Methods and Containers for Transporting, Transferring, Storing and Using Refrigerants

This application is a divisional of U.S. application Ser. No. 17/436,159 filed on Sep. 3, 2021, which is a 371 of international PCT/US20/21425 filed on Mar. 6, 2020 and claims the benefit of Application No. 62/815,528, filed on Mar. 8, 2019 and 62/952,788, filed on Dec. 23, 2019. The disclosures are all of which are hereby incorporated by reference.

The present invention is directed to refrigerant blending, transportation, transfer, and storage and use. In particular, the methods described herein prevent the formation of undesirable reaction products during any or all of these processes in combination.

Olefinic compounds are unsaturated hydrocarbons including one or more pairs of carbon atoms linked by double bond. The unsaturated double bond provides a reactive moiety which is subject to attack by various reactive species.

Many commercial refrigerants include halogenated olefinic compounds. Hydrofluoro olefins (HFOs) and Hydrochlorofluoro olefins (HCFOs) have found utility as modern refrigerants due to their low global warming potential (GWP). During the transfer, transportation, storage and use, olefinic refrigerants may encounter adverse materials or extremely undesirable conditions that cause the double bond to react to form unwanted by-products, which reduce the refrigerant's product performance and effectiveness.

What is therefore needed are systems and methods of transporting, transferring, storing and using olefinic refrigerants, which prevent the formation of possible undesirable reaction products.

In an embodiment, a method for delivering a refrigerant to a refrigerant system. The method includes providing a distribution system arranged and disposed to deliver the refrigerant to the refrigerant system and transferring the refrigerant to the refrigerant system with the distribution system. The method additionally includes measuring at least one distribution parameter of the refrigerant with one or more sensors within the distribution system and selectively directing refrigerant to either the refrigerant system or a recovery system based upon the refrigerant suitability for use in the refrigerant system in response to a comparison of at least one distribution parameter with respect to at least one threshold parameter.

In another embodiment, a system for delivering a refrigerant to a refrigerant system. The system includes a distribution system comprising a distribution vessel, a transfer line, at least one pump, a distribution line and a distribution line branch arranged and disposed to transfer refrigerant from the distribution vessel to the refrigerant system.

The transfer lines and hoses used are preferably constructed of non-polymeric material. Transfer lines and hoses should ideally be made of braided stainless steel. Additionally, the transfer lines coupling device can be of a type which limits product degradation and/or emissions such as a dry bulk coupler.

The system additionally includes a monitoring system comprising one or more sensors arranged and disposed to measure at least one distribution parameter within the distribution system and a recovery system arranged and disposed to selectively receive refrigerant based upon the refrigerant suitability for use in the refrigerant system in response to a comparison of at least one distribution parameter with respect to at least one threshold parameter.

One embodiment of the invention relates to a method for delivering a refrigerant to a refrigerant system, the method comprising:

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein at least one distribution parameter is selected from the group consisting of refrigerant temperature, refrigerant moisture concentration, refrigerant non-absorbable gas concentration, refrigerant non-volatile residue, refrigerant acidity and combinations thereof.

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein at least one threshold parameter is selected from the group consisting of a refrigerant temperature of 100° C., a refrigerant moisture concentration of 10 ppm by weight, per AHRI 700 (2016), a refrigerant non-absorbable gas concentration of about 0.9 to about 1.5, in some cases about 0.9 to about 1.1 and typically about 0.5 to about 0.9 volume percent at 25° C., per AHRI 700 (2016), non-volatile residue <20 ppm by weight, refrigerant acidity and combinations thereof.

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein the distribution system further includes a distribution vessel, a transfer line, at least one pump, a distribution line and a distribution line branch.

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein the distribution line selectively mates to the refrigerant system to deliver the refrigerant to the refrigerant system.

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein the sensors are arranged and disposed to measure the at least one distribution parameter at the distribution line branch prior to delivering the refrigerant to the refrigerant system.

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein the recovery system includes a recovery vessel.

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein the recovery system includes one or more of a recovery vessel, a dehydration module, an inert gas purge module, a non-absorbable gas reduction unit, and a filtration module.

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein the selectively directing includes directing refrigerant to the recovery system when the at least one distribution parameter measured with the one or more sensors exceeds the at least one threshold parameter.

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein the selectively directing includes directing refrigerant to the recovery system when a temperature measured with the one or more sensors exceeds a threshold parameter of a refrigerant temperature of 100° C.

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein the selectively directing includes directing refrigerant to the recovery system when a refrigerant moisture concentration measured with the one or more sensors exceeds a threshold parameter of a refrigerant moisture concentration of 10 ppm by weight, per AHRI 700 (2016).

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein the selectively directing includes directing refrigerant to the recovery system when a non-absorbable gas concentration measured with the one or more sensors exceeds a threshold parameter of a refrigerant non-absorbable gas concentration of 0.9-1.1 volume percent at 25° C., per AHRI 700 (2016).

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein the non-absorbable gas is oxygen.

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein the selectively directing includes directing refrigerant to the recovery system when one or more of the following threshold parameters are exceeded:

One embodiment of the invention relates to a system for delivering a refrigerant to a refrigerant system, the system comprising:

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein the one or more sensors arranged and disposed to measure distribution parameters selected from the group consisting of refrigerant temperature, refrigerant moisture concentration, refrigerant non-absorbable gas concentration, refrigerant acidity and combinations thereof.

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein the recovery system receives refrigerant when one or more of the following threshold parameters are exceeded:

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein the recovery system receives refrigerant when a refrigerant temperature measured with the one or more sensors exceeds a threshold parameter of 100° C.

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein the recovery system receives refrigerant when a refrigerant moisture concentration measured with the one or more sensors exceeds a threshold parameter of 10 ppm by weight, per AHRI 700 ().

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein the recovery system receives refrigerant when a non-absorbable gas concentration measured with the one or more sensors exceeds a threshold parameter gas concentration of 1.5 volume percent at 25° C., per AHRI 700 (2016).

Another embodiment of the invention relates to any combination of the foregoing embodiments wherein the recovery system includes a recovery vessel.

Another embodiment of the invention relates to any combination of the foregoing wherein the recovery system includes one or more of a recovery vessel, a dehydration module, an inert gas purge module, a non-absorbable gas reduction unit, and a filtration module.

Another embodiment of the invention relates to any combination of the foregoing wherein the recovery system includes one or more of a recovery vessel, a dehydration module, an inert gas purge module, a non-absorbable gas reduction unit, and a filtration module.

Another embodiment of the invention relates to any combination of the foregoing wherein the distribution line is configured to mate to the refrigerant system and deliver the refrigerant to the refrigerant system.

Another embodiment of the invention relates to any combination of the foregoing wherein the sensors are arranged to measure the at least one distribution parameter prior to delivering the refrigerant to the refrigerant system.

The various aspects and embodiments of the invention can be used alone or in combinations with each other. Other features and advantages of the present invention will be apparent from the following more detailed description, taken in conjunction with the accompanying drawings which illustrate, by way of example, the principles of the invention.

Wherever possible, the same reference numbers will be used throughout the drawings to represent the same parts.

The instant invention can solve problems caused by decomposition, contamination and undesired reaction of refrigerants (and refrigerant blends) caused by improper handling, storage and transferring refrigerants.

Provided is a method and system of transporting and transferring, olefinic refrigerants, which prevents the formation of undesirable reaction products

Embodiments of the present disclosure, for example, in comparison to concepts failing to include one or more of the features disclosed herein,

A refrigerant distribution system, is described in. In the example of, a delivery vesselcontaining a refrigerant compositionis sampled by a monitoring systemincluding a distribution sensor. The monitoring systemreceives at least one distribution parameter of the refrigerant compositionfrom the distribution sensor. At least one distribution parameter may include temperature, moisture concentration, non-absorbable gas (NAG) concentration, acidity, and combinations thereof. NAGs include atmospheric gases (which is typically comprised of 78% nitrogen, 21% oxygen, and about 1% argon), accumulated in the vapor phase of refrigerants where the solubility of air in the refrigerant liquid phase is relatively low. While reducing the total amount of NAG contained within said refrigerant (dissolved within the liquid refrigerant) may be desirable, it is typically more desirable to reduce the oxygen containing portion of the NAG preferentially over the nitrogen portion. The oxygen containing portion, under certain scenarios, may increase the propensity of the refrigerant to decompose or form unwanted polymeric materials.

In one embodiment, a stabilizer or polymer inhibitor material can be introduced into distribution system. The stabilizer or polymer inhibitor material can reduce (or eliminate formation of) unwanted polymeric materials. The stabilizer or polymer inhibitor material can be introduced in response to detection of an oxidant concentration exceeds a threshold. While any suitable polymer inhibitor or stabilizer can be employed, examples of suitable inhibitors or stabilizers are disclosed in WO2019213004A1; the disclosure of which is hereby incorporated by reference.

The monitoring systemdetermines whether the at least one distribution parameter is below at least one distribution predetermined threshold. If the at least one distribution parameter is below the at least one distribution predetermined threshold, the refrigerant compositionis suitable for distribution. In some embodiments, at least one distribution parameter includes temperature, moisture concentration, non-absorbable gas (NAG) concentration, acidity, oxidant, particles, and combinations thereof. In some embodiments, at least one distribution predetermined threshold includes a temperature of no more than 100° C., moisture level of 10 ppm by weight, per AHRI 700 (2016), a NAG concentration of less than 1.5 volume percent at 25° C., per AHRI 700 (2016), and combinations thereof. Althoughshows a sensoron the delivery vessel, in other embodiments, sensoron the delivery vesselmay be omitted. In other embodiments, at least one distribution predetermined threshold includes a temperature of no more than 120° C., moisture level of 10 ppm by weight, per AHRI 700 (2016), a NAG concentration of less than 0.9 volume percent at 25° C., per AHRI 700 (2016), and combinations thereof. Althoughshows a sensoron the delivery vessel, in other embodiments, sensoron the delivery vesselmay be omitted.

In one embodiment the monitoring system employs an in-line apparatus for detecting the presence of a distribution parameter. The in-line apparatus can be located at any suitable location or locations within the distribution system. For example, an in-line GC/MS apparatus for detecting the presence of oxidants.

In another embodiment, the one distribution predetermined threshold includes a temperature of no more than 100° C., moisture level of 10 ppm by weight, per AHRI 700 (2016), a NAG concentration of less than 0.9 volume percent at 25° C., per AHRI 700 (2016). Althoughshows a sensoron the delivery vessel, in other embodiments, sensoron the delivery vesselmay be omitted.

In some embodiments, the refrigerant compositionmay include a hydrofluoro olefin or hydrochlorofluoro olefin, or hydrofluoroidio olefin. In some embodiments, the refrigerant compositionincludes the a hydrofluoro olefin or hydrochlorofluoro olefin in an amount of at least 0.5 wt percent up to and including 99.5 weight percent, based on the total refrigerant composition. In some embodiments, the hydrofluoro olefin includes at least one:

The delivery vesselmay be transported from a first location to a second location. The delivery vesselmay be transported by any suitable mode of transportation.

At least a portion of the refrigerant compositionis transferred from the delivery vessel, via a distribution line, optionally including a transfer pump, to a distribution vessel, at the second location. The refrigerant compositionmay be sampled during, and/or after transfer to the distribution vessel, by the monitoring system. The monitoring systemmay include a distribution sensor, configured to sample the refrigerant compositionwithin the distribution vessel. The monitoring systemreceives at least one distribution parameter of the refrigerant compositionfrom the distribution sensor. The at least one distribution parameter may include temperature, moisture concentration, non-absorbable gas (NAG) concentration, acidity, and combinations thereof. The monitoring systemdetermines whether the at least one distribution parameter is below at least one distribution predetermined threshold. If the at least one distribution parameter is below the at least one distribution predetermined threshold, the refrigerant compositionis suitable for further distribution. Althoughshows a sensoron the distribution vessel, in other embodiments, sensoron the distribution vesselmay be omitted.

In some embodiments, the at least one distribution parameter includes temperature, moisture concentration, non-absorbable gas (NAG) concentration, acidity, and combinations thereof. In some embodiments, the at least one distribution parameter may include the at least one distribution parameter. In some embodiments the at least one distribution parameter and the at least one distribution parameter are the same.

In some embodiments, the at least one distribution predetermined threshold includes a temperature of 100° C., moisture level of 10 ppm by weight, per AHRI 700 (2016), a NAG concentration of less than 1.1 volume percent at 25° C., per AHRI 700 (2016), and combinations thereof. In some embodiments, the at least one distribution predetermined threshold may include the at least one predetermined threshold. In some embodiments the at least one predetermined threshold and the at least one distribution predetermined threshold are the same.

The distribution systemmay transfer at least a portion of the refrigerant compositionto an end user. A distribution lineis connected to the distribution vesselvia a distribution valve. The operation of the distribution valvemay be regulated by the monitoring system, based on user inputs, data from one or more sensors, other data, and combinations thereof. The distribution valvemay be used to regulate the flow of the refrigerant composition. The pressure within the distribution line may be regulated by one or more distribution pumps. One or more distribution sensorsare configured to sample the refrigerant compositionwithin the distribution line. The monitoring systemreceives at least one distribution parameter of the refrigerant compositionfrom the one or more distribution sensors. The at least one distribution parameter may include temperature, moisture concentration, non-absorbable gas (NAG) concentration, acidity, and combinations thereof. The monitoring systemdetermines whether the at least one distribution parameter is below at least one predetermined threshold. If the at least one distribution parameter is below the at least one predetermined threshold, the refrigerant compositionis suitable for transmission to the end user. Althoughshows a sensoron the distribution line, in other embodiments, sensoron the distribution linemay be omitted.