WO2011156661A1

WO2011156661A1 - In-situ method and system for controlling the flow of an organic liquid

Info

Publication number: WO2011156661A1
Application number: PCT/US2011/039882
Authority: WO
Inventors: Paul L. Edmiston
Original assignee: Abs Materials, Inc
Priority date: 2010-06-10
Filing date: 2011-06-09
Publication date: 2011-12-15

Abstract

Disclosed is a method and system for controlling the flow of an organic liquid by flowing an organic liquid through a pipe having an upstream end with an unconsidered portion and and a downstream end with a constricted portion, the constricted portion having an inner diameter that is at least 10% smaller than the inner diameter of the unconstricted portion, and a porous plug formed of sol-gel derived particles in the pipe, the plug having a length at least two times the diameter of the pipe. Also disclosed is a method and system, tire system including a housing having a liquid inlet and a liquid outlet and containing a sol-gel derived composition and a liquid pressure sensitive control means operatively connected to the liquid inlet for controlling the flow of the organic liquid, contacting the sol-gel derived composition to actuate the liquid pressure sensitive control means and controlling the flow of the organic liquid in response to the actuation.

Description

INSITU METHOD AND SYSTEM FOR CONTROLLING THE

FLOW OF AN ORGANIC LIQUID

Cross Reference to Related Application

This application claims the benefit of Provisional Patent Application Mos.

1 /353,472, filed June 10, 201 L

Background of the Invention

1. Field of the Invention

The present invention relates generally to the chemical arts. More particularly, the invention relates to an in-sitv method and system for the controlling the flow of an organic liquid.

2. Discussion of the Related Art

Controlling the flow of aqueous fluids in response to dissolved or dispersed organic substances is useful for a variety of applications including, but not limited to: 1) preventing release of contaminated water if such water is flowing into the environment, 2) Controlling process mixttires i n manufacturing; 3) Chemically induced valve actuation. Measurement of organic species in water is useful to many fields.

Accordingly, there is a definite need for new methods and systems that simply, efficiently and economically meet these needs.

Summary of the Invention

Now in accordance with the invention there has been found a method and system that meets these needs and provides additional advantages. Disclosed is a method and system for controlling the flow of an organic liquid that includes the step of flowing an organic liquid through a pipe having an upstream, end vvilh an unconstricted portion and and a downstream end with a constricted portion and a porous plug in the pipe. In some aspects, the constricted portion has an inner diameter that is at least 10% smaller than the inner diameter of the unconstricted portion and the plug has a length at least two times the diameter of the pipe. In some embodiments, the porous plug is contained in a fracturable housing. in some aspects, the plug is made of a sol-gel derived composition s e liable to at least 1.5 times its vol tune to cause the plug to swell and control the flow of liquid through the downstream end. And in some aspects, the plug is made of particles of an aromatically- bridged, organosiloxane sol-gel derived composition containing a plurality of alkylsiloxy substituents.

In some aspects, the sol-gel derived particles have an irregular shape. And in some aspects, the sol-gel derived particles have a particle size less than or equal to about 1 ran in at least one direction. In some embodiments, the sol-gel derived particles additionally include an embedded organic polymer. And in some of these embodiments, the embedded polymer is po!yamine, polystyrene or polyvinylphcnol having a molecular weight >1,000 g/mol.

Also disclosed is a method and system that includes flowing an organic liquid through a system made up of a housing having a liquid inlet and a liquid outlet and a liquid pressure sensitive control means operative!)' connected to the liquid inlet for controlling the flow of the organic liquid, contacting the soi-geJ derived composition with the organic liquid to swell the sol-gel derived composition and increase the pressure of the liquid inside the housing to actuate the liquid pressure sensitive control means and controlling tire flow of the organic liquid in response to the actuation o f the liquid pressure sensitive control means.

In some aspects, the housing contains a sol-gel derived composition swellable to at least 1.5 times its volume. And is some aspects, the housing contains a porous aromatically- bridged, organosiloxane sol-gel derived composition containing a plurality of alkylsiloxy substituents. in some embodiments, the pressure sensitive control means is a pressure sensitive valve and actuation of the pressure sensitive valve causes a change of direction in the flow of organic liquid . in some aspects the organic liquid is the only liquid. And in some aspects, the organic liquid forms part of a bi-phasic mixture with water.

In some aspects, the organic solvent is an alkyl hydrocarbon, an aromatic hydrocarbon, a chlorinated hydrocarbon, an alcohol, an aldehyde, an epoxide, a ketone or an organic acid. Such organic solvents include hexane, cyclohexane, octane, decane, octadecane, mineral oil, benzene, toluene, xylene, naphthalene, nitrobenzene, dtchloromethane, trichlcroethylene, perchloroethylene, dichloroethylene, methanol, ethanol. phenol, m-nitrophenoi, metbyl-i-butyl ether, acetone, gasoline, crude oil, aviation fuel and motor oil.

Brief Description of the Drawings

The foregoing a d other features of the present invention, will become apparent, to those skilled in the art to which, the present invention relates upon reading the following description with reference to tire accompanying drawings, in which:

Fig. la is a an illustration of a system in accordance with the invention where the plug has not been displaced.

Fig. l b is a an illustration of the system in accordance with the invention where the plug has been displaced.

Fig. 2 A is an illustration of a second embodiment of a system in accordance with the invention having a liquid pressure sensitive control valve in the dosed position.

Fig. 2A is an illustration of the second embodiment of a system in accordance widi the invention having a liquid pressure sensitive control valve in the closed position.

Detailed Description of the Preferred Embodiments Particular embodiments of the invention are described below in detail for the purpose of illustrating its principles and operation. However, various modifications may he made, and the scope of the invention is not limited to the exemplar}' embodiments described below.

Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in die art to which the present invention pertai s.

As used herein, "swellable" means an increase of at least 1 .5 times the volume of the sol-gel derived composition , when placed in excess acetone compared to the volume when dry.

As used herein, "nanoparticje" means a particle sized between about 2 and about 500 nanometers in one dimension.

In accordance with the invention, there has been discovered a novel method and system for controlling the flow of an organic liquid. In some aspects, the method includes the step of flowing an organic liquid through a. pipe containing a porous plug made of sol-gel derived particles to cause the plug to swell and control the flow of water through the downstream end of the pipe.

The method is useful in controlling the flow of liquids which are comprised entirely of organic liquids and the flow of liquids which are the combination of of the organic liquid and water as a bi-phasic mixture. In some aspects of the invention, when the liquid is comprised entirely of organic liquids, it has a Snyder Index of < 6.5aod when the organic liquid is part of a bi-phasic mixture it has a log k_nvr> -0.32.

Examples of organic liquids include alkyi hydrocarbons, such as hexane, cyclohexane, octane, decanc, oetadecane. and mineral oil; aromatic hydrocarbons, such as benzene, toluene, xylene, naphthalene, nitrobenzene; chlorinated hydrocarbons, such as dichloromethane, tnchloroethylene, perchloroethylene, dichloroethyiene, vinyl chloride and polychlorinated triphenylstsbme; alcohols, including both aliphatic alcohols, such as lower alkyl alcohols, including methanol and ethanoi, and phenols, including phenol and m-nitrophenol; naphthols; ethers, such as methyl-i-bulyi e! er; as well as aldehydes; epoxides: and ketones, such as acetone; organic acids, including organic species possessing at least one carboxylie acid group, at least one sulfonic acid group, at least cne thiol group, or at least one enol group, sulfuric; acids, protonated amines, and hydroxarnic acids: aceroniiriie and mixtures, such as gasoline, crude oil. aviation fuel and motor oil.

In some aspects, the porous plug is formed of sol-gel derived particles sweilabJe to at legist 1.5 times their volume. Preferred so!-gel derived compositions are swellable to at least two times their original volume, more preferably at least five times their original volume, and in some embodiments up to about eight to ten times their original volume. The swelling of the sol-gel derived composition is driven by the release of stored tensile force rather than by chemical reaction.

And in some aspects, the porous plug is formed of particles of an aromatically- bridged, organosiloxane sol-gel derived composition containing a plurality of alkylsiloxy substituents. In such embodiments, the sol-gel derived composition contains a plurality of flexibly tethered and interconnected organosiloxane particles having diameters on the nanometer scale. The organosiloxane nanoparticles form a disorganized porous matrix defined by a plurality of cross-linked aromatic siloxancs.

Jl e porous, aromaticaliy bridged, organosiloxane sol-gel derived compositions contains a plurality of polysiloxancs that include an aromatic bridging group flexibly linking the silicon atoms of the polysiJoxanes. Such organosiloxane nanoparticles have a multilayer configuration comprising a hydrophilic inner layer and a hydrophobic, aromatic-rich outer layer. in some embodiments, the sol-gel deri ed particles have an irregular shape and in some embodiments, the sol-gel derived particles have a particle size less than or equal to about 1 nm in at least one direction. The strength of the barrier created by the swollen ^" plug to prevent further flow f liquid through the pipe can be enhanced by using sol-gel derived particles embedded with organic polymers. Without wishing to be limited to a theory of operation, it is believed that upon swelling, the organic polymers diffuse out of individual sol-gei derived particles and enter neighboring particles leading to molecular- ievcl entanglement of the sol-gel derived particles. The organic polymer is typically included in an amount from about 1% to about 50% w w and in some embodiments from about 1% to about 50% w/w. Examples of suitable organic polymers include, without limitation polyarnine, polystyrene, and polyvinylphenol polymers having a molecular weight > 1.000 g/moL

'flic preparation of sol-gel derived particles is disclosed in U.S. Pat. No. US 7,790,830. issued September 7, 2010, which patent is herein incorporated by reference. A suitable swellable sol-gel derived composition is Osorb® swellable sol-gel derived composition available from ABS Materials, Wooster, Ohio.

In tire embodiment shown in FIGs. 1 a and b, a pipe 10 has an inner wall 1 1 , an upstream end 12 with an imconstricted portion 14 and a downstream end 1 6 with a constricted portion 18. In some aspects, the diameter a of the constricted portion is at least 10% smaller than the diameter b of the unconstricted portion.

A plug 20 is disposed inside the- tube. In some aspects, the plug has a length c that is at least two times the diameter b of the imconstricted portion 14. And is some- aspects of the invention, the plug is contained in a fracturable housing 22.

When the organic liquid is flowed through the pipe 10. it induces swelling of the plug 20. This causes the plug to exert force on the inside wull 1 Ϊ of the pipe. Tn instances of low flow rates and fluid, pressures, the force of the swelling may be sufficient to restrict further flow of organic through the system. As seen in FIG. 1 b, at higher flows rates and pressures the flow is be inhibited when the plug of swollen sol-gel derived particles encounters the constriction point, control is due to fl c viscoclastic properties of the sol-gei derived particles, particularly when swollen with organic liquids. When forced through tlie constriction the partially or fully swollen sol-gei derived articles will compress into a semi-solid preventing further flow beyond the constriction

In the embodiment shown in FIGs. 2a and 2b, the organic liquid is flowed through a housing 30 containing the sol-gel derived composition 1. The housing has a liquid inlet 32, a liquid outlet 34 and a liquid pressure sensitive control means 36 operatively connected to the liquid inlet for controlling the flow of the organic liquid. The sol-gei derived composition is contacted with the organic liquid causing the sol-gel derived composition to swell and increase the pressure of the liquid inside the housing - The increase in pressure actuates the liquid pressure sensitive control means and the flow of the organic liquid is controlled in response to the actuation of the liquid pressure sensitive control means.

This embodiment is also useful in controlling the flow of liquids which arc comprised entirely of organic liquids and the flow of liquids which are the combination of of the organic liquid and -water as a bL- phasic mixture. The housing 30 is made of any suitable material, such as stainless steel. It is an advantage of the inventive method that a wide variety of pressure sensitive control means 36 can be used, including, without limitation, a pressure sensitive valves. The pressure sensiti ve valves can be actuated between an open position, in which the flow of organic liquid is directed through the housing (as shown in FIG. 2a), and a closed position in which the flow of organic liquid is directed through a conduit 38(as shown in FIG. 2b).

The following example is for the purpose of illustration, only and are not intended to limit the scope of the claims, which are appended hereto.

EXAMPLE

A stainless steel tube with a inside diameter of ¼" was bent with a constriction of a dimple on both sides of the bend. Each dimple created a 5% reduction in the inside diameter of the tubing. An amount of fluid (20% transmission fluid, 80% water) was added to the tubing to fill it past the constriction point, ^'this was followed by the addition of 60g of sol-gel derived particles composed of 80% unmodified soi-gel derived particles and 20% sol-gel derived particles embedded with 5% w/w poiyamine. The remaining volume of the tube was filled with fluid (20% transmission fluid. 80% water). Flow was created by pumping fluid via a high pressure liquid chromatography pump a the direction that would cause the soi-gel derived particles material to travel toward the constriction. When the sol-gel derived particles plug encountered the constriction flow ceased. No flow could, be induced even at pressures up to 6,000 psi. Restriction of the flow was independent of initial flow rate.

From the above description of the invention, those skilled in the art will perceive improvements, changes and modifications. Such improvements, changes, and modifications are within the skill of the ait and are intended to be covered by the appended claims.

Claims

I claim

1. A method for controlling the flow of an organic liquid comprising:

flowing an organic liquid through a pipe having an upstream end with an uncoustricted portion and and a downstream end with a constricted portion, the constricted portion having an inner diameter that is at least 10% smaller than the inner diameter of the unconstricted portion, and a porous plug in the pipe, the plug having a length at least two times the diameter of the pipe, th plug comprising a sot-gel derived composition swellable to at least 1.5 times its volume to cause the plug to swell and control the flow of liquid through the downstream end.

2. The method of claim 1 where the organic solvent is an alkyl hydrocarbon, an aromatic hydrocarbon, a chlorinated hydrocarbon, an alcohol, an aldehyde, an epoxide, a ketone or an organic acid.

3. The method of claim 2 where the organic solvent is hexane. eyciohexane, octane, decane, octadecane, mineral oil, benzene, toluene, xylene, naphthalene, nitrobenzene, dichloromethane, trichloroethylene, perchloroethylene, dichloroemylene, methanol, ethanol, phenol, n nitxupheno.l, meiiiyl-f-butyl ether, aceione, gasoline, crude oil, aviation fuel or motor oil.

4. The method of claim 1 wherein the organic liquid is the only liquid.

5. The method of claim 1 wherein is organic liquid forms part of a bi-phasic mixture with water.

6. The method of claim 1 wherein the sol-gel derived particles have an irregular shape.

7. The method of claim wherein the sol-gel derived particles have a particle size less than or equal to about J n n in at least one direction.

8_. The method of claim I wherein the sol-gel derived particles further comprise an embedded organic polymer.

9. The method of claim S wherein the embedded polymer is polyamine, polystyrene or pol inylphenol having a molecular weight > i ,000 g/mol.

10. The method of claim 1 wherein the porous plug is contained in a fracturablc housing.

1 1. A method for controlling the flow of an organic liquid comprising:

flowing an organic liquid through a pipe having an upstream end with an unconstricted portion and a downstream end with a constricted portion, the constricted portion having an inner diameter that is at least 10% smaller than the inner diameter of the unconstrictcd portion, and a porous plug in the pipe, the plug having a length, at least two times the diameter of the pipe, the plug comprising particles of an aromatically- bridged, organosiloxane sol-gel derived composition containing a plurality of alkylsiloxy substituentb to cause the plug to swell and control the flow of liquid through the downstream end.

12. The method of claim I I where the organic solvent is an aJkyl

hydrocarbon, an aromatic hydrocarbon, a chlorinated hydrocarbon, an alcohol, an aldehyde, an epoxide, a ketone or an organic acid.

13. The method of claim 1 1 where the organic solvent is hexane, cyclohexane, octane, decanc, octadecane, mineral oil. benzene, toluene, xylene, naphthalene, nitrobenzene, dichloromethane, tricbdoroethyiene, perchloroeihyleiie, dichloroet ylene, methanol, sthanoi, phenol, m-nitiophenol. methy -butyl ether, acetone, gasoline, crude oil, aviation fuel or motor oil.

The method of claim 1 1 wherein the organic liquid is is the only liquid.

15. The method of claim 1 1 wherein is organic liquid fonns part of a bi-phasic mixture with water,

16. The method of claim 1 1 wherein the sol-gel derived particles have an irregular shape.

17. The method of claim 1 1 wherein the sol-gel derived particles ave a particle size less than or equal to about 1 nm in at least one direction.

18. The method of claim 1 1 wherein the sol-gel derived particles further comprise an embedded organic polymer.

19. The method of claim ί 8 wherei n the embedd cd pol mer is polyamine, polystyrene or polyvinylphenol having, a molecular weight >1 ,000 g/mol.

20. The method of claim 11 wherein, the porous plug is contained in a fracturab!e housing.

21. A system for controlling the flow of an organic liquid comprising:

a pipe having an upstream end with an unconstricted portion and and a downstream end with a constricted portion, the constricted portion having air inner diameter that is at least 10% smaller than die inner diameter of the unconstricted portion, and

a porous plug in the pipe, the plug having a length at least two times the. diameter of the pipe, the plug comprising a sweliabie, sol-get derived particles.

22. The system of claim 21 wherein the sol-gel derived particles have an irregular shape.

23. The system of claim 21 wherei n the s sol-gel derived parti cle have a particle size less than or equal to about 1 nm in at least one direction.

4 1 - 24- The system of claim 21 wherein the soi-gci derived particles further comprise an embedded organic polymer.

25. The system of claim 24 wherein the embedded polymer is polyamine. polystyrene or polyvinylphenol having a molecular weight >1 ,000 g/mol.

26. The system of claim 21 wherein the porous plug is contained in a fracturable housing.

27. A system for controlling the flow of an organic liquid comprising:

a pipe having an upstream end with an unconstrioted portion and and a downstream end with a constricted portion, the constricted portion having an inner diameter that is at ieast 10% smaller than the inner diameter of the vmconstricted portion, and

a porous plug in the pipe, the plug having a length at least two times the diameter of the pipe, the plug comprising particles of an aromatic ally- bridged, organosiioxane sol- gel derived composition containing a plurality of alkylsiioxy substiiuents.

28. The system of claim 27 wherein the sol-gel derived particles have an irregular shape.

29. The system of claim 27 wherein the sol-gel derived particles have a particle size less than or equal to about 1 am in at least one direction.

30. The system of claim 27 wherein the sol-gel derived particles further comprise an embedded organic polymer.

31. The system of claim 28 wherein the embedded polymer is polyamine, polystyrene or polyvinylphenol having a molecular weight > 1 ,000 g mo! .

32. The system of claim 27 wherein the porous plug is contained in a ftacturable housing.

33. A method for controlling the flow of an organic liquid comprising;

flowing an organic liquid through a system comprising:

a housing having a liquid inlet and a liquid outlet, the housing containing a. sol-gel derived composition swellable to at least 1.5 times its volume and

a liquid, pressure sensitive control means operaiively connected to the liquid inlet for controlling the flow of the organic liquid;

contacting the sol-gel derived composition with the organic liquid to swell the sol- gel derived composition and increase, the pressure of the liquid inside tire housing to actuate the liquid pressure sensitive control means: and

controlling the flow of the organic liquid in response to the actuation of the liquid pressure sensitive control means.

34. The method of claim 33 wherein the pressure sensitive control means is a pressure sensitive valve and actuation of the pressure sensitive, valve causes a change of direction in the flow of organic liquid.

35. The method of claim 33 where the organic solvent is an alky]

36. The method of claim 35 where the organic solvent is hexane. cyciohexane, octane, decane, oetadecane, mineral oil. benzene, toluene, xylene, naphthalene, nitrobenzene, dichloromethane, trichloro ethylene, pcreliioroethylene. dichloroetliyiene, methanol, elhanol, phenol, m-nitrophenol, methy -butyl ether; acetone, gasoline, crude oil, aviation fuel or motor oil. 7. The method of claim 33 wherein the organic liquid is is the only liquid

38. The method of claim 33 wherein is organic liquid forms pan of a bi-phasic mixture with water.

39. A method for controlling the flow of an organic liquid comprising:

flowing an organic liquid through through a system comprising:

a housing having a liquid inlet and a liquid outlet, the housing containing a porous aromaticaily- bridged, organosiioxane sol -gel derived composition containing a plurality of aikylsiloxv substituents and

a liquid pressure sensitive control means operatively connected to the liquid inlet, for controlling the flow of the organic liquid;

contacting the sol-gel derived composition with the organic liquid to swell the sol- gel derived composition and increase die pressure of the liquid inside the housing to actuate the liquid pressure sensitive control means; and

40. The method of claim. 39 wherein Lhe pressure sensitive control means is a pressure sensitive valve and actuation of the pressure sensitive valve causes a change of direction in the flow of organic liquid.

41 . The method of claim 39 where the organic solvent, is an. alkvl

hydrocarbon, an aromatic hydrocarbon, a chlorinated, hydrocarbon, an alcohol, an aldehyde, an epoxide, a ketone or an organic acid,

42. The method of claim 41 where the organic solvent is hexane, cyclohexane. octane, decane, octadecane, mineral oil, benzene, toluene, xylene, naphthalene, nitrobenzene, dichioromcthane. triciiiorocthylene, percliioroethy!ene, dichloroelhylene, methanol, ethanol, phenol, nvnitrophenoi, methyl-r-butyl ether, acetone, gasoline, crude oil, aviation fuel or motor oil.

43. The method of claim 39 wherein the organic liquid is is the only liquid.

44. The method of claim 39 wherein is organic liquid forms pan of a bt-phasic mixture with water.

45. A system for controlling the flow of an organic liquid comprising:

a housing havi g a liquid Met and a liquid outlet, the housing containing a sol-gel derived composition swehab!e to at least 1.5 times its volume and

a liquid pressure sensitive control means operalively connected to the liquid inlet for controlling the flow of the organic liquid.

46. The system of claim 45 wherein the pressure sensitive control means is a pressure sensitive valve.

47. A system for controlling the flow of an organic liquid comprising:

a housing having a liquid inlet and a liquid outlet, the housing containing an aromatically- bridged, organosiioxanc sol-gel derived composition containing a plurality of alky!siloxy substituents and

a liquid pressure sensitive control means operative!)' connected to the liquid inlet for controlling the flow of the organic liquid.

48. The system of claim 46 wherein the pressure sensitive control means is a pressure sensitive valve and actuation of the pressure sensitive valve causes a change of direction in the flow of organic liquid.