chamber with the liquid relief chamber, lead to these apertures and fluid passage, so that mix gas and the liquid that passes through.The fluid passage preferably is separated from each other by the fluid parallel regulator, and this fluid parallel regulator is set in the circular extension that hollow stem stretches out outwardly.

Cubic case of the present invention relates to a kind of method that produces bubble in liquid, and the average diameter of bubble is less than 0.5 millimeter, and especially less than 0.1 millimeter, this method comprises:

A. gas is placed under the pressure, when gas part or at least one hole on the element when being imported in the liquid by separating gas and liquid, this pressure is enough to form bubble;

B. make liquid flow through aperture, the Weber number that selected flow velocity produces surpasses the critical Weber number of this gas and liquid, to reach desirable bubble diameter.

Fig. 1 is an axial schematic sectional view of shear mixing apparatus according to the first embodiment of the invention and above-mentioned first scheme.

Fig. 2 is an axial schematic sectional view according to another shear mixing apparatus of the present invention, and it is a feature with above-mentioned alternative plan.

Fig. 3 is the axial schematic sectional view of shear mixing apparatus the 3rd embodiment of the present invention.

Fig. 4 is the top view of device shown in Figure 3.

Fig. 5 is the curve map of the data in the Table I.Table I is the compilation of oxygen transfer result of the test in the example 2.Vertical axis is represented KLa20, and trunnion axis is represented the gas flow of per minute in standard liter (SLM).

Fig. 6 is a curve synoptic diagram, and diagram is used traditional State Shear Compounding, for reaching that pressure that given bubble diameter produces descends or energy consumption (in kPa).

With reference to the accompanying drawings, Fig. 1,2 and 3 provides the schematic diagram that represents three relevant apparatus of the present invention. Fig. 4 is another view of device shown in Figure 3. Each device does not all has in proportion picture, and its feature as Size, position and the quantity of device only for signal, is not limited to as shown in the figure.

Fig. 1 shear mixing apparatus with reference number 10 expressions that drawn. Device 10 comprises a sky 15, one in the pipeline of 11, one conveyings of heart blender, first fluid to be mixed provides second fluid Pipeline 20, this pipeline 20 comprises passage 21 and stopple 25.

Blender 11 has first end 12 and away from second end 13 of this first end. Blender 11 has surrounded Space 30 between its first and

second end

12 and 13. An aperture 14 is arranged in second end 13. Blender 11 suitable shapes (in order to observe, ignoring second fluid service 20) are skies The positive cylinder of the heart, one end opening (second end 13) is with the opposed end (first end of openend 12) sealing keeps an aperture. When blender is such shape and when only pipeline 15 being arranged, little Hole 14 and pipeline 15 axis best and blender are coaxial. When having two pipelines 15 at least, aperture 14 quantity increases, and matches with the quantity of pipeline 15.

Stopple 25 is fixed in the blender 11, and near its second end 13. When stopple 25 by like this In the time of fixedly, it is desirable to define therein at least one aperture or nozzle 26. When only having a pipeline 15 o'clock, aperture 26 axis best and blender were coaxial. When having two pipelines 15 at least, each Aperture 26 is preferably coaxial with corresponding pipeline 15.

Pipeline 15 has first end 16 and away from second end 17 of first end 16. First end 16 openings also Preferably link to each other with the first moving fluid source (not showing). Second end 17 be sealing or by being covered with, To prevent that first moving fluid from flowing out through this end. Pipeline 15 passes and is fixed on first of blender 11 In the aperture 14 of end 12. Preferably with such method pipeline 15 is fixed in the aperture 14, namely exists Pipeline 15 is by the place of aperture 14, and abundant leakproof, preferably airtight sealing are provided. Pipeline 15 Also pass the aperture 26 of stopple 25. Like this, pipeline 15 and stopple 25 have formed jointly with respect to sky Between 30 resistance nozzle 27, it is shaped as near second end 17, limits along the length of pipeline 15 A thin narrow annular space also has one group of aperture 19 in the pipeline 15. Each aperture 19 and resistance spray Mouth 27 leads to. When operating by cubic case of the present invention, the quantity of aperture 19, size, Interval and position are enough to provide minute bubbles.

On the first end 12 and the intermediate point between second end 13 of blender 11, second fluid is supplied with Pipeline 20 is connected with blender 11 effectively. Like this, second pipe 20 effectively with blender 11 Connect. Like this, the passage 21 of second pipe 20 leads to space 30. It is desirable to same side Method allows one or more additional pipeline for fluids effectively be connected on the blender 11, so that with attached The fluid that adds (gas or liquid, preferably liquid) offers blender 11, make they with from one A kind of gas of individual pipeline 15 or a plurality of pipeline 15 (can be the gas of single kind or mixing of each gas Compound) or multiple gases mix.

Refer now to Fig. 2, wherein drawn the shear mixing apparatus according to alternative plan of the present invention, by ginseng Examine several 40 expressions. Device 40 comprises a hollow blender 41, pipeline 50 with holes and one The pipeline for fluids 60 that comprises passage 61.

Blender 41 has first end 42 and away from second end 43 of first end 42. Blender 41 surrounds Space between its first end and

second end

42 and 43. Aperture 44 is arranged in first end 42. Second In the end 43 aperture 45 is arranged. Each aperture 44 is preferably coaxial with opposed aperture 45. Blender 41 Suitable shape (for the purpose of observing, ignoring pipeline for fluids 60) is a hollow positive cylinder Body, its two ends all are closed, and only keep

aperture

44 and 45. When blender is such shape, Each pipeline 50 is preferably straight, and is coaxial with the opposed aperture of a pair of 44 and 45.

Pipeline 50 has first end 51 and away from second end 52 of first end 51. Pipeline 50 passes and is solid Fix in the

aperture

44 and 45 of blender 41. Preferably be fixed on pipeline 50 little by this way In the

hole

44 and 45, namely provide in the place that pipeline passes

aperture

44 and 45 leakproof, gas preferably Close sealing. Because first end 42 and second end 43 are mutually to separate, thereby blender 41 surrounds One segment length of pipeline 50. In the said length of this section, pipeline 50 has one group of aperture 54. Whenever Individual aperture 54 leads to space 55. When operating according to cubic case of the present invention, aperture 19 Quantity, size, interval and position be enough to provide minute bubbles.

On the first end 42 and the intermediate point between second end 43 of blender 11, pipeline for fluids 60 are connected with blender 41 effectively. The passage 61 of pipeline 60 leads to space 55 like this. Desirable Be to allow one or more additive fluid services effectively connect with blender 11 with same method Connect, in order to additive fluid is supplied with blender 11.

First end 16 through effectively connecting first pipeline 15, first moving fluid under pressure, Be gas well, such as air or oxygen, from the pipeline of a fluid source (not having to show) inflow device 10 In 15 (as shown in Figure 1). If need, this first moving fluid advances through the aperture 19 of pipeline 15 Enter in the resistance nozzle 27. Through effectively connecting pipeline for fluids 20, the second moving fluids, best Be liquid, such as water or salt solution, from a fluid source (not showing) flow channel 21. Second fortune Moving fluid is from passage 21 inflow spaces 30. When being full of second moving fluid in the space 30, should The fluid inflow is also passed through resistance nozzle 27. The cross-sectional area of resistance nozzle 27 is transversal less than space 30 Area is so second moving fluid passes through passage 21 and space 30 by the speed of nozzle 27 greater than it Speed. The pressure that flows through first moving fluid of aperture 19 be enough to prevent fully second moving fluid by Aperture 19 enters pipeline 15. When first fluid is gas, and second fluid is when being liquid, this pressure Be enough to equally produce bubble. Can believe by the flowing of second moving fluid of nozzle 27 and arrive by force foot Overcoming the interfacial tension between gas and the liquid, thereby force bubble to be broken into minute bubbles. If two Planting moving fluid all is gas or liquid, can be conducive to mix this moving fluid by phase T unit 10. As Fruit second moving fluid is liquid, and first moving fluid is the gas that dissolves in this liquid, can believe Device 10 has promoted the disperse of soluble gas in the liquid.

Device 40 shown in Figure 2 mixes first kind of moving fluid aptly with the second moving fluid, Wherein first kind of fluid is preferably liquid and flows through pipeline 50 with holes, and the second fluid is preferably gas Body, and flow through the passage 61 of pipeline for fluids 60. When relating to device 10 illustrated gas and Liquid equally also can be used for device 40. By the first passage 51 of connecting pipe 50 effectively, can Allow first moving fluid from fluid source (not showing) flow ipe 50. Because cross-sectional area does not change Become, when first moving fluid flow through pipeline 50, flow velocity is significant the variation not. By effective connection Pipeline for fluids 60 can allow second moving fluid from fluid source (not showing) flow channel 61. Second moving fluid is from passage 61 inflow spaces 55, and from then on 54 enters pipeline 50 through the hole. Second The pressure of moving fluid is enough to produce bubble and prevents that fully first moving fluid from entering space 55. The picture dress Put 10 like that, the flow velocity of liquid moving fluid is enough to preferably cause that bubble segments again, these bubbles be The moving fluid of gaseous state is by the generation when liquid moving fluid contacts of this when device. In addition, dress Putting 40 can be used for and device 10 identical purposes.

Fig. 3 illustrates the 3rd embodiment who relates to shear mixing apparatus of the present invention, by reference number 100 expressions. Device 100 comprises that a hollow gas and 110, one bubbles of liquid receiving-member send out Give birth to parts 140 and an optional handle 190. Handle 190 is conducive to device 100 is installed to appearance (do not show) these containers such as polymer reactor or bioreactor on the device.

Receiving-member 110 comprises a center tube 111 gentle body receiving chambers 120. Center tube 111 An openend 112 and a port of export 113 are arranged, and this port of export 113 is away from first end 112, and Lead to bubble generation part 140. Define an axle that is suitable for carrying liquid in the center tube 111 To passage 114. Gas receiving chamber 120 preferably is made of an independent structural member, or such as Fig. 3 institute Show that it comprises the gas receiving chamber 121 of an annular and the gas conveying chamber 123 of annular. Gas connects Receive in the chamber 121 and have a gas receive path 122 at least. Internal thread is preferably arranged in the passage 122, with Be beneficial to airtightly and be connected with source of the gas (not showing). Gas receiving chamber 121 surrounds cavity 124, should Cavity 124 leads to gas receive path 122. The gas conveying chamber 123 of annular has one at least directly Part and center tube 111 combinations, form long narrow annular space 126, so as with gas from gas Body receiving chamber 121 is delivered to bubble generation part 140. The first end 125 of chamber 123 inserts space 124 In, second end 127 is away from first end 125. Chamber 123 is preferably near second end, 127 places outer spiral shell Line. Annular space 126 is same to be led to space 124, first of admission passage 122 moves and flows like this Body (preferably gas) energy inflow space 124, and subsequently by annular space 126. Receiving-member 110 part is with suitable fixing means, as mutually effectively connecting with angle welding 115.

Bubble generation part 140 comprises substrate 141, gas and liquid distributor chamber 150 and cover plate 180. One group of aperture 142 is arranged in the substrate 141. Also have an annular sealed chamber 145 in the substrate 141, can hold Receive seal 146. Seal 146 can be an O shape circle, carries between substrate 141 and chamber 150 For airtight sealing. Preferably also have central authorities or axial aperture 149 in the substrate 141. Aperture 149 In internal thread is preferably arranged, fill as shown in Figure 3 when bubble generation part 140 and receiving-member like this Timing, the end 127 of chamber 123 can be screwed in the aperture 149.

Distributor chamber 150 comprises the outer wall 151 and the central fluid pressure-reducing chamber 160 of an effective combination.Chamber 160 is preferably infundibulate (generally including pipe or hollow stem that a hollow frustum of a cone element and extend from the small end of this element), and have hollow stem 170 and one from bar 170 towards cover plate 180 circular extension 161.Preferably 151 extensions from its effective junction towards outer wall of this circle extension 161, this effective connection is preferably continuous angle welding or other gratifying method of attachment.An interior annular space 171 is arranged in the hollow stem 170.This annular space 171 can hold a seal 172 that is generally O shape circle, when the straightway near its second end 113 that is fixed on center tube 111 slidably with convenient bar 170 is partly gone up, provides airtight and the close sealing of liquid.

Circle stretches out has one group of aperture 162 in the part 161.Also has one group of fluid passage 163 in the extension 161.Each fluid passage 163 is all separated by fluid parallel regulator 164 (as shown in Figure 4).Also has one group of aperture 165 in the extension 161.Aperture 165 is by fluid parallel regulator 164 (see figure 4)s and internal thread is preferably arranged.

It is a space 143 that effective combination in outer wall 151 and central fluid pressure-reducing chamber 160 is just surrounded.Lead to aperture 162 in space 143, and when device 100 assembles as shown in Figure 3, and it also leads to elongated annular space 126.

Outer wall 151 stops at flange 152 places.Flange 152 separates with outwardly directed circular extension 161.One group of aperture 154 is arranged in the flange 152.Aperture 154 preferably has corresponding aperture 142 on internal thread and the align substrates 141.Outer wall 151 is connected with substrate 141 effectively by suitable fixture such as cap screw 144.

One group of aperture 181 is arranged in the cover plate 180.Aperture 181 preferably axially aligns corresponding aperture 165 on the outer rim 161.By fixture 183 as by aperture 181 and 165 screws that effectively are connected, cover plate is fixed on the distributor chamber 150.A central axial flow of fluid parallel regulator 185 is preferably arranged in the cover plate 180.When device 100 when installing as shown in Figure 3, the shape of this parallel regulator 185 is preferably a circular cone, its summit towards and aim at the axis of center tube 111.

After the assembling, cover plate 180 and central fluid pressure-reducing chamber 160 define a hollow fluid allocation space 158.Cover plate 180 and pressure-reducing chamber 160 have also surrounded fluid passage 163.When device 100 was installed as shown in Figure 3, allocation space 158 was led to fluid passage 163 and center tube 111.

When adopting handle 190, cover plate 180 also has a centre bore 188.There is internal thread in hole 188 and holds one externally threaded handle, so that assembling.

Fig. 4 has shown the top view of a distributor chamber 150.Aperture 162 is aimed at fluid passage 163.Fluid passage 163 separates shape such as sawtooth by fluid parallel regulator 164.

Device 100 is sent into allocation space 158 from fluid source (not showing) by center tube 111 with second moving fluid (preferably liquid), and sends into fluid passage 163 subsequently.Simultaneously, device 100 is sent into chamber 143 from fluid source (not showing) by passage 122, chamber 124, circular passage 126 with first moving fluid (being preferably gas), and is discharged from through aperture 162 from this

chamber.Tracing device

10 and 40 fluid and equipment also can be used for device 100 fully.

The speed of moving fluid or linear (for volume) fluid rate will according to different device as install 10, device 40, device 100 or their modification select, so that reach a Weber number that surpasses critical Weber number, make the gaseous state of access to plant and liquid fluid produce desirable bubble diameter or size, as described below.Skilled skilled worker can just choose suitable device and determine gratifying operating condition without experiment.Skilled skilled worker can also and not exceed essence of the present invention and scope without experiment, and described device is done suitable repairing.

Device within the scope of the present invention as those devices of being described among Fig. 1,2,3, has usually very widely and uses.Intuitively, nonrestrictive purposes comprises: improve the transfer in the water of oxygen or air in handling the bioreactor of waste water, the performance of the improvement polymerization inhibitor that oxygen activates in one or more stages of polymerisation, in a word, improve the solubility of at least a gas in liquid.Based on this point, application of the present invention with commercial significance, be to produce Merlon with dissolving method or interfacial process, wherein the carbonic acid derivative of gaseous state such as carbonic acid chlorine and dihydroxy compounds such as aromatic dihydroxy compound double mutual-hydroxy phenenyl oxide (being commonly referred to " bisphenol-A ") react (dissolving method) in the homologue solution that comprises bisphenol-A and carbonic acid chlorine, or in a binary system, wherein bisphenol-A is dissolved in or is suspended in a kind of aqueous solution and organic solvent (as methylene chlorine) of organic base, and solubilized carbonic acid chlorine and bisphenol-A product Merlon (interfacial process).Various intermittences or continuous unit operation process and configuration comprise the stirred tank reactor of piston type or continous way, all in prior art for example at United States Patent (USP) 4,737,573 and 4,939,230 and variously in the reference book that this quotes, description was arranged.The people who is familiar with polycarbonate technology will appreciate that shear mixing apparatus of the present invention can suitably be used for a lot of such technical process also satisfactoryly, be based upon wherein running system with improvement, and for those carbonic acid chlorine is blown out bubble and feed process in the methylene chlorine organic solvent, this device will advantageously improve the disperse of carbonic acid chlorine in methylene chlorine.

Further widely aspect, the people who is familiar with this area can understand, the present invention can be used for reducing the reaction time aspect equipment and the method two, like this, limit dynamic fast reaction gas-liquid reaction system for any by mass transfer, produce at needs under the condition of product of scheduled volume, just reduced the quantity and the size (correspondingly having reduced the expense of producing this product) of required reaction vessel, or can increase production potentially with regard to existing reactor and process.To recognize that below a lot of oxidations and hydro-combination process all belong to this type.

For example, producing the vinylbenzene peracid and crossing t-butyl acid oxidase technical process has the very long reaction time (to be approximately 1 to 4 hour, see " propylene oxide ", Kirk-Othmer EncyclopediaofChemical, Technology, the third edition, the 19th volume, 257-261 page or leaf (1982)) also may need a large amount of reaction vessels, and the vinylbenzene peracid is that one side is produced propylene oxide and styrene is produced the intermediate product of the famous commercial process process of propylene oxide and tert-butyl group ethanol on the other hand with crossing the acid of t-butyl.In this respect, usually under the situation of the tert-butyl group ethanol that percent 10-30 is arranged, is that 95 to 150 degrees centigrade, pressure are under 2075 to 5535 kPas the condition by the iso-butane air oxidation thing of liquid state in temperature, prepared the acid of t-butyl, the iso-butane of percent 20-30 is transformed, wherein percent 60-80 changes into TBHP, and percent 20-40 changes into TBA.The TBA that produces of a unreacted iso-butane and a part separates from product stream, is recovered to the reactor that forms hydroperoxide, sees United States Patent (USP) 4,128,587.The vinylbenzene peracid can be the oxide of the air or oxygen of vinylbenzene by a kind of oxide of liquid state in the case also, in the preparation of getting off of the condition of 140 to 150 degrees centigrade and 30 to 30 psia (206-275 kPa absolute pressure power).It is reported that in 2 to 2.5 hours reaction time the conversion ratio of hydroperoxide is percent 10 to 15, sees United States Patent (USP) 3,351,635; 3,459,810 and 4,066,706.

The commercially important application of another one relates to through the olefin chlorohydrin of correspondence makes epoxides, for example, makes chloropropylene oxide by allyl chloride, makes epoxy butane by methaform, makes propylene oxide by 1-chloro-2-propanol.Like this, on wide significance, for invention can make the technical process of producing epoxides more effective, perhaps as mentioned above, help other two-phase, gas-liquid reaction technology more widely in these technologies, improve the mass transfer of gas in liquid and can obtain some benefits.

The special production of considering to make epoxides by the olefin chlorohydrin intermediate, this is normally by forming olefin chlorohydrin, and subsequently in epoxidation step, this chlorhydrin is contacted with moisture alkali metal hydroxide, comprise the aqueous solution of the salt of at least a epoxides with formation.Apparatus and method of the present invention (following will the explanation) are particularly suitable for helping and improving the formation of olefin chlorohydrin.

At this, form olefin chlorohydrin preferably by at least a undersaturated organic compound is contacted with a kind of hypochloric acid water solution (HOCl) of low chlorine, to form a kind of organic product aqueous solution that comprises at least a olefin chlorohydrin.Should " undersaturated organic compound " comprise 2 to 10 carbon atoms, better comprise 2 to 8 carbon atoms, preferably comprise 2 to 6 carbon atoms.This organic compound is selected from and comprises alternative and non-alternative alkene family, may be chain, divide dendritic or ring-type, chain preferably.Suitable alkene comprises amylene, allene, butadiene, isoprene, allyl alcohol, cinnamyl alcohol, methacrylaldehyde, Mesityl oxide, allyl acetate, allyl ether, vinyl chloride, allyl bromide, bromoallylene, metallyl alcohol, propylene, butylene, ethene, styrene, hexene, allyl chloride and its homologue and analog.Propylene, butylene, ethene, styrene, hexene, allyl chloride are alkene preferably, and more preferably propylene, butylene and allyl chloride are preferably propylene.It is non-alternative that alkene is preferably, but also can be inertia substitute." inertia ground " means that alkene is substituted by any group of the formation of chlorhydrin or epoxides of can not interfering.The substitute of inertia comprises chlorine, fluorine, phenyl etc.For the more detailed description of such epoxidation technique process of summing up at this with the formation step of corresponding chlorhydrin, can be at the common United States Patent (USP) of transferring the possession of 5,486,627 and 5, find in 532,389 (these documents have comprised in the reference of this paper).

Though the preferred embodiment of this method and patent comprises the HOCl aqueous solution that uses low chlorine, those skilled in the art will be easy to recognize that this method also is applicable to the employing hypochlorite solutions, particularly under the situation that the chloride that stoichiometric amount is arranged exists, this method also is used for chlorine partly or entirely is dissolved into water simultaneously.

In order to obtain optimum, add the organic compound of sufficient amount usually, the mole rate of organifying compound and low chlorine HOCl is greater than 0.8.In order to ensure low chlorine HOCl complete reaction, the quantity of the organic compound that is provided will reach stoichiometric amount at least.Be preferably the weight organic compounds of crossing that 0 to 25 mole percent is provided, the weight organic compounds of crossing that is more preferably 0-10 mole percent infeeds in the reactor.Recyclable subsequently unreacted organic compound makes it contact with HOCl.When the organic compound that surpasses the reaction aequum was provided, a skilled skilled worker can adopt the whole bag of tricks fully, reclaims unreacted organic compound.

The weight concentration of the low chlorine HOCl solution that imports be generally 1.0% to about 10%, be preferably 2% to 7%, preferably make the weight of HOCl in water be about 7%.Like this, between the formation of needed water and byproduct, set up balance.Surprisingly, use shear mixing apparatus of the present invention, can form before insoluble organic matter-a kind of increases the condition that byproduct generates greatly, make concentration ratio when carrying out this technical process need not be of the present invention want high by percent 20 during shear mixing apparatus.Certainly, operating with higher H OCl concentration, is desirable for the size and the expense that reduce with this technology relevant devices.

Organic compound can be contacted with HOCl solution with any method that is enough to form chlorhydrin.Normally organic compound and HOCl are someways imported in the reactor, make product all in the reactor that the maximum uniformity be arranged.HOCl preferably occurs in the continuous or semi-continuous reactor with contacting of organic compound.In continuous reactor such as continuous tubular reactor, carry out the importing of reactant and the discharge of product simultaneously.On the contrary, the example of a semi batch reacor may be a such reactor, and promptly the organic compound of existing specified quantity is placed in this reactor, then HOCl solution is infeeded reactor continuously, produces chlorohydrin product and is accumulated in the reactor.Come in contact when preferably in flow reactor such as piston type reactor or backmixed reactor, mixing.Reactant imports and product is discharged from the other end from an end in the piston type reactor, and along this reactor some back-mixings is arranged, and continuous tubular reactor is exactly an example.Reactant mixes with transfer material fully in the reactor of back-mixing formula, makes that product and reactant concentration are even in the entire reaction container.Continuous-flow stirred tank (CSTR) is an example of such flow reactor.

Temperature, pressure condition and reaction time are not strict.The condition of any HOCl of making and organic compound reaction all is suitable for.The temperature that imports the HOCl solution of reactor is approximately 30-60 ℃, is preferably 40 ℃.HOCl/ organic compound suitable reaction temperature is at least 40 ℃, because lower temperature needs freezing or other cooling.Be more preferably and make reaction temperature be at least 60 ℃.Reaction temperature less than 100 ℃ for well, be more preferably less than 90 ℃ (to avoid the evaporation of water and organic compound in the reactor), be more preferably less than 80 ℃ (to avoid poorly increasing more than the temperature formation of byproduct) at this.

When adopting the piston type reactor, by one perpendicular to the HOCl flow of solution to pipe, olefin gas is imported in the HOCl solution.In this respect, shear mixing apparatus of the present invention is this design, be that liquid surface speed is at least about 15 feet per seconds (4.6 meter per second), be preferably about 22 feet per seconds (6.7 meter per second), more preferably at least about 30 feet per seconds (9.1 meter per second), and less than about 100 feet per seconds (30.5 meter per second), preferably less than about 50 feet per seconds (15.2 meter per second).In the time of in importing liquid stream, the gas meter face velocity is at least about 3 feet per seconds (0.9 meter per second), better at least about 6 feet per seconds (1.8 meter per second), and less than about 30 feet per seconds (9.1 meter per second), preferably less than about 20 feet per seconds (6.1 meter per second).Liquid surface speed is at least 1.0 with the ratio of gas meter face velocity, preferably is at least about 1.5, and less than about 10, preferably less than 8.For satisfying these conditions,, may need a plurality of shear mixing apparatus of the present invention when the volume of gas during generally greater than the volume of liquid.When adopting multiple arrangement, between device, provide enough spaces, like this import extra organic compound in the liquid stream before, just have percent 80 at least, preferably 90 at least percent organic matter reacts.

With CSTR as reactor, by utilizing recovery train, available higher liquid volume flow, this recovery train liquid removing from reactor makes liquid get back in the reaction vessel by mixing arrangement.In such operation, new HOCl solution or before shear mixer of the present invention with reclaim stream and mix, perhaps be imported in the CSTR container by a separate lines.This CSTR container is randomly subsidiary an auxiliary conventional mixing arrangement, and Chang Gui mechanical agitator for example is with maintenance reactant and the even distribution of product in container.In particular cases this, the design of shear mixing apparatus of the present invention is such, be that liquid surface speed is at least about 15 feet per seconds (4.6 meter per second), be preferably about 22 feet per seconds (6.7 meter per second), more preferably at least about 30 feet per seconds (9.1 meter per second), and less than about 100 feet per seconds (30.5 meter per second), preferably less than about 50 feet per seconds (15.2 meter per second).In the time of in importing liquid stream, the superficial velocity of gas is at least about 3 feet per seconds (0.9 meter per second), better at least about 6 feet per seconds (1.8 meter per second), and less than about 30 feet per seconds (9.1 meter per second), preferably less than about 20 feet per seconds (6.1 meter per second).Liquid surface speed is at least 1.0 with the ratio of gas meter face velocity, preferably is at least about 1.5, and less than about 10, preferably less than 8.Though the general device of playscript with stage directions invention that only needs satisfies these needs, according to the geometry of reactor and the size of employed shear mixing apparatus, can consider to adopt more device.

Adopt in the preferred embodiment of CSTR the operation of CSTR isothermal, and the general adiabatic ground operation of piston type reactor at great majority.Therefore, reaction heat is removed from CSTR expediently, for example comes heat extraction by recycle heat exchanger and/or reactor jacket.In order to make outside heating or cooling to reactor reduce to minimum, reaction heat preferably matches with the temperature that infeeds that supplies raw material, and reaction heat will infeed temperature and bring up to desirable reaction temperature like this.Temperature is cooperated be the prior art in this area.For example, one mole HOCl infeeds concentration (HOCl of about percent 5 weight concentrations) and reacts with propylene adiabaticly and improve about 55 ℃ of temperature.Therefore, if reaction temperature is desirable for about 90 ℃, then infeeds temperature and should be about 35 ℃.Infeed that the gap of temperature and reaction temperature is less then to need cooling, this gap more then needs heating.With the prior art of any this area,, all can realize temperature controlling as the heat exchanger in the coil pipe of submersible in the reaction vessel, reactor of band overcoat or the external circuit.

Suitable pressure is at least about atmospheric pressure (about 101 kPas), preferably is at least about 2 atmospheric pressure (202.6 kPas).Higher pressure strengthens the mass transfer of organic compound toward HOCl solution, has increased the speed of entire reaction.Suitable pressure is more preferably less than about 100psig (691 kPas) less than about 150psig (1037 kPas), because lower pressure demand has reduced the manufacturing cost of reactor and gas imported the energy consumption of reactor.

Chlorhydrin forms the reaction time of step, by the decision of following factor: the transforming degree of used reactant, reaction temperature, anticipation, liquid and the volume ratio of gas, excessive organic compound, the pressure of reactor, HOCl by shear mixing apparatus of the present invention infeed muriatic content in the material, and HOCl infeed concentration.Can determine HOCl and the required time enough of organic compound reaction this area veteran.For example,, under above-mentioned optimum condition, can will be reduced in the reaction time very ideally and be about two minutes, and better can be reduced to and be about 1 minute when with propylene during as the organic compound among the CSTR.The suitable reaction time was more preferably less than about 5 minutes less than 10 minutes, so that reduce to produce the required container dimensional of predetermined quantity product.The reaction of allyl chloride is faster than the reaction of propylene, thereby the reaction time is shorter, and butylene or hexene is anti-just slow than the reaction of propylene, the reaction time that needs are longer.

The conversion of HOCl in CSTR is at least about 90 mole percents, more preferably greater than 98 mole percents.In reactor,, be no more than weight concentration 0.2% like this, preferably less than weight concentration 0.1% by the concentration of the HOCl that water diluted from react HOCl solution.Lower transforming degree causes from chlorhydrin, as producing higher chlorinated ketone in the oxidation of propylene chlorethanol (PCH), as monochloroacetone (MCA) and other non-desired byproduct.Conversion ratio suitable in CSTR is less than about 99.8 mole percents; Though higher conversion ratio is possible, needs the longer time of staying, thereby need bigger equipment to produce the product of predetermined quantity.

Consistent with the requirement that Motarjemi and Jameson found and expressed mentioned in the introduction of the present invention, application characteristic of the present invention relates to and produce minute bubbles in liquid.Close the average diameter of bubble less than 0.5 millimeter at a lot of field boundarys of using, the unique distinction of apparatus and method of the present invention is, can produce the bubble of such size for various application economically, and use field boundarys in other some and close, the average diameter of bubble can also be less than 0.1 millimeter.The device that belongs in the scope of the invention is specially adapted to method feature of the present invention.This method comprises two independently actions, is used for gas is contacted with flowing liquid.An action is that gas is placed under the pressure, at least one aperture on the element of separating gas and liquid through one, with this gas import liquid, preferably in the flowing liquid time, this pressure is enough to produce bubble.Another action is the physical property according to this gas and liquid, makes working fluid pass through aperture, and the Weber number that its linear flow speed produces is enough to surpass the critical Weber number of desirable bubble size.In fact, this flow velocity impels the bubble segmentation that has just produced at aperture.Segmentation causes producing the littler bubble with ideal noise diode effectively.

Like this, method of the present invention can be controlled at the size of the bubble that produces in the liquid effectively.Device 10,40,100 and their modification are all used with this method.The control of bubble size has caused the method with the surface area that determines accessible mass transfer conversely again, controls the mass transfer of gas in liquid.

A dimensionless number of being Weber is used to predict the relation between bubble size and the working fluid.G.J.Jameson is at " bubble motion ", mentioned the article of being shown by D.A.Lewis and J.F.Davidson " bubble splitting in shear flow ", Trans.ICHemE. the 60th volume, 283-291 page or leaf (1982) in the 588th page.Jameson says that Lewis and Davidson adopt " critical Weber number " or Wecrit, describe power and the capillary critical ratio of attempting to divide or segment bubble, this surface tension attempts to keep the size of given bubble, perhaps, if it is enough big, make bubble recover bigger size.Surpass critical Weber number and make bubble splitting.

The present invention utilizes fluid to flow through the size that stress field that aperture produces is controlled bubble, and bubble produces from aperture at first.If the fluid that flows has enough speed, stress field will be even as big as surpassing critical Weber number, and bubble will segment.The segmentation of bubble will constantly be carried out till the size of the bubble that produces satisfies this critical Weber number.The Weber number is defined by following equation:

We＝r ^*u ^2*dm/s

Wherein:

The r=density of liquid

The speed of fluid in the u=stress field

The dm=bubble diameter

Surface tension between each phase of s=

The present invention both can be applied to polymeric liquid such as clear water, also can be applicable to the salt waste water (waste water with sodium chloride 0.9% weight more than in publication be reported as non-polymeric) of non-polymeric liquid as from some commercial processes, producing, also can be applicable to monomer flow, this monomer flow is according to factors such as for example hydrogen bonds, both can be polymerization, also can be non-polymeric.Here said " polymerization ", the meaning are bubbles in case produce, and just trend towards promptly being merged into relatively bigger bubble.Here said " non-polymeric ", the meaning are bubbles in case produce, and just trend towards keeping its size separately.

Monomer flow or infeed and be suitable for having a kind of polymerization inhibitor in the stream, this polymerization inhibitor is by gas activation.Gas can be a kind of reactant of polymerisation, in this reaction gas in the liquid effectively mass transfer be desired.In another embodiment, this gas dissolves in this liquid.

In actual applications, for example above-mentioned when brine waste (for example, sodium chloride content is about percent 3 weight concentration or bigger in the waste water of commercial processes) ventilation, strengthen the mass transfer of oxygen in brine waste, increased the speed of biochemical reaction.In other words, along with the improvement of mass transfer, the utilization rate of oxygen has increased.Method and apparatus of the present invention by producing littler bubble than traditional bubble generator, has improved mass transfer effectively.

This improvement produces stress field by consumed energy and takes place.The consumption of energy descends with pressure by mixing tube and square being directly proportional of liquid velocity.Practical point that reduces the energy output quantity with respect to bubble size occurs in 50 to 70 kPas the scope, as shown in Figure 6.Though the surface area of mass transfer increases along with the increase of energy consumption, the cost of energy will be above the interests that obtained by mass transfer.A decision cost of energy becomes uneconomic turning point (accordingly, although determine that promptly what bubble size-by the present invention is attainable technically, and no matter whether with 0.5 millimeter of average diameter or littler be feature-can realize economically) will change according to selected final application.In other words, the final application as the efficient of promoting oxygen-activation polymerization inhibitor allows ratio wastewater to handle and consumes bigger energy.Yet, usually believe method and apparatus of the present invention, can produce than having the littler bubble that device can produce up to now can control for given application with economic mode, and method and apparatus of the present invention can produce very little bubble uniquely, it is of a size of 0.5 millimeter of mean air bubble diameter or littler, particularly less than 0.1 millimeter or littler, though as mentioned above, producing so little bubble in application may not be worthwhile economically.

Further illustrate below, but be not to have limited scope of the present invention.Unless add explanation in addition, all marks and percentage are all based on weight.

Embodiment 1

Technical process according to the present invention is carried out in the rectangle polypropylene box of high 36 inches (91.4 centimetres) at one the 6 inches cross sections of taking advantage of 6 inches (taking advantage of 15.2 centimetres for 15.2 centimetres).The NaCl aqueous solution of the concentration expressed in percentage by weight with 10% this chest of packing into reaches 29.7 inches (75.4 centimetres) height.This chest top end opening, temperature be 68 degrees Fahrenheits (°F), promptly 20 degrees centigrade (℃).

The two-phase mixing arrangement that is adopted in this embodiment is similar to the sort of device shown in Figure 1.It comprises the interior air duct (15) of stainless steel of one 3/8 inch (0.9 centimetre) external diameter (OD), this pipeline one end seals, and has bored the aperture of three 1/64 inch (0.04 centimetre) in the interval angle of sentencing 120 ° apart from 3/8 inch of this blind end (0.9 centimetre).The outside of this two-phase blender comprises that the pvc pipe of 3/8 inch (0.9 centimetre) connects cover, and this pipe connects cover by the internal diameter (ID) of 0.423 inch of machining (1.1 centimetres).The remainder of this device comprises the PVC three-way pipe of 1/2 inch (1.3 centimetres), the stainless steel male-pipe of one 1/2 inch (1.3 centimetres) is screwed on the tube connection piece of 3/8 inch (0.9 centimetre), this connector is holed with the pipe by 3/8 inch (0.9 centimetre), and the pipe bushing of two 1/2 inch (1.3 centimetres) to 3/8 inch (0.9 centimetre).A pipe bushing links to each other with an openend of three-way pipe, links to each other with this pipe bushing and the pipe of 3/8 inch (0.9 centimetre) connects cover.Facing to another openend of the pipe of pipe connections and threeway and 3/8 inch (0.9 centimetre) be inserted into and pipe by tube connection piece links to each other, the end of sealing makes the head of pipe just connect the end of cover through pipe, makes the hole of three 1/64 inch (0.04 centimetre) just in time connect in the cover at pipe.

This two-phase mixing arrangement is connected in the chest bottom center with the Internal Pipe Thread interface that utilizes second pipe bushing with 1/2 inch (1.3 centimetres), and blender discharges in case vertically upward like this.The discharge pipe of March TE-5C-MD centrifugal pump links to each other with the remaining mouth of three-way pipe.The suction pipe of this pump is connected with the Internal Pipe Thread interface of 1/2 inch (1.3 centimetres) of chest bottom.The flowmeter of a Wallace and Tiernanmodel 5120M12333XXL Varea-Meter type is set in the discharge pipe to measure the flow velocity of liquid.An air supply pipe links to each other with 3/8 inch (0.9 centimetre) pipe, and air velocity is measured by the Matheson mass velocity converter of band Matheson integrated flow rate controller model8274.

The flow velocity of liquid is 1.75 gallons of (GPM) (11 * 10 cubic metres of per seconds) of per minute, and the flow velocity of air is per minute 1.235 standard liters (SLM, standard conditions are 0 degree centigrade and 760 millimetress of mercury).With such flow velocity, be full of minute bubbles in the case, outward appearance is a milky, and is transparent hardly.

Hang the one 1/8 inch black rubber plate that (0.3 centimetre) is thick from the top of this chest, and this plate extends down under the liquid level in the case about one and 1/2nd foot (0.46 meter) and locates.This plate has been created a background from the several millimeters of the antetheca of chest (mm), and making can be at this shortsighted each bubble of field boundary regional observation.Recorded a video in a little zone in the propylene wall of chest with little video camera of taking the photograph annex with one.Stick on the grid of a 1mm on the chest pellucidly and also videoed, so that demarcate little magnifying power of taking the photograph annex.

(VCR) watches this video-tape with the video recorder that has the Jog/Shuttle function, can analyze each frame video recording like this.With a millimeter scale the shown bubble of each frame video recording on the video recorder screen is measured.Also in this way each frame video recording of expression 1mm grid is observed, on same screen, measured each lattice simultaneously.Confirmed that like this magnifying power is 60 to 1 (the 1.0mm=actual size 0.0154mm of measurement).

In a frame, observe 20 sizes and arrive the bubble in the 0.046mm scope, ten sizes at 0.047 bubble that arrives in the 0.154mm scope 0, four sizes are at 0.155 bubble that arrives in the 0.231mm scope, and three sizes are at 0.232 bubble that arrives in the 0.384mm scope.The minimum bubble that can measure is 0.0154mm, and observed largest air bubbles is 0.385mm in this frame.

Embodiment 2

According to (ASCE) clean water unsteady state method-" measuring the standard that oxygen shifts for one in clean water " Amer.Soc.of Civil Eng. of U.S. civil engineering association (American Society of Civil Engineers), New York, N.Y. (1984) are designed at one and carry out oxygen on the such shear mixing apparatus of salt waste water, structure device as shown in Figure 2 and shift test.Result of the test and with the correction data of known commercially available air pocket sprinkler as shown in Table I:

Table I tested number sprayer air velocity water flow velocity KLa20 SAE ^*

Type (SLM/SCFM) (per minute liter/(L/ hour) (1b oxygen HP/ hour)

Gallons per minute) 1 air pocket 50.9/1.7 0 1.6 1.7

Sprinkler ^*2 shear mixer 22.4/0.75,49.2/13 3.3 2.63 shear mixer 38.9/1.3,49.2/13 5.1 2.54 shear mixer 50.9/1.7,49.2/13 6.2 2.55 shear mixer 53.9/1.8,49.2/13 6.3 2.56 shear mixer 101.8/3.4,49.2/13 9.7 1.87 shear mixer 53.9/1.8 49.2/13 15.4 5.7

(5% salt)

^*Every horsepower of power of SAE=oxygen standard ventilation efficiency in pound hourly.

^*Non-example of the present invention.

For the purpose that between shear mixing apparatus and air pocket sprinkler, directly contrasts, adopted the alpha value (to be defined as the K of two pilot systems _La ₂₀The ratio of value).In this case, state standard or reference is test 1, is to be used for clear water with air pocket sprinkler (CBD).Adopt test 1 and 4, in clear water, alpha=K _La ₂₀Shear mixer (test 4)/K _LA20 CBD (test 1)=3.9.Adopt test 1 and 7, in 5% salt solution, alpha=K _La ₂₀Shear mixer (test 7)/K _La ₂₀CBD (test 1)=9.6.

Data in the Table I show the validity of the present invention with respect to traditional air pocket sprinkler.It is more effective to show that greater than the alpha value of unit value (1.0) shear mixing apparatus carries out mass transfer with respect to the air pocket sprinkler.Can believe that mass transfer increases, and causes owing to having increased surface area at least in part.The increase of surface area mainly be because the average bubble size of shear mixer less than the bubble size of general air pocket sprinkler.The alpha value of salt test solution (test 7) points out the improvement of the mass transfer of (testing 1) with respect to the air pocket sprinkler in clear water at least partially because the non-polymeric character of liquid.In other words, bubble just trends towards keeping its individuality in case form, rather than merges or polymerization with other bubble.

Embodiment 3-the be installed in general introduction of the gas/liquid shear mixer in the monomer process process.

In order in the first seven stage of one ten stage reactors, to eliminate the formation of free radical polyalcohol, the gas/liquid shear mixer of seven playscripts with stage directions inventions has been installed, each is in a stage, to improve the disperse of air in reactant mixture.Except only having in first pipeline 50 the aperture/nozzle 54, this shear mixer is similar to device shown in Figure 2 (device 40).Airborne oxygen activated free radical inhibitors in the system.Before these shear mixer were installed, polymer was present in the stage 1 to 10, and was approximately 0.5 cubic feet (0.014 cubic metre) through per eight hours filtration collected polymers.This gas/liquid shear mixer is with 1.0 gallon (6.3 * 10 of the air velocity of 11.5SLM and per minute ^-5Cube meter per second) solvent flow rate is carried out operation.The nozzle diameter of shear mixer (diameter with each single-nozzle 54 is a benchmark) is 3/16 inch (0.5 centimetre), and the length of nozzle (from the single injector 54 of each blender to pipeline 50 second, output 52) is 1 inch (2.5 centimetres).Air and solvent mix outside given reactor and are transported to the shear mixer that is arranged in reactor by a tipping tube.Owing to shear mixer has been installed, eliminated polymer in seven stages in front, and the formation of polymer has been reduced to per 8 hours 0.25 cubic feet (0.007 cubic metre).

Though blender has only an aperture that forms bubble in the present embodiment, more aperture will be strengthened its performance.Skilled skilled worker can determine easily that just also needing to increase how many apertures just is fit to their application without test.

Embodiment 4

A gas/liquid shear mixer is installed in the container of 2000 gallons (56.6 side's cubic meters), and this container is used to propose water by air from a kind of organic compound that is vulnerable to radical polymerization.Airborne oxygen activated free radical inhibitors in the system.This gas/liquid shear mixer (with employed in figure 3 similar) is carried out operation with per minute 4.0 standard cubic foots (SCFM) air velocity and per minute 50 gallons (0.19 cubic metre/minute) flow velocity that reclaims monomer (119.7SLM).The inside diameter of this shear mixer is 1 inch (2.4 centimetres), and length is about 4 feet (1.2 meters).The initial a collection of water that contains weight about 2% in organic monomer, gas is carried to being less than percent 0.0500 in 12 hours.Gas is carried absolute pressure that condition is 80 millimetress of mercury and 60 ℃.In four batches that the gas that carries out with this method is carried, do not form any polymer.

Embodiment 5

In 0.6 meter high container of 4.57 meters of a diameter high 4.27 meters liquid is arranged, wherein be full of the activation mud of who change (acclimated) from Industrial Wastewater Treatment equipment.Total suspended solid (TSS) is 2600 mg/litre.0.086 the space on the liquid level of cubic meter is cleaned with the nitrogen of the 5SLM that measured by BrooksInstrument Mass Controller (model 5851 I).Liquid infeeds with 0.19 cubic metre/hour, and the time of staying is 6.3 hours.This liquid is the waste water that comes out from industrial oxygenated hydrocarbon factory, and its salinity is 70 grams per liters (about 7% concentration expressed in percentage by weights).The concentration of agent is 150 mg/litre.This system's nozzle diameter is the oxygen that 0.005 meter air pocket sprinkler feeds 1.14SLPM, surveys as Brooks Instrument Mass Controller (model5851 I), and allows it reach to stablize 1 hour.Such as Ingold Electronics Inc.DoSensor/Transmitter (model 4300) survey, the oxygen concentration of dissolving is 0.1 mg/litre, survey as Teledyne Analytic Instruments Model TAI 322 multichannel oxygen surveillances, oxygen in the exit is 15.9%, and the calculating oxygen transfer efficient that is produced is 23%.At this, suddenly this Oxygen Flow is directed in the representative shear mixing apparatus as shown in Figure 2 of the present invention, keep flow and other parameter constant of oxygen.The oxygen concentration in exit begins to descend immediately and oxygen transfer efficient that product calculates begins to increase.After 7 minutes, transfer efficiency is 50%, and the oxygen concentration in exit is 10.2%.After 13 minutes, transfer efficiency is 70%, and the oxygen concentration in exit is 6.4%.After 52 minutes, transfer efficiency is 90%, and the oxygen concentration in exit is 2.2%, and has set up new steady state value.After this, the oxygen of dissolving begins to rise to rapidly 5 milliliters/liter steady state value.

Embodiment 6-8

Embodiment 6-8 and comparative experiments A and B carry out in one 30 liters, vertically arranged cylindrical shape CSTR, and this CSTR is equipped with four vertical baffle plates and an agitator that has one or two impeller.The bottom impeller that comparative experiments A and B adopt is the Chemineer of one 5 inch diameter ^TMCD-6, and the top impeller is the Chemineer of 5 inch diameters ^TMA-315.Embodiment 6-8 only adopts Chemineer ^TMThe A-315 impeller.

Among the embodiment 6-8, the HOCl aqueous solution is added near the center of impeller continuously.Liquid pumps from the bottom of CSTR and turns back to the CSTR through recovery train, this recovery train links to each other with the shear mixing apparatus (structure as shown in Figure 2) of 0.295 inch internal diameter of the present invention, this mixing arrangement is to be contained on the outer wall of container, exhausting line also from shear mixing apparatus through chamber wall just extend under the wheel bottom a bit on.By internal diameter is 0.295 inch pipe, and olefin gas flows to into mixing arrangement perpendicular to liquid.Continuously output object is removed from container with the speed identical with feed rate, constant with liquid level among the maintenance CSTR.

Among experiment A and the B, the HOCl aqueous solution is added near the center of bottom impeller continuously.The sprinkling ring of 4 inch diameters that olefin gas constitutes by a pipe by 1/4 inch diameter, be added to the bottom impeller below.Spraying the hole that is uniform-distribution with 12 1/32 inch on the ring at interval.Pump by a bottom is constantly removed product from container, and is constant with liquid level among the maintenance CSTR.

Embodiment 6-produce the propylene chlorethanol with shear mixing apparatus of the present invention.

Above-mentioned CSTR is in the pressure of 50psig, 69 ℃ condition operation, and a speed is arranged is that per minute 400 changes the agitator of (rpm).A kind of HOCl solution of 5.8% concentration expressed in percentage by weight together adds with the flow of water with 215 Pounds Per Hours with 255 Pounds Per Hours flow.Liquid reclaims by the flow of blender with 3200 Pounds Per Hours, and the superficial velocity of liquid is 31 feet per seconds.Propylene gas adds by the flow of blender with 12.5 Pounds Per Hours, and the superficial velocity of gas is 10 feet per seconds, and liquid is 3.1 to the ratio of the superficial velocity of gas.Product is removed from the bottom of CSTR continuously with 483 Pounds Per Hours flow.In 2 minutes reaction time, the conversion ratio of HOCl is 99%, and the output capacity that with the propylene is the propylene chlorethanol of benchmark is 98%.

Contrast test A-produce the propylene chlorethanol with traditional gas sprinkler.

CSTR is in the pressure of 50psig, 71 ℃ condition operation, and agitator speed is that per minute 560 changes (rpm).A kind of HOCl solution of 5.65% concentration expressed in percentage by weight together adds with the flow of water with 63 Pounds Per Hours with 115 Pounds Per Hours flow.New propylene is that 10 Pounds Per Hours propylene together adds by spraying ring with 4.7 Pounds Per Hours flow and the flow that reclaims from the reactor head space.Product is with continuous the removing of 183 Pounds Per Hours flow.Reaction time is 12 minutes, and the conversion ratio of HOCl is 99.8%, and the output capacity that with the propylene is the propylene chlorethanol of benchmark is 97.5%.

Embodiment 7-produce the butylene chlorethanol with shear mixing apparatus of the present invention

With speed is the operation procedure of 8.1 Pounds Per Hours butylene gas repetition embodiment 6.Reaction condition comprises pressure/66 ℃ of 20psig, the agitator speed 400rpm of single impeller.The liquid that infeeds is that flow is 150 Pounds Per Hours HOCl solution of 5.6% concentration expressed in percentage by weight and the water that flow is 168 Pounds Per Hours.Liquid reclaims by the flow of shear mixing apparatus with 3400 Pounds Per Hours, and its superficial velocity is 31.9 feet per seconds.The superficial velocity of gas is 11.8 feet per seconds, and liquid is 2.7 to the ratio of the superficial velocity of gas.Product is removed from CSTR continuously with 326 Pounds Per Hours flow.Reaction time is 3 minutes, and the conversion ratio of HOCl is 99.8%, and the output capacity that with the butylene is the butylene chlorethanol of benchmark is 94.9%.

Contrast experiment B-produce the butylene chlorethanol with traditional gas sprinkler

According to the operation sequence of contrast experiment B, butylene infeeds by 4.7 Pounds Per Hours the amount of infeeding with the form of gas and sprays ring.Reaction condition comprises the pressure of 20psig, 52 ℃, and agitator speed 550rpm.The liquid that infeeds is that flow is 95.5 Pounds Per Hours HOCl solution of 4.9% concentration expressed in percentage by weight and the water that flow is 57.5 Pounds Per Hours.Product is removed continuously with 158 Pounds Per Hours flow.Reaction time is 15 minutes, and the conversion ratio of HOCl is 99.5%, and the output capacity that with the butylene is the butylene chlorethanol of benchmark is 94.2%.

Embodiment 8-produce the operation sequence of hexene chlorethanol according to embodiment 6 with shear mixing apparatus of the present invention replaces propylene with 7.2 Pounds Per Hours 1-hexenes.Reaction condition comprises the pressure of 3.8psig, 78 ℃, and agitator speed 450rpm.The liquid that infeeds is the HOCl solution of 2.14% concentration expressed in percentage by weight.Liquid reclaims by the flow of shear mixing apparatus with 3080 Pounds Per Hours, and its superficial velocity is 29 feet per seconds.The superficial velocity of gas is 29 feet per seconds, and liquid is 1.0 to the ratio of the superficial velocity of gas.Product is removed continuously with 166 Pounds Per Hours flow.Reaction time is 14.4 minutes, and the conversion ratio of HOCl is 100%, and the output capacity that with the hexene is the hexene chlorethanol of benchmark is 88.2%.

Claims

1. shear mixing apparatus comprises:

At least one pipeline of carrying first fluid to be mixed, first end of this pipeline is opened, and receives first fluid to be mixed, second end is closed, one or more apertures being arranged near its second end place that closes, by this aperture, the fluid that is subjected to by first termination of opening is discharged from pipeline;

A blender, it is generally round one or more above-mentioned pipelines, and first end of a sealing is arranged, and corresponding one or more aperture is arranged on this first end, wherein passes corresponding one or more pipeline; This blender also has one second end, this second end and each above-mentioned pipeline define a resistance nozzle, a corresponding space, this space is by the blender sealing and be limited between first end and second end of above-mentioned blender sealing the resistance nozzle place that the aperture on each said pipeline is placed in basically and this given pipeline interrelates:

The pipeline that second fluid is provided, this pipeline leads to the space of being sealed by blender, so that provide second fluid to it, this second fluid is by one or more resistance nozzles at blender second end, and with certain cut mode with mix by the first fluid that aperture was provided that is positioned at each resistance nozzle place.

2. shear mixing apparatus comprises:

One or more pipelines of first fluid to be mixed are provided, on a segment length of each pipeline, one or more apertures are arranged;

A blender, it has one first end and one second end, and a usually space of sealing arranged between its first end and second end, lead in fluid supply tube road and this space, first end of blender and second end respectively have a corresponding opening, so that pipeline with holes is passed therethrough, like this, provide hole and space on the pipeline of first kind of fluid to be mixed to lead to.

3. a shear mixing apparatus comprises hollow gas and liquid receiving-member, a bubble generation part and an optional handle, and gas is connected and leads to the bubble generation part with the liquid receiving-member.

4. according to the device of claim 3, it is characterized in that: gas and liquid receiving-member comprise:

A center tube, it has the arrival end of opening, is used for receiving liquid wherein, also has a port of export and bubble generation part to lead to;

A gas receiving chamber, it generally separates round center tube and with center tube, thereby form a passage, make air communication cross arrival bubble generation part, which comprises at least the passage of a receiver gases, so that receive the gas flow through and make it to lead to the bubble generation part through passage, an end of gas receiving chamber is connected on the center tube airtightly, its tie point is nearer from the input of center tube, and is far away from output.

5. according to the device of claim 4, it is characterized in that: the bubble generation part comprises a substrate, and this substrate is being connected with center tube airtightly near the center tube output; Gas and liquid distributor chamber are used for holding and distributing respectively from the gas and the liquid of gas receiving chamber and center tube, and this distributor chamber is connected on the substrate airtightly; A cover plate, it is connected with the liquid distributor chamber airtightly with gas, gas and liquid distributor chamber have funnelform fluid pressure chamber, a center, and this pressure-reducing chamber is divided into the liquid relief chamber on top and the gas relief chamber of bottom with substrate, cover plate with the bubble generation part; Funnelform fluid pressure chamber has a hollow stem, this hollow stem is fixed on close port of export place and circular extension of stretching out from above-mentioned hollow stem of center tube usually airtightly outwardly, one group of aperture and one group of fluid passage that leads to the liquid relief chamber that leads to the gas relief chamber is arranged in this hollow stem, lead to these apertures and fluid passage, so that mix gas and the liquid that passes through.

6. according to the device of claim 5, it is characterized in that: the fluid passage is separated from each other by the fluid parallel regulator, and this fluid parallel regulator is arranged in the circular extension that hollow stem stretches out outwardly.

7. method that produces bubble in liquid comprises:

B. make liquid flow through aperture, the Weger number that selected flow velocity 8 produces surpasses the critical Weger number of this gas and liquid, so that produce diameter less than 0.1 millimeter bubble in liquid.

8. according to the method for claim 7, it is characterized in that: liquid is the aqueous solution of a kind of hypochlorous acid of low chlorine, a kind of hypochlorite or water-soluble chlorine, and gas comprises a unsaturated organic compound, this compound with condition that one or more these liquid compositions mix under, can react generates the product that comprises the alkene chlorhydrin.

9. method according to Claim 8, it is characterized in that: this unsaturated organic compound is selected from propylene, butylene and allyl chloride.

10. according to the method for claim 9, it is characterized in that: this unsaturated organic compound is propylene or allyl chloride.

11. the method according to claim 10 is characterized in that: this unsaturated organic compound is a propylene, and is the propylene chlorethanol by the alkene chlorhydrin that it forms.

12. one kind produces the method for diameter less than the bubble of about 0.1mm in liquid, this method comprises the device that adopts claim 1, this gas is imported a share zone, this share zone is set up by the resistance nozzle that liquid flows through this device, liquid flows with such method, promptly in the pressure differential of passing through to set up on the resistance nozzle less than 49,000 handkerchiefs, and gas flow speed is enough to set up the pressure differential less than 35,000 handkerchiefs between pipeline and corresponding resistance nozzle.

13. be suitable for forming under the condition of alkene chlorhydrin, in the reactor of a back-mixing formula, by the unsaturated organic compound of gaseous state and liquid low chlorine compound, hypochlorous acid aqueous solution are produced the alkene chlorhydrin, in a little methods, the improvement of carrying out comprises: with the form of average diameter less than 0.1 millimeter minute bubbles, in the hypochlorous acid solution of liquid state, provide unsaturated organic compound, by this method, the mass transfer among the previous solution chlorate of unsaturated organic compound of increase gaseous state.