Nitrogen based hydrogen sulfide scavengers and method of use thereof

Abstract

The present invention relates to a hydrogen sulphide scavenging additive composition for scavenging hydrogen sulphide including sulfur containing compounds and mercaptans, particularly for scavenging hydrogen sulfide in hydrocarbons, wherein the additive composition comprises substantially reduced amount of nitrogen based hydrogen sulfide scavengers, and is also required in substantially reduced amount, and wherein the additive composition scavenges the sulfur containing compounds not only at room temperature, but also at higher temperatures, and comprises at least a combination of: (A) at least one nitrogen based hydrogen sulfide scavenger; and (B) at least one aliphatic tertiary amine, wherein the nitrogen based hydrogen sulfide scavenger comprises triazine based hydrogen sulfide scavenger. In one embodiment, it also relates to a method for scavenging hydrogen sulfide in hydrocarbons, and in another embodiment it relates to a method of using an additive composition of the present invention for scavenging hydrogen sulfide in hydrocarbons. In yet another embodiment, it relates to a composition comprising (i) a hydrocarbon and (ii) a hydrogen sulfide scavenging additive composition for scavenging hydrogen sulfide in hydrocarbons.

Claims

1. A hydrogen sulfide scavenging additive composition for scavenging hydrogen sulfide in hydrocarbon comprising sulfur containing compounds, wherein said additive composition consists of a combination of: (A) at least one nitrogen based hydrogen sulfide scavenger; and (B) at least one aliphatic tertiary amine, wherein the nitrogen based hydrogen sulfide scavenger comprises triazine based hydrogen sulfide scavenger; and wherein the aliphatic tertiary amine comprises tri-isopropanolamine (TIPA), N,N,N,N-Tetrakis (2-hydroxyethyl) ethylene-diamine (THEED), ethylene oxide (EO) derivative of TIPA (EO-TIPA), propylene oxide (PO) derivative of TIPA (PO-TIPA), ethylene oxide (EO) derivative of ethylene diamine (EO-EDA), propylene oxide (PO) derivative of ethylene diamine (PO-EDA), or a mixture thereof; and wherein the composition does not comprise: a) monoethanol amine (MEA); b) diethanol amine (DEA); and c) triethanol amine (TEA).

2. The additive composition as claimed in claim 1, wherein the triazine based hydrogen sulfide scavenger comprises mono-ethanolamine triazine (MEAT) based hydrogen sulfide scavenger.

3. The additive composition as claimed in claim 1, wherein the composition further comprises oxide derivative of nonyl phenol (NP).

4. The additive composition as claimed in claim 3, wherein the oxide derivative of nonyl phenol comprises an ethylene oxide (EO) derivative of nonyl phenol (EO-NP) or propylene oxide (PO) derivative of nonyl phenol (PO-NP), or a mixture thereof.

5. The additive composition as claimed in claim 1, wherein the hydrocarbon comprising sulfur containing compounds comprises hydrocarbon stream selected from the group comprising crude oil, fuel oil, sour gas, asphalts and refined products.

6. The additive composition as claimed in claim 1, wherein the sulfur containing compounds comprise hydrogen sulfide containing compounds, mercaptans, or a mixture thereof.

7. A composition comprising: (a) a hydrocarbon; and (b) a hydrogen sulfide scavenging additive composition; wherein the hydrogen sulfide scavenging additive composition consists of a combination of: (A) at least one nitrogen based hydrogen sulfide scavenger; and (B) at least one aliphatic tertiary amine, wherein the hydrocarbon comprises sulfur containing compounds; wherein the nitrogen based hydrogen sulfide scavenger comprises triazine based hydrogen sulfide scavenger; and wherein the aliphatic tertiary amine is as claimed in claim 1.

8. The composition as claimed in claim 7, wherein the triazine based hydrogen sulfide scavenger comprises mono-ethanolamine triazine (MEAT) based hydrogen sulfide scavenger.

9. The composition as claimed in claim 7, wherein the composition further comprises oxide derivative of nonyl phenol (NP).

10. The composition as claimed in claim 9, wherein the oxide derivative of nonyl phenol comprises an ethylene oxide (EO) derivative of nonyl phenol (EO-NP) or propylene oxide (PO) derivative of nonyl phenol (PO-NP), or a mixture thereof.

11. A method for scavenging hydrogen sulphide in hydrocarbon comprising sulfur containing compounds, wherein the method comprises contacting the hydrocarbon with the hydrogen sulfide scavenging additive composition, wherein the hydrogen sulfide scavenging additive composition is as claimed in claim 1.

12. A method of using the hydrogen sulfide scavenging additive composition for scavenging hydrogen sulphide in hydrocarbon comprising sulfur containing compounds, wherein the method comprises adding to the hydrocarbon the hydrogen sulfide scavenging additive composition as claimed in claim 1.

Description

DETAILED DESCRIPTION

(1) With aim to overcome above-described problems of prior art and to achieve above-described objects of the invention, the inventor has found that when an hydrocarbon comprising sulfur containing compounds including, but not limited to hydrogen sulfide and mercaptans is treated with an additive composition comprising at least a combination of (a) at least one nitrogen based hydrogen sulfide scavenger; and (b) at least one aliphatic amine comprising at least one aliphatic tertiary amine, the sulfur containing compound including hydrogen sulfide is scavenged or removed.

(2) With aim to overcome above-described problems of prior art and to achieve above-described objects of the invention, the inventor has also found that the scavenging of the sulfur containing compounds is achieved even when the additive composition of the present invention comprises a substantially reduced amount of nitrogen based hydrogen sulfide scavengers, i.e. triazines, and/or is used in a substantially reduced amount.

(3) With aim to overcome above-described problems of prior art and to achieve above-described objects of the invention, the inventor has further found that the additive composition of the present invention scavenges the sulfur containing compounds not only at room temperature, but also at higher temperatures.

(4) Accordingly, in main embodiment, the present invention, relates to a hydrogen sulfide scavenging additive composition for scavenging hydrogen sulfide in hydrocarbons comprising sulfur containing compounds including, but not limited to hydrogen sulfide and mercaptans, wherein said additive composition comprises at least a combination of (a) at least one nitrogen based hydrogen sulfide scavenger; and (b) at least one aliphatic amine comprising at least one aliphatic tertiary amine, wherein the nitrogen based hydrogen sulfide scavenger comprises triazine based hydrogen sulfide scavenger.

(5) Accordingly, in another embodiment, the present invention, relates to a method for scavenging hydrogen sulfide in hydrocarbons comprising sulfur containing compounds including, but not limited to hydrogen sulfide and mercaptans, wherein the method comprises adding a hydrogen sulfide scavenging additive composition comprising at least a combination of (a) at least one nitrogen based hydrogen sulfide scavenger; and (b) at least one aliphatic amine comprising at least one aliphatic tertiary amine, wherein the nitrogen based hydrogen sulfide scavenger comprises triazine based hydrogen sulfide scavenger to the hydrocarbons.

(6) Accordingly, in still another embodiment, the present invention, relates to a method of using a hydrogen sulfide scavenging additive composition comprising at least a combination of (a) at least one nitrogen based hydrogen sulfide scavenger; and (b) at least one aliphatic amine comprising at least one aliphatic tertiary amine, wherein the nitrogen based hydrogen sulfide scavenger comprises triazine based hydrogen sulfide scavenger for scavenging hydrogen sulfide in hydrocarbons comprising sulfur containing compounds including, but not limited to hydrogen sulfide and mercaptans, wherein the method comprises treating the hydrocarbon with the additive composition to scavenge the sulfur containing compounds including hydrogen sulfide.

(7) Accordingly, in yet another embodiment, the present invention, relates to a composition for scavenging hydrogen sulfide in hydrocarbons comprising sulfur containing compounds including, but not limited to hydrogen sulfide and mercaptans, wherein the composition comprises at least a combination of (A) a hydrocarbon; and (B) a hydrogen sulfide scavenging additive composition, wherein the hydrogen sulfide scavenging additive composition comprises at least a combination of (a) at least one nitrogen based hydrogen sulfide scavenger; and (b) at least one aliphatic amine comprising at least one aliphatic tertiary amine, wherein the nitrogen based hydrogen sulfide scavenger comprises triazine based hydrogen sulfide scavenger.

(8) In accordance with one of the preferred embodiments of the present invention, the nitrogen based hydrogen sulfide scavengers comprise triazine based hydrogen sulfide scavengers.

(9) In accordance with one of the preferred embodiments of the present invention, the triazines comprise (or include) monoethanolamine triazine (MEAT) based hydrogen sulfide scavengers.

(10) In accordance with one of the preferred embodiments of the present invention, the MEAT of any activity may be used.

(11) In accordance with one of the preferred embodiments of the present invention, the MEAT may be of 32% activity or 50% activity or as may be supplied by its supplier/manufacturer.

(12) In accordance with one of the preferred embodiments of the present invention, the aliphatic tertiary amine comprises tri-isopropanolamine (TIPA).

(13) In accordance with one of the preferred embodiments of the present invention, the aliphatic tertiary amine comprises N,N,N,N-Tetrakis (2-hydroxyethyl) ethylene-diamine (THEED).

(14) In accordance with one of the preferred embodiments of the present invention, the aliphatic tertiary amine comprises ethylene oxide (EO) derivative of TIPA or ethoxylated TIPA (EO-TIPA).

(15) In accordance with one of the preferred embodiments of the present invention, the aliphatic tertiary amine comprises propylene oxide (PO) derivative of TIPA or propoxylated TIPA (PO-TIPA).

(16) In accordance with one of the preferred embodiments of the present invention, the aliphatic tertiary amine comprises ethylene oxide (EO) derivative of ethylene diamine or ethoxylated EDA (EO-EDA).

(17) In accordance with one of the preferred embodiments of the present invention, the aliphatic tertiary amine comprises propylene oxide (PO) derivative of ethylene diamine or propoxylated EDA (PO-EDA).

(18) In accordance with another preferred embodiment of the present invention, the aliphatic tertiary amine comprises tri-isopropanolamine (TIPA), N,N,N,N-Tetrakis (2-hydroxyethyl) ethylene-diamine (THEED), ethylene oxide (EO) derivative of TIPA (EO-TIPA), propylene oxide (PO) derivative of TIPA (PO-TIPA), ethylene oxide (EO) derivative of ethylene diamine (EO-EDA), propylene oxide (PO) derivative of ethylene diamine (PO-EDA), or a mixture thereof.

(19) In accordance with one of the preferred embodiments of the present invention, the mixture of aliphatic tertiary amines may be obtained by mixing one or more of the aliphatic tertiary amines of the present invention, i.e. TIPA, THEED, EO-TIPA, PO-TIPA, EO-EDA, and PO-EDA in any weight (or mole) ratio.

(20) In accordance with one of the preferred embodiments of the present invention, the ethoxylated TIPA (EO-TIPA) may be obtained by reacting 1 mole of TIPA with at least 1 mole of ethylene oxide (EO).

(21) For example, the ethoxylated TIPA may be obtained by reacting 1 mole of TIPA with 1 to 50 moles of ethylene oxide (EO).

(22) For example, the ethoxylated TIPA may comprise: TIPA ethoxyated by 5 moles of ethylene oxide (EO), herein after may be referred to as TIPA-5 mole EO or TI5E; TIPA ethoxyated by 10 moles of ethylene oxide (EO), herein after may be referred to as TIPA-10 mole EO or TI10E; TIPA ethoxyated by 15 moles of ethylene oxide (EO), herein after may be referred to as TIPA-15 mole EO or TI15E; TIPA ethoxyated by 20 moles of ethylene oxide (EO), herein after may be referred to as TIPA-20 mole EO or TI20E; TIPA ethoxyated by 25 moles of ethylene oxide (EO), herein after may be referred to as TIPA-25 mole EO or TI25E; TIPA ethoxyated by 30 moles of ethylene oxide (EO), herein after may be referred to as TIPA-30 mole EO or TI30E.

(23) In accordance with one of the preferred embodiments of the present invention, the propoxylated TIPA (PO-TIPA) may be obtained by reacting 1 mole of TIPA with at least 1 mole of propylene oxide (PO).

(24) For example, the propoxylated TIPA may be obtained by reacting 1 mole of TIPA with 1 to 50 moles of propylene oxide (PO).

(25) For example, the propoxylated TIPA may comprise: TIPA propoxylated by 5 moles of propylene oxide (PO), herein after may be referred to as TIPA-5 mole PO or TI5P; TIPA propoxylated by 10 moles of propylene oxide (PO), herein after may be referred to as TIPA-10 mole PO or TI10P; TIPA propoxylated by 15 moles of propylene oxide (PO), herein after may be referred to as TIPA-15 mole PO or TI15P; TIPA propoxylated by 20 moles of propylene oxide (PO), herein after may be referred to as TIPA-20 mole PO or TI20P; TIPA propoxylated by 25 moles of propylene oxide (PO), herein after may be referred to as TIPA-25 mole PO or TI25P. TIPA propoxylated by 30 moles of propylene oxide (PO), herein after may be referred to as TIPA-30 mole PO or TI30P.

(26) In accordance with one of the preferred embodiments of the present invention, the ethoxylated EDA (EO-EDA) may be obtained by reacting 1 mole of EDA with at least 1 mole of ethylene oxide (EO).

(27) For example, the ethoxylated EDA may be obtained by reacting 1 mole of EDA with 1 to 50 moles of ethylene oxide (EO).

(28) For example, the ethoxylated EDA may comprise: EDA ethoxyated by 5 moles of ethylene oxide (EO), herein after may be referred to as EDA-5 mole EO or EDA5E; EDA ethoxyated by 10 moles of ethylene oxide (EO), herein after may be referred to as EDA-10 mole EO or EDA10E; EDA ethoxyated by 15 moles of ethylene oxide (EO), herein after may be referred to as EDA-15 mole EO or EDA15E; EDA ethoxyated by 20 moles of ethylene oxide (EO), herein after may be referred to as EDA-20 mole EO or EDA20E; EDA ethoxyated by 25 moles of ethylene oxide (EO), herein after may be referred to as EDA-25 mole EO or EDA25E; EDA ethoxyated by 30 moles of ethylene oxide (EO), herein after may be referred to as EDA-30 mole EO or EDA30E.

(29) In accordance with one of the preferred embodiments of the present invention, the propoxylated EDA (PO-EDA) may be obtained by reacting 1 mole of EDA with at least 1 mole of propylene oxide (PO).

(30) For example, the propoxylated EDA may be obtained by reacting 1 mole of EDA with 1 to 50 moles of propylene oxide (PO).

(31) For example, the propoxylated EDA may comprise: EDA propoxyated by 5 moles of propylene oxide (PO), herein after may be referred to as EDA-5 mole PO or EDA5P; EDA propoxyated by 10 moles of propylene oxide (PO), herein after may be referred to as EDA-10 mole PO or EDA10P; EDA propoxyated by 15 moles of propylene oxide (PO), herein after may be referred to as EDA-15 mole PO or EDA15P; EDA propoxyated by 20 moles of propylene oxide (PO), herein after may be referred to as EDA-20 mole PO or EDA20P; EDA propoxyated by 25 moles of propylene oxide (PO), herein after may be referred to as EDA-25 mole PO or EDA25P; EDA propoxyated by 30 moles of propylene oxide (PO), herein after may be referred to as EDA-30 mole PO or EDA30P.

(32) With aim to overcome above-described problems of prior art and to achieve above-described objects of the invention, the inventor has also found that if the hydrogen sulfide scavenging additive composition of the present invention further comprises oxide derivative of nonyl phenol (NP), then the scavenging of the sulfur containing compounds is also achieved even when the additive composition of the present invention comprises a substantially reduced amount of nitrogen based hydrogen sulfide scavengers, i.e. triazines, and/or is used in a substantially reduced amount.

(33) Therefore, in accordance with another embodiment of the present invention, the present additive composition may further comprise at least one oxide derivative of nonyl phenol (NP).

(34) In accordance with one of the preferred embodiments of the present invention, the oxide derivative of nonyl phenol may comprise an ethylene oxide (EO) derivative of nonyl phenol (EO-NP), propylene oxide (PO) derivative of nonyl phenol (PO-NP), or a mixture thereof.

(35) In accordance with one of the preferred embodiments of the present invention, the present composition does not comprise aliphatic secondary amine, aliphatic di-amine, aliphatic primary amine, aliphatic mono-amine, alkanolamine including monoalkanolamine, particularly including monoethanolamine (MEA), and triethanolamine (TEA).

(36) In accordance with one of the preferred embodiments of the present invention, the hydrocarbon comprises (or includes) hydrocarbon stream including, but not limited to crude oil, fuel oil, sour gas, asphalts and refined products contained in storage tanks, vessels, and pipelines.

(37) In accordance with one of the preferred embodiments of the present invention, the hydrogen sulfide containing compounds comprise (or include) sulfur containing compounds, or mercaptans, or a mixture thereof.

(38) Accordingly, in accordance with one of the preferred embodiments of the present invention, in carrying out the method of scavenging or method of use of the present additive composition for scavenging the hydrogen sulfide in hydrocarbon including hydrocarbon stream, the scavenging additive composition is added to the hydrocarbon or gas stream or hydrocarbon stream in a concentration sufficient to substantially scavenge hydrogen sulfide therein.

(39) In accordance with one of the preferred embodiments of the present invention, the present invention relates to a composition for scavenging hydrogen sulfide, wherein the composition comprises: (a) a hydrocarbon comprising sulfur containing compounds; and (b) a hydrogen sulfide scavenging additive composition; wherein the hydrogen sulfide scavenging additive composition comprises at least a combination of: (A) at least one nitrogen based hydrogen sulfide scavenger; and (B) at least one aliphatic tertiary amine, wherein the nitrogen based hydrogen sulfide scavenger comprises triazine based hydrogen sulfide scavenger; and wherein the aliphatic tertiary amine is the one as described herein.

(40) In accordance with one of the preferred embodiments of the present invention, the present invention also relates to a hydrogen sulfide scavenging additive composition for scavenging hydrogen sulfide in hydrocarbon comprising sulfur containing compounds, wherein said additive composition comprises at least a combination of: (A) at least one nitrogen based hydrogen sulfide scavenger; and (B) at least one aliphatic tertiary amine, wherein the nitrogen based hydrogen sulfide scavenger comprises triazine based hydrogen sulfide scavenger; wherein the aliphatic tertiary amine comprises: (i) tri-isopropanolamine (TIPA); (ii) N,N,N,N-Tetrakis (2-hydroxyethyl) ethylene-diamine (THEED); (iii) ethylene oxide derivative of TIPA (EO-TIPA); (iv) propylene oxide derivative of TIPA (PO-TIPA); (v) ethylene oxide derivative of ethylene diamine (EO-EDA); (vi) propylene oxide derivative of ethylene diamine (PO-EDA); or (vii) a mixture thereof.

(41) In accordance with one of the preferred embodiments of the present invention, the present invention also relates to a hydrogen sulfide scavenging additive composition for scavenging hydrogen sulfide in hydrocarbon comprising sulfur containing compounds, wherein said additive composition does not comprise: a) monoethanol amine (MEA); b) diethanol amine (DEA); and c) triethanol amine (TEA).

(42) In accordance with one of the embodiments of the present invention, it also relates to a method for scavenging hydrogen sulphide in hydrocarbon comprising sulfur containing compounds, wherein the method comprises contacting the hydrocarbon with the hydrogen sulfide scavenging additive composition of the present invention, wherein the hydrogen sulfide scavenging additive composition comprises at least a combination of: (A) at least one nitrogen based hydrogen sulfide scavenger; and (B) at least one aliphatic tertiary amine, wherein the nitrogen based hydrogen sulfide scavenger comprises triazine based hydrogen sulfide scavenger.

(43) In accordance with one of the embodiments of the present invention, it also relates to a method of using the hydrogen sulfide scavenging additive composition of the present invention for scavenging hydrogen sulphide in hydrocarbon comprising sulfur containing compounds, wherein the method comprises adding to the hydrocarbon the hydrogen sulfide scavenging additive composition of the present invention, wherein the hydrogen sulfide scavenging additive composition comprises at least a combination of: (A) at least one nitrogen based hydrogen sulfide scavenger; and (B) at least one aliphatic tertiary amine, wherein the nitrogen based hydrogen sulfide scavenger comprises triazine based hydrogen sulfide scavenger.

(44) In accordance with one of the preferred embodiments of the present invention, the hydrogen sulfide scavenging may be carried at a suitable temperature.

(45) From the foregoing description and following supported examples, a reference to which is drawn here, it may be noted that:

(46) Efficiency of nitrogen based hydrogen sulphide scavengers including triazine based hydrogen sulphide scavengers for scavenging hydrogen sulphide improves substantially on addition of the aliphatic tertiary amine of the present invention both at room temperature and at high temperature.

(47) The improvement in efficiency of the nitrogen based hydrogen sulphide scavengers including triazine based hydrogen sulphide scavengers for hydrogen sulphide scavenging is substantially much higher on addition of the aliphatic tertiary amine of the present invention at high temperature as compared to that at room temperature.

(48) The present invention is now described with the help of following examples, which are not intended to limit scope of present invention, but have been incorporated to illustrate advantages of present invention and best mode to perform it. The following examples also demonstrate surprising and unexpected effectiveness (synergistic effects) of the scavenging additive composition of present invention.

EXAMPLES

(49) In the present examples, following abbreviations have been used:

(50) MEAT is mono-ethanolamine triazine, it is taken in its two concentrations of 50% or 32%;

(51) TIPA is tri-isopropanolamine;

(52) EO-TIPA is ethylene oxide (EO) derivative of TIPA;

(53) PO-TIPA is propylene oxide (PO) derivative of TIPA;

(54) THEED is N,N,N,N-Tetrakis (2-hydroxyethyl) ethylene-diamine;

(55) EDA is ethylene diamine;

(56) EO-EDA is ethylene oxide (EO) derivative of EDA;

(57) PO-EDA is propylene oxide (PO) derivative of EDA;

(58) NP is nonyl phenol;

(59) EO-NP is ethylene oxide (EO) derivative of NP;

(60) PO-NP is propylene oxide (PO) derivative of NP;

(61) TIPA-PO 4 mole or may be written as TIPA-4 mole PO or TI4P is propylene oxide (PO) derivative of TIPA, and is obtained by reacting 1 mole of TIPA with 4 moles of propylene oxide (PO);

(62) TIPA-PO 8 mole or may be written as TIPA-8 mole PO or TI8P is propylene oxide (PO) derivative of TIPA, and is obtained by reacting 1 mole of TIPA with 8 moles of propylene oxide (PO);

(63) TIPA-PO 10 mole or may be written as TIPA-10 mole PO or TI10P is propylene oxide (PO) derivative of TIPA, and is obtained by reacting 1 mole of TIPA with 10 moles of propylene oxide (PO);

(64) TIPA-PO 16 mole or may be written as TIPA-16 mole PO or TI16P is propylene oxide (PO) derivative of TIPA, and is obtained by reacting 1 mole of TIPA with 16 moles of propylene oxide (PO);

(65) TIPA-PO 20 mole or may be written as TIPA-20 mole PO or TI20P is propylene oxide (PO) derivative of TIPA, and is obtained by reacting 1 mole of TIPA with 20 moles of propylene oxide (PO);

(66) TIPA-PO 25 mole or may be written as TIPA-25 mole PO or TI25P is propylene oxide (PO) derivative of TIPA, and is obtained by reacting 1 mole of TIPA with 25 moles of propylene oxide (PO);

(67) TIPA-PO 30 mole or may be written as TIPA-30 mole PO or TI30P is propylene oxide (PO) derivative of TIPA, and is obtained by reacting 1 mole of TIPA with 30 moles of propylene oxide (PO);

(68) TIPA-EO 10 mole or may be written as TIPA-10 mole EO or TI10E is ethylene oxide (EO) derivative of TIPA and is obtained by reacting 1 mole of TIPA with 10 moles of ethylene oxide (EO).

(69) TIPA-EO 15 mole or may be written as TIPA-15 mole EO or TI15E is ethylene oxide (EO) derivative of TIPA and is obtained by reacting 1 mole of TIPA with 15 moles of ethylene oxide (EO).

(70) TIPA-EO 20 mole or may be written as TIPA-20 mole EO or TIDE is ethylene oxide (EO) derivative of TIPA and is obtained by reacting 1 mole of TIPA with 20 moles of ethylene oxide (EO).

(71) TIPA-EO 20.8 mole or may be written as TIPA-20.8 mole EO or TI208E is ethylene oxide (EO) derivative of TIPA and is obtained by reacting 1 mole of TIPA with 20.8 moles of ethylene oxide (EO).

(72) TIPA-EO 26 mole or may be written as TIPA-26 mole EO or TI26E is ethylene oxide (EO) derivative of TIPA and is obtained by reacting 1 mole of TIPA with 26 moles of ethylene oxide (EO).

(73) NP-EO 16 mole or may be written as NP-16 mole EO or NP16E is ethylene oxide (EO) derivative of nonyl phenol (NP) and is obtained by reacting 1 mole of nonyl phenol (NP) with 16 moles of ethylene oxide (EO).

(74) NP-EO 20 mole or may be written as NP-20 mole EO or NP20E is ethylene oxide (EO) derivative of nonyl phenol (NP) and is obtained by reacting 1 mole of nonyl phenol (NP) with 20 moles of ethylene oxide (EO).

(75) NP-EO 40 mole or may be written as NP-40 mole EO or NP40E is ethylene oxide (EO) derivative of nonyl phenol (NP) and is obtained by reacting 1 mole of nonyl phenol (NP) with 40 moles of ethylene oxide (EO).

(76) NP-PO 40 mole or may be written as NP-40 mole PO or NP40P is propylene oxide (PO) derivative of nonyl phenol (NP) and is obtained by reacting 1 mole of nonyl phenol (NP) with 40 moles of propylene oxide (PO).

(77) EDA-PO 8 mole or may be written as EDA-8 mole PO or EDA8P is propylene oxide (PO) derivative of ethylene diamine (EDA) and is obtained by reacting 1 mole of EDA with 8 moles of propylene oxide (PO).

(78) EDA-PO 16 mole or may be written as EDA-16 mole PO or EDA16P is propylene oxide (PO) derivative of ethylene diamine (EDA) and is obtained by reacting 1 mole of EDA with 16 moles of propylene oxide (PO).

(79) EDA-PO 20 mole or may be written as EDA-20 mole PO or EDA20P is propylene oxide (PO) derivative of ethylene diamine (EDA) and is obtained by reacting 1 mole of EDA with 20 moles of propylene oxide (PO).

(80) EDA-PO 25 mole or may be written as EDA-25 mole PO or EDA25P is propylene oxide (PO) derivative of ethylene diamine (EDA) and is obtained by reacting 1 mole of EDA with 25 moles of propylene oxide (PO).

(81) EDA-PO 31 mole or may be written as EDA-31 mole PO or EDA31P is propylene oxide (PO) derivative of ethylene diamine (EDA) and is obtained by reacting 1 mole of EDA with 31 moles of propylene oxide (PO).

(82) Polypropylene glycol having molecular weight of about 400 Daltons (PPG400);

(83) Polypropylene glycol having molecular weight of about 1000 Daltons (PPG1000);

(84) Polypropylene glycol having molecular weight of about 2000 Daltons (PPG2000);

(85) Polypropylene glycol having molecular weight of about 3000 Daltons (PPG3000);

(86) Polypropylene glycol having molecular weight of about 4000 Daltons (PPG4000),

(87) which are polymers made from propylene oxide.

(88) Polyethylene glycol having molecular weight of about 200 Daltons (PEG200);

(89) Polyethylene glycol having molecular weight of about 400 Daltons (PEG400);

(90) Polyethylene glycol having molecular weight of about 600 Daltons (PEG600).

(91) which are polymers made from ethylene oxide.

(92) One of ordinary skill in the art may calculate active content dosage and ratio of the components (ingredients) of the present composition as known in the art. For example, as follows:

(93) TABLE-US-00001 Active dosage Dosage (in ppm) Additive (in ppm) would be MEAT (32%) + TIPA-PO 30 500 + 17.5 160 + 17.5 mole in 90/10 weight ratio

(94) Total active dosage=160+17.5=177.5 ppm

(95) MEAT contribution would be=160/177.5100=90.14%90%;

(96) TIPA-PO contribution would be=17.5/177.5100=9.86%10%.

(97) Therefore, the weight ratio of MEAT(32%) and TIPA-PO 30 mole would be 90:10.

(98) By applying the above method, one of ordinary skill in the art may calculate the weight ratio, as taken in the present examples from the ppm dosages thereof.

(99) The average molecular weight of the additives used in the present examples may be calculated by using gel permeation chromatography (GPC) in Daltons. For example, the average molecular weight of some of the additive amines used in the present invention is as tabulated herein below merely for the sake of information without any intention to limit the scope thereof:

(100) TABLE-US-00002 TABLE I Mol. Wt. Additive (by GPC in Daltons) TIPA as such 193 TIPA-PO, 30 mole 2264 EDA-PO, 16 mole 1117 TIPA-EO, 26 mole 1328 NP-PO, 40 mole 1921 NP-EO, 20 mole 1193

(101) The H.sub.2S was purged in 100 ml of kerosene till concentration of H.sub.2S vapor reaches to 2000 ppm in blank sample [Blank-I]. To the resulted solution, a dosage of the prior art additive consisting of triazine and the additive composition of the present invention as given in following tables was added and H.sub.2S scavenging capabilities in % efficiency were measured at 50 C. for 15 minutes. The residual H2S in vapor was detected by a gas detector tube (Unifos). The results are presented in the following tables.

(102) The hydrogen sulphide scavenging efficiency of some of the individual amines was also measured for dosages of 10 ppm, 100 ppm and 200 ppm. It may be noted that in the compositions of the present examples, the amine was added in an amount of less than 50 ppm, therefore, these comparative tests with dosages of 10 ppm, 100 ppm and 200 ppm are sufficient to know whether the individual amine would have hydrogen sulphide scavenging efficiency or not. It was found that the individual amines do not have hydrogen sulphide scavenging efficiency.

(103) TABLE-US-00003 TABLE II Efficiency Amine Dosage (in ppm) (in % at 50 C.) TIPA 50 5 TIPA 100 10 TIPA 200 12.5 EDA 50 10 TIPA-PO, 25 mole 50 10 TIPA-PO, 30 mole 50 10 TIPA-PO, 30 mole 100 10 TIPA-PO, 30 mole 200 15 EDA-PO 16 mole 100 7.5 EDA-PO 16 mole 200 12.5

(104) Similarly, the hydrogen sulphide scavenging efficiency of MEAT of 32% activity and of 50% activity was also measured. It was found that the MEAT has hydrogen sulphide scavenging efficiency, but it was found to be substantially low.

(105) TABLE-US-00004 TABLE III Dosage (in ppm) MEAT [MEAT] (32% active) 500 45.5 600 72.7 700 77.3 900 84.1

(106) TABLE-US-00005 TABLE IV Dosage % % % (ppm) % Efficiency Efficiency Efficiency Efficiency Additive as such (RT, 26 C.) (60 C.) (80 C.) (100 C.) MEAT 50 25 15 11 5 (50% active) 100 50 40 20 15 200 65 50 30 20 300 75 70 60 45

(107) The hydrogen sulphide scavenging efficiency of the present compositions comprising combination of MEAT (50% active) and amines of the present invention was measured at various temperatures, i.e. at room temperature (26 C.), and at 60 C., 80 C. and 100 C., and has been presented in Table V. It has been found that the hydrogen sulphide scavenging efficiency of the MEAT surprising and unexpectedly improves on addition of amines of the present invention, thereby confirming the synergistic effect of the present compositions.

(108) TABLE-US-00006 TABLE V Dosage (ppm) % Efficiency % Efficiency % Efficiency % Efficiency Composition as such (RT, 26 C.) (60 C.) (80 C.) (100 C.) Blank MEAT 50 25 15 11 5 100 50 40 20 15 200 65 50 30 20 300 75 70 60 45 MEAT (50 ppm) + TIPA 50 + 2.5 35 45 65 69 (5 ppm) 100 + 5 60 75 85 90 MEAT (50 ppm) + TIPA- 50 + 2.5 50 60 63 72 10 mole EO (5 ppm) 100 + 5 80 80 80 90 MEAT (50 ppm) + TIPA- 50 55 60 70 75 15 mole EO (5 ppm) + 100 80 80 85 85 MEAT (50 ppm) + TIPA- 50 60 65 75 80 20.8 mole EO (5 ppm) 100 85 85 90 90 MEAT (50 ppm) + TIPA- 50 55 65 75 80 26 mole EO (5 ppm) 100 85 85 90 90 MEAT (50 ppm) + TIPA-4 50 + 2.4 30 40 65 74 mole PO (5 ppm) 100 + 5 55 70 90 90 MEAT (50 ppm) + TIPA- 50 40 50 70 81 4 mole PO (5 ppm) 100 65 80 95 100 MEAT (50 ppm) + TIPA-8 50 + 2.5 60 75 85 98 mole PO (5 ppm) 100 + 5 70 90 100 100 MEAT (50 ppm) + TIPA- 50 65 70 85 98 10 mole PO (5 ppm) 100 70 85 100 100 MEAT (50 ppm) + TIPA- 50 75 80 90 100 16 mole PO (5 ppm) 100 90 97 100 100 MEAT (50 ppm) + TIPA- 50 72 78 ND ND 10 mole PO + TIPA 16 100 87 95 ND ND mole PO (5 ppm in 1:1 ratio) MEAT (50 ppm) + TIPA- 50 79 75 90 95 20 mole PO (5 ppm) 100 95 90 100 100

(109) The hydrogen sulphide scavenging efficiency of the present compositions comprising combination of MEAT (50% active) and amines of the present invention was also measured at temperature of 50 C. for different durations, i.e. at 1 hr., 2 hrs., 4 hrs., 6 hrs., and 48 hrs., and has been presented in Table VI. It has been found that the hydrogen sulphide scavenging efficiency of the MEAT surprising and unexpectedly improves on addition of amines of the present invention even after longer durations of time, thereby confirming the synergistic effect of the present compositions.

(110) TABLE-US-00007 TABLE VI Dosage ppm Efficiency, % Efficiency, % Efficiency, % Efficiency, % Efficiency, % Additive as such (1 hr.) (2 hrs) (4 hrs) (6 hrs) (48 hrs) MEA Triazine (50%) 50 ppm 20 25 30 35 50 MEA Triazine (50%) + 50 + 2.5 ppm 50 75 85 90 99 TIPA-PO 20 mole SR 1954 (MEAT-50, 50 ppm 35 45 55 60 90 BKC80-5/water-45)

(111) For the comparative purpose, the hydrogen sulphide scavenging efficiency of the compositions comprising combination of MEAT (50% active) and PPG and PEG of various molecular weights (as measured by GPC in Daltons), and prior art additive BKC (benzalkonium quaternary ammonium salt) was also measured at various temperatures, i.e. at room temperature (26 C.), and at 60 C., 80 C. and 100 C., and has been presented in Table VII. It has been found that the hydrogen sulphide scavenging efficiency of the MEAT improves, but very marginally on addition of PPG, PEG, prior art additive BKC, thereby confirming that the PPG and PEG do not have synergistic effect.

(112) TABLE-US-00008 TABLE VII Dosage Composition (ppm) % Efficiency % Efficiency % Efficiency % Efficiency (dosage in ppm) as such (RT, 26 C.) (60 C.) (80 C.) (100 C.) Blank MEAT 50 25 15 11 5 100 50 40 20 15 200 65 50 30 20 300 75 70 60 45 MEAT/PPG-400 50 30 15 13 8 (MEAT-50/PPG400-5) 100 49 38 23 18 MEAT/PPG-1000 50 26 18 15 10 (MEAT-50/PPG1000-5) 100 49 40 25 20 MEAT/PPG-2000 50 30 15 15 10 (MEAT-50/PPG2000-5) 100 49 40 30 25 MEAT/PPG-3000 50 28 20 20 15 (MEAT-50/PPG3000-5) 100 51 43 35 30 MEAT/PPG-4000 50 31 23 23 20 (MEAT-50/PPG4000-5) 100 54 48 40 35 MEAT/PEG-200 50 28 18 10 10 (MEAT-50/PEG200-5) 100 50 44 20 15 MEAT/PEG-400 50 25 18 15 10 (MEAT-50/PEG400-5) 100 48 46 20 20 MEAT/PEG-600 50 35 21 15 10 (MEAT-50/PEG600-5) 100 58 49 18 23 SR 1954 50 45 30 30 30 (MEAT-50/BKC-5) 100 80 60 50 45 200 99 70 65 60 300 100 80 80 70

(113) The hydrogen sulphide scavenging efficiency of the present compositions comprising combination of MEAT (50% active) and amines of the present invention was also measured at temperature of 50 C. for duration of 15 min., and compared with diethyl amine (DEA, which contains OH group, but is a secondary amine), trimethylamine (TEA), tetraethylenepentamine (TEPA, which is a secondary and mono amine, and does not contain OH group), and has been presented in Table VIII. It has been found that the hydrogen sulphide scavenging efficiency of the MEAT surprising and unexpectedly improves on addition of amines of the present invention even after shorter durations of 15 mins., thereby confirming the synergistic effect of the present compositions.

(114) For example, there is substantial improvement in the hydrogen sulphide scavenging efficiency at all dosages for composition comprising MEAT and TIPA, particularly at 700 ppm dosage the % efficiency for H2S scavenging improves from 70% to 95% and at 900 ppm dosage the improvement is from 77.5% to >99.5%. Same synergistic effect was found for the present compositions comprising MEAT and PO-TIPA. Similarly, there is substantial improvement at all dosages, particularly at 700 ppm dosage the % efficiency for H2S scavenging improves from 70% to 87.5%, and at 900 ppm dosage the improvement is from 77.5% to 95% for the present composition comprising MEAT and THEED.

(115) On the contrary, the comparative composition comprising MEAT and DEA did not show improvement at all dosages. For example, at 700 ppm dosage the % efficiency for H2S scavenging improves very marginally from 70% to 72.5%, and at 900 ppm dosage there is no improvement. i.e. it remains at 77.5%.

(116) Similarly, the another comparative composition comprising MEAT and TEA also did not show improvement at all dosages. For example, at 700 ppm dosage the % efficiency for H2S scavenging improves very marginally from 70% to 75%, and at 900 ppm dosage there is no improvement. i.e. it remains at 77.5%.

(117) Similarly, the another comparative composition comprising MEAT and TEPA also did not show improvement at all dosage. For example, at 700 ppm dosage the % efficiency for H2S scavenging improves marginally from 70% to 75%, and at 900 ppm dosage also it improves marginally from 77.5% to 80%.

(118) TABLE-US-00009 TABLE VIII Composition Dosage (in ppm) % Efficiency [MEAT + Amine] [MEAT + Amine] (at 50 C.) MEAT 500 37.5 600 65.0 700 70.0 900 77.5 MEAT + TIPA 500 + 25 55.0 (Present Composition) 600 + 30 90.0 700 + 35 95.0 900 + 45 >99.5 MEAT + TIPA-PO, 25 mole 500 + 25 98.9 (Present Composition) 600 + 30 >99.95 700 + 35 >99.95 900 + 45 >99.95 MEAT + TIPA-PO, 30 mole 500 + 25 99.1 (Present Composition) 600 + 30 >99.95 700 + 35 >99.95 900 + 45 >99.95 MEAT + THEED 500 + 25 47.5 (Present Composition) 600 + 30 75.0 700 + 35 87.5 900 + 45 95.0 MEAT + DEA 500 + 25 40.0 (Comparative Composition) 600 + 30 67.5 700 + 35 72.5 900 + 45 77.5 MEAT + TEA 500 + 25 42.5 (Comparative Composition) 600 + 30 67.5 700 + 35 75.0 900 + 45 77.5 MEAT + TEPA 500 + 25 45.0 Comparative Composition) 600 + 30 70.0 700 + 35 75.0 900 + 45 80.0

(119) The hydrogen sulphide scavenging efficiency of the present compositions comprising combination of MEAT (32% active) and amines of the present invention was also measured at temperature of 50 C. for duration of 15 min., and has been presented in Tables IX to XV. It has been found that the hydrogen sulphide scavenging efficiency of the MEAT surprisingly and unexpectedly improves on addition of amines of the present invention, thereby confirms the synergistic effect of the present compositions.

(120) TABLE-US-00010 TABLE IX Dosage (in ppm) MEAT + TIPA in [MEAT + Amine] 90:10 weight ratio 500 + 17.5 75 600 + 21 82.5 700 + 24.5 89 900 + 31.5 91

(121) The data in Table IX confirms that on addition of TIPA to MEAT, a synergistic effect (improvement in percent (%) hydrogen sulfide scavenging efficiency) is seen.

(122) TABLE-US-00011 TABLE X MEAT + MEAT + TIPA + TIPA + Dosage (in ppm) NP-EO Dosage (in ppm) NP-EO [MEAT + Amine + 40 mole [MEAT + Amine + 40 mole Oxide derivative in 90:7:3 Oxide derivative in 90:5:5 of NP] weight ratio of NP] weight ratio 300 + 7.35 + 3.15 93 300 + 5.25 + 5.25 66.25 400 + 9.8 + 4.2 99.8 400 + 7 + 7 80 500 + 12.25 + 5.25 >99.95 500 + 8.75 + 8.75 92.5 600 + 14.7 + 6.3 600 + 10.5 + 10.5 99.2

(123) The data in Table X confirms that on addition of (ethylene) oxide derivative of nonyl phenol (NP) to a combination of MEAT and TIPA, a synergistic effect (improvement in percent (%) hydrogen sulfide scavenging efficiency) is seen.

(124) TABLE-US-00012 TABLE XIa Dosage (in Dosage (in ppm) MEAT + ppm) MEAT + [MEAT + TIPA-PO 30 [MEAT + MEAT + TIPA- Dosage (in TIPA-PO 30 Amine + mole + NP- Amine + PO 30 mole + ppm) mole in Oxide EO 20 mole in Oxide NP-EO 20 [MEAT + 90:10 weight derivative of 90:7:3 weight derivative of mole in 90:5:5 Amine] ratio NP] ratio NP] weight ratio 500 + 17.5 91.2 300 + 7.35 + 72.7 300 + 5.25 + 72.5 3.15 5.25 600 + 21 99.6 400 + 9.8 + 87.5 400 + 7 + 7 87.5 4.2 700 + 24.5 99.95 500 + 12.25 + 99.9 500 + 8.75 + 98 5.25 8.75 900 + 31.5 >99.95 600 + 14.7 + >99.95 600 + 10.5 + >99.95 6.3 10.5

(125) The data in Table XIa confirms that on addition of TIPA-PO to MEAT, and on addition of (ethylene) oxide derivative of nonyl phenol (NP) to a combination of MEAT and TIPA-PO, a synergistic effect (improvement in percent (%) hydrogen sulfide scavenging efficiency) is seen.

(126) TABLE-US-00013 TABLE XIb MEAT + MEAT + MEAT + MEAT + TI16P in TI20P in TI25P in TI30P in Dosage (in 90:10 90:10 90:10 90:10 ppm of weight weight weight weight composition) MEAT ratio ratio ratio ratio 500 45.5 81.8 90.9 90.0 91.2 600 72.7 ND 99.1 99.5 99.6 700 77.3 97.7 99.8 99.95 99.95 900 84.1 99.5 99.95 >99.95 >99.95

(127) The data in Table XIb confirms that on addition of TIPA-PO to MEAT, a synergistic effect (improvement in percent (%) hydrogen sulfide scavenging efficiency) is seen.

(128) TABLE-US-00014 TABLE XII Dosage (in Dosage (in ppm) ppm) MEAT + [MEAT + MEAT + [MEAT + MEAT + Dosage (in TIPA-PO 30 Amine + TIPA-PO 30 Amine + TIPA-PO 30 ppm) mole in Oxide mole + NP- Oxide mole + NP- [MEAT + 90:10 weight derivative of PO 40 mole in derivative of PO 40 mole in Amine] ratio NP] 90:7:3 wt. ratio NP] 90:5:5 wt. ratio 500 + 17.5 91.2 300 + 7.35 + 67.5 300 + 5.25 + 67.5 3.15 5.25 600 + 21 99.6 400 +9.8 + 82.5 400 + 7 + 7 82.5 4.2 700 + 24.5 99.95 500 + 12.25 + 95 500 + 8.75 + 94 5.25 8.75 900 + 31.5 >99.95 600 + 14.7 + >99.95 600 + 10.5 + 99.8 6.3 10.5

(129) The data in Table XII confirms that on addition of TIPA-PO to MEAT, and on addition of (propylene) oxide derivative of nonyl phenol (NP) to a combination of MEAT and TIPA-PO, a synergistic effect (improvement in percent (%) hydrogen sulfide scavenging efficiency) is seen.

(130) TABLE-US-00015 TABLE XIII MEAT + MEAT + TIPA-EO 26 TIPA-EO 26 mole + Dosage (in ppm) mole + Dosage (in ppm) NP-EO 40 [MEAT + NP-EO 40 [MEAT + Amine + mole in Amine + mole in Oxide derivative of 90:7:3 Oxide derivative 90:5:5 NP] weight ratio of NP] weight ratio 300 + 7.35 + 3.15 67.5 300 + 5.25 + 5.25 66.25 400 + 9.8 + 4.2 82.5 400 + 7 + 7 81.25 500 + 12.25 + 5.25 94.5 500 + 8.75 + 8.75 93.75 600 + 14.7 + 6.3 99.9 600 + 10.5 + 10.5 98

(131) The data in Table XIII confirms that on addition of (ethylene) oxide derivative of nonyl phenol (NP) to combination of MEAT and TIPA-EO, a synergistic effect (improvement in percent (%) hydrogen sulfide scavenging efficiency) is seen.

(132) TABLE-US-00016 TABLE XIV MEAT + EDA-PO MEAT + 16 mole + EDA-PO Dosage (in ppm) NP-EO 40 16 mole in [MEAT + Amine + mole in Dosage (in ppm) 90:10 Oxide derivative 90:7:3 [MEAT + Amine] weight ratio of NP] wt. ratio 500 + 17.5 92 300 + 7.35 + 3.15 75 600 + 21 94.1 400 + 9.8 + 4.2 92 700 + 24.5 99.5 500 + 12.25 + 5.25 99.9 900 + 31.5 >99.95 600 + 14.7 + 6.3 >99.95

(133) The data in Table XIV confirms that on addition of EDA-PO to MEAT, and on addition of (ethylene) oxide derivative of nonyl phenol (NP) to combination of MEAT and EDA-PO, a synergistic effect (improvement in percent (%) hydrogen sulfide scavenging efficiency) is seen.

(134) TABLE-US-00017 TABLE XV MEAT + MEAT + EDA-PO 16 EDA-PO 16 mole + mole + Dosage (in ppm) NP-PO 40 Dosage (in ppm) NP-PO 40 [MEAT + Amine + mole in [MEAT + Amine + mole in Oxide derivative of 90:7:3 Oxide derivative of 90:5:5 NP] weight ratio NP] weight ratio 300 + 7.35 + 3.15 80 300 + 5.25 + 5.25 82.5 400 + 9.8 + 4.2 95 400 + 7 + 7 96.5 500 + 12.25 + 5.25 99.9 500 + 8.75 + 8.75 99.9 600 + 14.7 + 6.3 >99.95 600 + 10.5 + 10.5 >99.95

(135) The data in Table XV confirms that on addition of EDA-PO and NP-PO to MEAT, a synergistic effect (improvement in percent (%) hydrogen sulfide scavenging efficiency) is seen.

(136) The foregoing examples confirm synergistic effects, i.e. surprising and unexpected effects of the present invention over the prior art.

(137) Therefore, the foregoing experiments confirm that nitrogen based compositions are capable of scavenging H.sub.2S. However, when the present composition comprising a combination of nitrogen based H.sub.2S scavengers and one or more aliphatic tertiary amine is used, the H.sub.2S scavenging efficiency of the nitrogen based H.sub.2S scavengers is, surprisingly and unexpectedly, substantially increased confirming synergistic effect of the scavenging additive composition of the present invention.

(138) The above experimental findings confirm surprising, and unexpected technical effects and advantages, and synergistic property of the presently provided hydrogen sulfide scavenging additive compositions.

(139) The above findings also confirm that compositions of the present invention have technical advantages and surprising effects over the prior art and comparative additives and compositions.

(140) It may be noted that the present invention has been described with the help of foregoing examples, which are not intended to limit scope of the present invention, but are only illustrative.

(141) Furthermore, as amount of the prior art additive (i.e. triazine) has been substantially reduced to achieve desired scavenging efficiency, the present compositions are more economical and environmental friendly.

(142) It may be noted that the term about as employed herein is not intended to enlarge scope of claimed invention, but has been incorporated only to include permissible experimental errors of the field of the present invention.