A METHOD FOR PREVENTING OR RETARDING THE FORMATION OF GAS HYDRATES

Abstract: A composition for preventing or retarding the formation of gas hydrates or for reducing the tendency of gas hydrates to agglomerate, during the transport of a fluid comprising water and a hydrocarbon, through a conduit, comprising, (a) a polymer or copolymer selected from a terpolymer of vinyl pyrrolidone, vinyl caprolactam and an ammonium derivative monomer having from 6 to 12 carbon atoms, selected from the group consisting of dialkyl aminoalkyl methacrylamide, dialkyl dialkenyl ammonium halide and a dialkylamino alkyl acrylate or methacrylate, a copolymer of vinyl pyrrolidone and vinyl caprolactam, and a homopolymer of vinyl caprolactam, and (b) an alcohol containing three to five carbon atoms and one hydroxy group, or a low molecular weight glycol ether containing an alkoxy group having at least 3 carbon atoms.

Description: A METHOD FOR PREVENTING OR RETARDING THE FORMATION OF GAS HYDRATES BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to a method for preventing or retarding the formation of gas hydrates or for reducing the tendency of such hydrates to agglomerate during the transport of a fluid comprising water and a hydrocarbon through a conduit, and, more particularly, to the addition of a mixture of a polyvinyl pyrrolidone or caprolactam polymer and an alcohol or a glycol ether to the fluid to inhibit such gas hydrate formation. 2. Description of the Prior Art It is well known in the art that the formation of gas hydrates in a conduit, e.g. a pipeline, during the transport of liquids, such as oil, and gases, particularly lower hydrocarbons, e.g. methane, ethane, propane, butane, isobutane and natural gas is a serious problem, especially in areas with a low temperature in the winter season or in the sea. Generally the temperatures are so low that gas hydrate formation, due to the inevitable presence of co-produced water in the wells takes place, if no special steps are taken. Insulation decreases the chance of gas hydrate formation; however, if the field is relatively small and far away from the production platform, the costs of using insulation are too high to make such field economically attractive. It is also known to add anti-freeze compounds, for example, glycol or methanol, during transport to minimize gas hydrate formation; however, large quantities of these compounds are required to be effective which is expensive. Alkyl glycosides also have been used for this purpose. A representation of the prior art in this field are the following patents: U.S. Pats. 5,420,370; 5,432,292; 4,915,176; EPA 0526929A1; EPO 0323774A1; Can. Pat. Appln 2,073,577; WO 93/25798; WO 95/17579; Gas Hydrates and Hydrate Prevention 73 GPA Annual Convention, pgs 85-93; WO 96/08456; WO 96/08636; WO 93/25798; EPA 0457375A1; WO 9412761. SUMMARY OF THE INVENTION What is described herein is a composition for effectively preventing or retarding the formation of gas hydrates, or for reducing the tendency of gas hydrates to agglomerate, during the transport of a fluid comprising water and a hydrocarbon, through a conduit, comprising, (a) a polymer or copolymer of vinyl pyrrolidone (VP) and/or vinyl caprolactam (VC ) , preferably a terpolymer of vinyl pyrrolidone, vinyl caprolactam and an ammonium derivative monomer having from 6 to 12 carbon atoms, selected from the group consisting of dialkyl aminoalkyl methacrylamide, dialkyl dialkenyl ammonium halide and a dialkylamino alkyl acrylate or methacrylate, or a vinyl caprolactam homopolymer, and (b) an alcohol containing three to five carbon atoms and one hydroxy group, or a low molecular weight glycol ether containing an alkoxy group having at least 3 carbon atoms . In one embodiment of the invention, the polymer component of the inhibitor composition is a terpolymer of vinyl pyrrolidone, vinyl caprolactam and a dialkylaminoalkyl acrylate or methacrylate . DETAILED DESCRIPTION OF THE INVENTION Suitable terpolyτners for use in the composition of the invention are described in detail by Lorenz et al . in U.S. Pat. 4,521,404. A preferred terpolymer is Gaffix ® VC-713, which is sold by International Specialty Products, Wayne, New Jersey. Gaffix ® VC-713 is a terpolymer of 17-32% vinyl pyrrolidone, 65-80% vinyl caprolactam and 3-6% dimethylaminoethyl methacrylate, by weight . Another preferred polymer which exhibits inhibitory characteristics in the composition of the invention is a homopolymer of vinyl caprolactam (VCL) . Generally, the polymer is used in an amount of about 30 to 50% by weight of the composition, i.e. in admixture with the alcohol or glycol ether solvent . The polymer inhibition concentration in the pipeline, i.e. the aqueous phase is about 0.1 to 3% by weight; the solvent inhibition concentration accordingly, is about 0.1 to 5% by weight in the aqueous phase. Alcohols which are effective in providing the advantageous gas hydrate inhibition contain one hydroxy group and three to five carbon atoms. Representative alcohols are 1-pentanol; 1-butanol, also known as n-butyl alcohol; 2-methyl-2-propanol, also known as tert-butyl alcohol; 2-butanol, also known as sec-butyl alcohol; 2-propanol, also known as isopropyl alcohol; and 1-propanol, also known as propyl alcohol. Low molecular glycol ethers which are effective in providing the advantageous gas hydrate inhibition contain an alkoxy group having at least 3 carbon atoms . Representative glycol ethers are butyl cellosolve, which is ethylene glycol monobutyl ether; propylene glycol butyl ether; butyl carbitol or di (ethylene glycol) monobutyl ether; and 2-isopropoxy-ethanol . The following examples are provided to illustrate the invention. GENERAL METHOD The gas hydrate inhibition tests were conducted in a 300 ml stainless steel stirred autoclave at high pressure and low temperature. In a typical experiment, 0.25 to 1.0 wt% of the inhibitor composition was added to 120 g of a 3.5 wt% sea salt solution. The resulting mixture was transferred to the 300 ml autoclave and immersed in a constant temperature bath at 4°C. The pressure was then increased to 1000 psig with green canyon gas and held constant to within about 5 psi throughout the experiment with a programmable syringe pump. After the pressure reached 1000 psig, the autoclave stirrer was turned on to 1000 rpm. The gas volume, as measured by the syringe pump, the gas pressure, and the fluid temperature were measured and electronically recorded at 1 minute intervals throughout the experiment. Gas consumption indicates hydrate formation. The results are shown below in Tables 1 and 2. An extended inhibition time e.g. 350 minutes or greater, preferably 500 to > 1200, is indicative of a composition which provides the desired gas hydrate inhibition. Standard and comparative results are shown in Tables 3 and 4. TABLE 1 Composition Inhibition Polymer * Solvent** Time (min) Gaffix ® VC-713 1-pentanol 300 Gaffix ® VC-713 n-butyl alcohol 400 Gaffix ® VC-713 sec-butyl alcohol 700 Gaffix ® VC-713 tert-butyl alcohol 400 Gaffix ® VC-713 propyl alcohol 600 Gaffix ® VC-713 isopropyl alcohol 250 PVCL sec-butyl alcohol 540 VP/VCL (50:50) sec-butyl alcohol 450 * 0.5 wt% ** 0.75 wt' TABLE 2 Composition Inhibition Polymer * Solvent** Time i (min) Gaffix ® VC-713 Butyl Cellosolve > 1200 VCL Butyl Cellosolve > 1200 Gaffix ® VC-713 2-Isopropoxy ethanol 800 Gaffix ® VC-713 Butyl Carbitol 500 Gaffix ® VC-713 propylene glycol 600 propyl ether Gaffix ® VC-713 propylene glycol 450 butyl ether Gaffix ® VC-713 ethylene glycol 350 monopropyl ether VP/VCL (50:50) Butyl Cellosolve 350 * 0.5 wt% ** 0.75 wt' TABLE 3 None None 0 None n-butyl alcohol 0 Gaffix ® VC-713 None 2 Gaffix ® VC-713 Methanol 5 Gaffix ® VC-713 Ethanol 20 VCL Methanol 0 VCL/VP Methanol 0 TABLE 4 None None 0 None Butyl Cellosolve 0 Gaffix ® VC-713 None 2 Gaffix ® VC-713 Ethanol 43 VCL Methanol 0 VC /VP Methanol 0 Ganex ® P904 Butyl Cellosolve 50 Gaffix ® VC-713 Carbitol 0 Gaffix ® VC-713 Cellosolve 10 While the invention has been described with particular reference to certain embodiments thereof, it will be understood that changes and modifications may be made which are within the skill of the art. Accordingly, it is intended to be bound only by the following claims, in which:

Claims: WHAT IS CLAIMED IS 1. A composition for preventing or retarding the formation of gas hydrates or for reducing the tendency of gas hydrates to agglomerate, during the transport of a fluid comprising water and a hydrocarbon, through a conduit, comprising, (a) a polymer or copolymer selected from a terpolymer of vinyl pyrrolidone, vinyl caprolactam and an ammonium derivative monomer having from 6 to 12 carbon atoms, selected from the group consisting of dialkyl aminoalkyl methacrylamide, dialkyl dialkenyl ammonium halide and a dialkylamino alkyl acrylate or methacrylate, a copolymer of vinyl pyrrolidone and vinyl caprolactam, and a homopolymer of vinyl caprolactam, and (b) an alcohol containing three to five carbon atoms and one hydroxy group, or a low molecular weight glycol ether containing an alkoxy group having at least 3 carbon atoms . 2. A composition according to claim 1 wherein said terpolymer includes an ammonium derivative monomer which is dimethylaminoethyl methacrylate . 3. A composition according to claim 1 wherein said terpolymer comprises, by weight, about 17-32% vinyl pyrrolidone, about 65-80% vinyl caprolactam and about 3-6% of said ammonium derivative monomer. 4. A composition according to claim 1 wherein said copolymer comprises vinyl pyrrolidone and vinyl caprolactam, or a homopolymer of vinyl caprolactam. 5. A composition according to claim 1 wherein said glycol ether is ethylene glycol monobutyl ether, di (ethylene glycol) monobutyl ether, 2-isopropoxyethanol, propylene glycol propyl ether, propylene glycol butyl ether, or ethylene glycol monopropyl ether. 6. A composition according to claim 1 wherein said alcohol is propyl alcohol, sec-butyl alcohol, n-butyl alcohol, tert-butyl alcohol, isopropyl alcohol, or 1-pentanol . 7. A composition according to claim 1 wherein said polymer comprises about 20 to 50% by weight of said composition. 8. A method of preventing or retarding the formation of gas hydrates or for reducing the tendency of gas hydrates to agglomerate, during the transport of a fluid comprising water and a hydrocarbon, through a conduit which comprises including a composition comprising (a) a polymer or copolymer selected from a terpolymer of vinyl py rrolidone, vinyl caprolactam and an ammonium derivative monomer having from 6 to 12 carbon atoms, selected from the group consisting of dialkyl aminoalkyl methacrylamide, dialkyl dialkenyl ammonium halide and a dialkylamino alkyl acrylate or methacrylate, a copolymer of vinyl pyrrolidone and vinyl caprolactam, and a homopolymer of vinyl caprolactam, and (b) an alcohol containing three to five carbon atoms and one hydroxy group, or a low molecular weight glycol ether containing an alkoxy group having at least 3 carbon atoms to said fluid.

Inventors: COHEN JEFFREY M, WOLF PHILIP F, YOUNG WILLIAM D, COHEN, JEFFREY, M., WOLF, PHILIP, F., YOUNG, WILLIAM, D.
Applicants: ISP INVESTMENTS INC, ISP INVESTMENTS INC.
Application year: 1997
Main classification: C07C7
IPC codes: C07C7, C07C9, C09K8, C10L1, C10L3