Patent Application
20240082753
Firstly, the present invention is not for the purpose of defence.
Particularly, the present invention relates to a polymerization inhibiting and emulsion breaking composition and method of use thereof for inhibiting polymerization and breaking emulsions formed between hydrocarbon and caustic.
More particularly, the present invention relates to a polymerization inhibiting and emulsion breaking composition comprising: an amino acid and a borohydride for inhibiting polymerization and breaking emulsions formed between hydrocarbon and caustic.
The present invention also relates to a use of an additive composition comprising: an amino acids and a borohydride for prevention of fouling caused due to polymerization in a basic solution that is in contact with a gaseous or liquid hydrocarbon stream that is effluent from a hydrocarbon cracking operation.
In pyrolytic cracking operations, feedstocks such as ethane, propane, naphtha, kerosene, gas oil, fuel oil and the like undergo “cracking”, i.e. the removal of hydrogen, to form unsaturated hydrocarbons. Pyrolytic cracking also tends to produce oxygenated hydrocarbons, including carbonyl compounds such as acetaldehyde. In a typical operation, the cracked effluent stream is quenched and fractionated and compressed. Acidic contaminants such as hydrogen sulfide, carbon dioxide and mercaptans are typically then removed from the effluent hydrocarbon stream by washing in a caustic scrubber.
The caustic scrubber partially removes the oxygenated hydrocarbons. At the same time, however, the basic conditions in the scrubber tend to cause base-induced condensation reactions of the carbonyl compounds, including in particular aldehydes (e.g., acetaldehyde) and/or ketones, which in turn result in the formation of polymers.
The polymerization of oxygenated compounds, such as carbonyl-containing organics in basic solutions, has been stopped by adding amine compounds such as hydroxylamine hydrochloride, hydroxylamine sulfate, hydrazine, carbohydrazides and the like. Several patents relate to methods of inhibiting carbonyl fouling.
The inventor had earlier reported, in the U.S. Pat. No. 6,986,839 B2 (US839), a method to inhibit polymerization, which had also been found to have advantage to dissolve the deposits formed on polymerization. In US839, to inhibit polymerization and to solubilize deposits formed on polymerization, the inventor had suggested use of lactams or amino acids. As per the disclosure of US839, additive selected from the group consisting of 6-amino hexanoic acid, taurine, NH2(CH2)xYOzOH, where x is an integer from 1 to 12, Y can be S or C, and z=1 to 2, isomers, salts, and combinations thereof, and beta alanine and salts thereof is effective to inhibit polymerization and dissolve deposits formed on the polymerization.
The inventor had also reported in US839 that additive selected from the group consisting of an acid salt of 6-amino hexanoic acid with an acid selected from the group consisting of hydrochloric acid, sulfuric acid, perchloric acid and organic acids is effective to inhibit polymerization and dissolve deposits formed on the polymerization.
The inventor had also reported in US839 that additive selected from the group consisting of 6-amino hexanoic acid and sodium salts of 6-amino hexanoic acid is also effective to inhibit polymerization and dissolve deposits formed on the polymerization when the component in the feed stream is a carbonyl compound and when the molar ratio of carbonyl compound to 6-amino hexanoic acid or sodium salts of 6-amino hexanoic acid is between 1:10 and 1:0.01.
However, the inventor has found that the additive disclosed in the US839, which is:
The inventor has observed that time to break the emulsions formed is substantially higher when the additive of US839 is used. As per the experimental data presented in the Table-1 of the present invention, the inventor has found that:
From the above-discussed experimental data of Table 1 of the prior art US839, it is clearly understood that time to break the emulsion is substantially higher at each dosage, which substantially increases further from about 4 min to about 14 min with the increase in dosage from 0.25 ml (0.29 g) to 0.50 ml (0.57 g) of the additive of the US839, and such a composition and a method are highly uneconomical.
Therefore, there is a need for an additive or an additive composition, which is not only effective in inhibiting and controlling polymerization but is also effective in reducing or almost eliminating a tendency to form emulsions, and if the emulsions are formed, then has tendency to break the emulsions.
Accordingly, there is a need for an additive composition, which is not only effective in inhibiting and controlling polymerization, but is also effective in reducing or almost eliminating a tendency to form emulsions, and if the emulsions are formed, then is effective in breaking the emulsions formed, and time to break the emulsions formed is substantially reduced or lowered even at a lower dosage of the additive composition; and furthermore the time to break the emulsions formed does not increase substantially with increase in the dosage of the additive composition, hence be economical.
Therefore, aim of the present invention is to provide an additive composition, which is not only effective in inhibiting and controlling polymerization but is also effective in reducing or almost eliminating tendency to form emulsions, and if the emulsions are formed, then has tendency to break the emulsions.
Accordingly, aim of the present invention is to solve the problems of the prior art by providing an additive composition, which should not only be effective in inhibiting and controlling polymerization, but should also be effective in reducing or almost eliminating tendency to form emulsions, and if the emulsions are formed, then should also be effective in breaking the emulsions formed, and time to break the emulsions formed should be substantially reduced or lowered even at a lower dosage of the additive composition; and furthermore the time to break the emulsions formed should not increase substantially with increase in the dosage of the additive composition, hence be economical.
Therefore, this is an object of the present invention to provide an additive composition, which is not only be effective in inhibiting and controlling polymerization, but is also be effective in reducing or almost eliminating tendency to form emulsions, and if the emulsions are formed, then is also be effective in breaking the emulsions formed, and time to break the emulsions formed is substantially reduced or lowered even at a lower dosage of the additive composition; and furthermore the time to break the emulsions formed is not increased substantially with increase in the dosage of the additive composition, hence is economical.
This is also an object of the present invention to provide a method for inhibiting and controlling polymerization and simultaneously for breaking emulsions by treating a polymerizable material with the additive composition of the present invention.
This is also an object of the present invention to provide a use of an additive composition for inhibiting and controlling polymerization and simultaneously for breaking emulsions formed by treating a polymerizable material with the additive composition of the present invention.
This is also an object of the present invention to provide a use of an additive composition for prevention of fouling by inhibiting polymerization in a basic solution that is in contact with a gaseous or liquid hydrocarbon stream that is effluent from a hydrocarbon cracking operation.
Further objects of the present invention would be apparent from the following description of the invention.
With aim to solve the above-discussed problems of the prior art, the inventor has found that if a composition comprising: an amino hexanoic acid and a borohydride is added to a polymerizable material or a stream of the polymerizable material, then it, surprisingly and unexpectedly, demonstrates a synergistic effect by being effective in reducing or almost eliminating the tendency to form emulsions, and if the emulsions are formed, then to break the emulsions formed, and also by being effective in inhibiting and controlling the polymerization.
The inventor has found that the composition comprising: an amino hexanoic acid and a borohydride has been surprisingly and unexpectedly found to be suitable to substantially reduce the time to break the emulsions formed even at lower dosage of the additive composition; and furthermore it has also been surprisingly and unexpectedly found that the time to break the emulsions formed does not increase substantially with increase in dosage of the additive composition of the present invention.
Accordingly, in first embodiment, the present invention relates to an additive composition to inhibit and control polymerization, and simultaneously to reduce or almost eliminate tendency to form emulsion, and if the emulsion is formed, then to break the emulsion formed, wherein the additive composition comprises: an amino hexanoic acid and a borohydride.
Accordingly, in second embodiment, the present invention relates to a method to inhibit and control polymerization, and simultaneously to reduce or almost eliminate formation of emulsion, and if the emulsion is formed, then to break the emulsion formed by treating the polymerizable material with the additive composition of the present invention.
Accordingly, in third embodiment, the present invention relates to use of an additive composition for inhibiting and controlling polymerization, and simultaneously for reducing or almost eliminating formation of emulsion, and if the emulsion is formed, then to break the emulsion formed by using the additive composition of the present invention in the stream of the polymerizable material.
Therefore, in one aspect, the present invention relates to an additive composition comprising: an amino hexanoic acid and a borohydride for inhibiting and controlling polymerization and simultaneously for breaking emulsions formed.
In accordance with one of the embodiments of the present invention, the amino hexanoic acid is a 6-amino hexanoic acid, or may be used as: an acid salt of 6-amino hexanoic acid or a sodium salt of 6-amino hexanoic acid, or any other salt of 6-amino hexanoic acid.
In accordance with a preferred embodiment of the present invention, the amino hexanoic acid is preferably a 6-amino hexanoic acid.
In accordance with one of the embodiments of the present invention, the borohydride may be sodium borohydride, potassium borohydride, lithium borohydride, ammonium salt of borohydride, or sodium triisopropoxy borohydride. The ammonium salt of borohydride may be tetramethylammonium borohydride, or tetraethylammonium borohydride.
In accordance with a preferred embodiment of the present invention, the borohydride is preferably a sodium borohydride (NaBH4).
Therefore, in accordance with first embodiment, the present invention relates to an emulsion breaking additive composition comprising:
Therefore, in accordance with second embodiment, the present invention also relates to an additive composition for breaking emulsions, and simultaneously for inhibiting and controlling polymerization, wherein the additive composition comprises:
In accordance with the first and second embodiments of the present invention, the amino hexanoic acid is preferably 6-amino hexanoic acid.
In accordance with the first and second embodiments of the present invention, the borohydride is preferably sodium borohydride (NaBH4).
In accordance with the first and second embodiments of the present invention, the polymerizable material is selected from a material having tendency to get polymerized on heating, on condensation, or on cracking.
In accordance with the first and second embodiments of the present invention, the polymerizable material is a polymer formed on aldol condensation, preferably on aldol condensation of acetaldehyde.
In accordance with the first and second embodiments of the present invention, the ammonium salt of borohydride is selected from the group comprising: tetramethylammonium borohydride, and tetraethylammonium borohydride.
Therefore, in accordance with third embodiment, the present invention relates to a method for breaking emulsion, and simultaneously inhibiting and controlling polymerization of a polymerizable material, wherein the method comprise a step of treating the polymerizable material with an additive composition, wherein the additive composition comprises:
In accordance with the third embodiment of the present invention, the amino hexanoic acid is preferably 6-amino hexanoic acid.
In accordance with the third embodiment of the present invention, the borohydride is preferably sodium borohydride (NaBH4).
In accordance with the third embodiment of the present invention, the amino hexanoic acid and the borohydride are preferably added in a one step process as a blend or a mixture in the polymerizable material.
In accordance with the third embodiment of the present invention, the emulsion is formed between a hydrocarbon and caustic.
In accordance with the third embodiment of the present invention, the polymerizable material is selected from a material having tendency to get polymerized on heating, on condensation, or on cracking.
In accordance with the third embodiment of the present invention, the polymerizable material is a polymer formed on aldol condensation, preferably on aldol condensation of acetaldehyde.
Accordingly, in accordance with fourth embodiment, the present invention relates to a use of an additive composition for breaking the emulsion, and simultaneously for inhibiting and controlling polymerization of a polymerizable material, wherein the method comprise a step of adding the additive composition to the polymerizable material, wherein the additive composition comprises:
In accordance with the fourth embodiment of the present invention, the amino hexanoic acid is preferably 6-amino hexanoic acid.
In accordance with the fourth embodiment of the present invention, the borohydride is preferably sodium borohydride (NaBH4).
In accordance with the fourth embodiment of the present invention, the amino hexanoic acid and the borohydride are preferably added in a one step process as a blend or a mixture in the polymerizable material.
In accordance with the fourth embodiment of the present invention, the emulsion is formed between a hydrocarbon and caustic.
In accordance with the fourth embodiment of the present invention, the polymerizable material is selected from a material having tendency to get polymerized on heating, on condensation, or on cracking.
In accordance with the fourth embodiment of the present invention, the polymerizable material is a polymer formed on aldol condensation, preferably on aldol condensation of acetaldehyde.
Accordingly, in accordance with fifth embodiment, the present invention relates to a use of an additive composition for preventing fouling, wherein the method comprises a step of adding the additive composition to the polymerizable material, wherein the additive composition comprises:
In accordance with the fifth embodiment of the present invention, the amino hexanoic acid is preferably 6-amino hexanoic acid.
In accordance with the fifth embodiment of the present invention, the borohydride is preferably sodium borohydride (NaBH4).
In accordance with the fifth embodiment of the present invention, the emulsion is formed between a hydrocarbon and caustic.
In accordance with the fifth embodiment of the present invention, the polymerizable material is selected from a material having tendency to get polymerized on heating, on condensation, or on cracking.
In accordance with the fifth embodiment of the present invention, the polymerizable material is a polymer formed on aldol condensation, preferably on aldol condensation of acetaldehyde.
In accordance with the fifth embodiment of the present invention, the fouling is caused or formed by polymerization of a polymerizable material in a basic solution,
In accordance with the fifth embodiment of the present invention, the basic solution is in contact with a gaseous stream or a liquid hydrocarbon stream.
In accordance with the fifth embodiment of the present invention, the gaseous stream and the liquid hydrocarbon stream is an effluent from a hydrocarbon cracking operation.
In accordance with the fifth embodiment of the present invention, the amino hexanoic acid and the borohydride are preferably added in a one step process as a blend or a mixture in the polymerizable material.
In accordance with the fifth embodiment of the present invention, the fouling is caused by polymerization in a basic solution that is in contact with a gaseous or liquid hydrocarbon stream that is effluent from a hydrocarbon cracking operation.
In accordance with one of embodiments of the present invention, the components: the amino hexanoic acid and the borohydride of the present additive composition may be added in any order in the polymerizable material.
However, it has been found that if the components: the amino hexanoic acid and the borohydride of the present additive composition are added together as a blend or a mixture in the polymerizable material, then it has been surprisingly and unexpectedly found that the time to break the emulsions formed is substantially lowered as compared to separately adding the components: the amino hexanoic acid and the borohydride of the present additive composition.
Therefore, in accordance with one of the more preferred embodiments of the present invention, it relates to a method for inhibiting and controlling polymerization, and to break emulsions by treating a polymerizable material with an additive composition, wherein the additive composition comprises:
wherein the amino hexanoic acid and the borohydride are added together as a blend or a mixture in the polymerizable material.
In accordance with one of the preferred embodiments of the present invention, it has been surprisingly and unexpectedly found that:
In accordance with one of the preferred embodiments of the present invention, the 6-amino hexanoic acid may be prepared by any method known in the art including, but not limited to the methods described in examples 3, 4 or 10 of the U.S. Pat. No. 6,986,839 B2 (US839).
As per one of the preferred embodiments, the polymer control may be measured by any known method. In the examples of the present invention, the polymer control is measured by toluene soluble readings, and emulsion breaking tendency is measured by time taken for the toluene and caustic phase to separate.
As can be understood from the foregoing discussions of the experimental findings, the problems of the prior art have been solved, and the additive composition of the present invention has been surprisingly and unexpectedly found to have technical advantages of being effective not only in inhibiting and controlling the polymerization, but also being effective in reducing or almost eliminating a tendency to form emulsions, and if the emulsions are formed, then to break the emulsions within substantially reduced time.
Based on the experimental results of the present invention, the inventor, without being bound by the theory or the mechanism, has found that the emulsion is formed on adding the prior art additive: 6-amino hexanoic acid to the polymerizable material, and this appears to be the reason for substantial increase in time to break the emulsion in a two-step process of the present invention. However, on combining the 6-amino hexanoic acid with the NaBH4, that is, on adding the additive composition of the present invention in a one step process as a blend or as a mixture, the emulsion formed breaks much faster than on individually using the prior art additives, i.e. the 6-amino hexanoic acid additive of the U.S. Pat. No. 6,986,839 B2 (US839) and the NaBH4 additive of the U.S. Pat. No. 5,582,808 (US808), which confirms synergistic effect of the present invention.
Therefore, the present invention has been found to have both of the following technical advantages:
It may be noted herein, that neither US839 nor US808 discuss problems of emulsions formed between hydrocarbon and caustic, then question of providing a solution to this problem does not arise in US839 and US808.
Therefore, in accordance with the present invention, time to break the emulsions formed has been substantially reduced even at the lower dosages of the present additive composition; and furthermore the time to break the emulsions formed is also not increased substantially with increase in dosage of the additive composition of the present invention.
The present invention also overcomes the problems of borohydrides as used in the prior art U.S. Pat. No. 5,582,808 (US808), wherein substantially higher amount of the borohydride was required, particularly at about 4:1::carbonyl:borohydride molar ratio or at least about 25%. Furthermore, the time to break the emulsions may have been reduced on using the borohydride, but the polymerization is still higher. As can be observed from the attached experimental data, as per the present invention, the amount of the borohydride is generally very low, which not only results in faster breaking of emulsions, but also results in inhibition and control of polymerization.
In accordance with embodiments of the present invention, the present composition may comprise:
as aim of the present invention is to reduce the amount of the borohydride,
In accordance with embodiments of the present invention, the amount of the present composition as may be added to the polymerizable material may vary:
as aim of the present invention is to reduce the amount of additive composition.
The polymerizable material as referred herein is a material which has tendency to get polymerize either on heating, or on condensation, or on cracking. As per one of the embodiments of the present invention, the polymerizable material as referred herein is a polymer formed due to aldol condensation, preferably due to aldol condensation of acetaldehyde, which may also be referred to as aldol or red tide polymers in the industry, wherein vinyl acetate (VA) is the source of acetaldehyde.
The emulsions as referred herein are the emulsions formed between hydrocarbon and caustic, which hamper hydrocarbon and caustic separation process. The presently provided additive composition has technical advantage of not only lowering the polymerization, i.e. polymer formation, but also reducing or almost eliminating tendency to form emulsion, and if the emulsion is formed, then tendency to break emulsion formed between hydrocarbon and caustic.
The present additive composition may be prepared in any manner, and may be used in any manner for inhibiting polymerization and simultaneously breaking emulsions formed between hydrocarbon and caustic.
In accordance with one of the embodiments of the present invention, 6-amino hexanoic acid used in the present examples may be prepared by any method known in the art including, but not limited to the methods described in examples 3, 4 or 10 of the U.S. Pat. No. 6,986,839 B2 (US839), and sodium borohydride (NaBH4) used in the present examples is as commercially available.
For experimental results, a reference may be drawn to the experimental data presented in the following tables: Table-I and Table-II, which are not intended to limit the scope of the present invention.
In the present examples, the polymer control is measured by toluene soluble readings, and emulsion breaking tendency is measured by time taken for the toluene and caustic phase to separate. It may be noted that tighter the emulsion more time it will take to break the emulsion, and higher the tendency to form an emulsion longer the time to break.
As can be observed from the accompanying experimental results, the prior art additive: NaBH4 takes a shorter time for toluene (a hydrocarbon) and caustic phase to separate, but the amount of the polymer formed is higher, therefore, it is not a preferred choice of the industry.
As can also be observed from the accompanying experimental results, the prior art additive: 6-amino hexanoic acid takes a longer time for toluene (a hydrocarbon) and caustic phase to separate, therefore, it is also not a preferred choice of the industry.
As can also be observed from the accompanying experimental results, the comparative additive compositions comprising: (a) 6-amino hexanoic acid and (b) hydroxylamine chloride, or sodium dithionite, or ethylene diamine, take a longer time for toluene (a hydrocarbon) and caustic phase to separate, therefore, these are also not a preferred choice of the industry.
However, the present invention composition comprising: (a) 6-amino hexanoic acid and (b) NaBH4 takes a shorter time for toluene (a hydrocarbon) and caustic phase to separate, and the amount of the polymer formed is also lower, therefore, it is a preferred choice of the industry.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202121002790 | Jan 2021 | IN | national |
This application is a filing under 35 U.S.C. 371 of International Application No. PCT/IB2022/050021 filed Jan. 3, 2022, entitled “Polymerization Inhibiting And Emulsion Breaking Composition And Method Of Use Thereof”, which claims priority to Indian Patent Application No. 202121002790 filed Jan. 20, 2021, which applications are incorporated by reference herein in their entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/IB2022/050021 | 1/3/2022 | WO |
