CA2023298C - Process for the preparation of a new polymer useful for drag reduction in hydrocarbon fluids in exceptionally dilute polymer solutions - Google Patents
Process for the preparation of a new polymer useful for drag reduction in hydrocarbon fluids in exceptionally dilute polymer solutionsInfo
- Publication number
- CA2023298C CA2023298C CA002023298A CA2023298A CA2023298C CA 2023298 C CA2023298 C CA 2023298C CA 002023298 A CA002023298 A CA 002023298A CA 2023298 A CA2023298 A CA 2023298A CA 2023298 C CA2023298 C CA 2023298C
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- CA
- Canada
- Prior art keywords
- polymer
- monomers
- monomer
- acrylate
- hydrocarbon fluid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 79
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 31
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 31
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 31
- 239000012530 fluid Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 42
- 239000000178 monomer Substances 0.000 claims abstract description 51
- 239000000654 additive Substances 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 229940048053 acrylate Drugs 0.000 claims description 10
- 239000003350 kerosene Substances 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000004159 Potassium persulphate Substances 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 5
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical class C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical class CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical class [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 229940047670 sodium acrylate Drugs 0.000 claims description 4
- 235000010234 sodium benzoate Nutrition 0.000 claims description 4
- 239000004299 sodium benzoate Substances 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 4
- 239000004296 sodium metabisulphite Substances 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 239000010779 crude oil Substances 0.000 claims description 3
- -1 diesel Substances 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004153 Potassium bromate Substances 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000006184 cosolvent Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 239000003502 gasoline Substances 0.000 claims description 2
- 235000019396 potassium bromate Nutrition 0.000 claims description 2
- 229940094037 potassium bromate Drugs 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000012875 nonionic emulsifier Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 10
- 239000002798 polar solvent Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002113 octoxynol Polymers 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- AZNBLDHKBIGSFE-UHFFFAOYSA-M 1-ethenylpyridin-1-ium;acetate Chemical compound CC([O-])=O.C=C[N+]1=CC=CC=C1 AZNBLDHKBIGSFE-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- SFNKFWTXVGXCKP-UHFFFAOYSA-M dodecyl 2-methylprop-2-enoate;1-ethenylpyridin-1-ium;styrene;acetate Chemical compound CC([O-])=O.C=CC1=CC=CC=C1.C=C[N+]1=CC=CC=C1.CCCCCCCCCCCCOC(=O)C(C)=C SFNKFWTXVGXCKP-UHFFFAOYSA-M 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- FFUKBEULKQOABB-UHFFFAOYSA-M sodium;dodecyl 2-methylprop-2-enoate;2-methylprop-2-enoate;styrene Chemical compound [Na+].CC(=C)C([O-])=O.C=CC1=CC=CC=C1.CCCCCCCCCCCCOC(=O)C(C)=C FFUKBEULKQOABB-UHFFFAOYSA-M 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Novel polymer for drag reduction in hydrocarbon fluids is dis-closed which comprises polymerising a C-12 to C-18 acrylate or methacrylate monomer and an ionic with or without other monomers acting as fillers or additives at a temperature between 20 and 30°C with constant stirring and separating the resultant polymer.
The preparation of the polymers is simple, shear stability is good even at high shear rates, insensitivity to the presence of any other polar solvent and good solubility in almost all the hydrocarbon liquids. The novel polymer reduces friction in the flow of a hydrocarbon fluid by a factor around 5 at concentra-tions as low as 1 to 25 ppm.
The preparation of the polymers is simple, shear stability is good even at high shear rates, insensitivity to the presence of any other polar solvent and good solubility in almost all the hydrocarbon liquids. The novel polymer reduces friction in the flow of a hydrocarbon fluid by a factor around 5 at concentra-tions as low as 1 to 25 ppm.
Description
'_ This invention relates to a process for the preparation of a novel polymer useful for drag reduction in hydrocarbon fluids in exceptionally dilute polymer solutions.
In the pipe line transportation of fluids, there is drop in fluid pressure due to friction at pipe wall. Therefore, for a given pipe line, fluid must be transported with sufficient pressure to achieve the desired throughput. Since the pressure drops with the increase in flow rate, more pressure must be applied to increase the flow rate. There are design limitations for a given pipe line to withstand higher levels of pressure.
However, when the flow is turbulent in pipe lines, flow rate can be enhanced by the addition of high molecular weight polymeric additives. The role of these additives is to suppress the growth of turbulent eddies, which results in higher flow rate at a constant pumping pressure. The phenomenon is described as drag reduction and can be used to boost flows of crude oil and other hydrocarbon liquids in commercial pipe lines.
Use of polymeric additives for drag reduction is known.
Polymers based on alpha-olefins and other diene monomers have been reported to reduce drag in commercial pipe lines. For example reference is made to U.S. Patent Nos. 3,559,664 (1971), 3,827,447 (1974), 3,857,402 (1974) and 3,865,124 (1975). ~se of polymers based on vinyl monomers and co-monomers has also been reported. Reference is also made to Polymer Engineering And Science, Mid-May, 1980, Vol. 20, No. 7. Some reports are avail-able in which interpolymer complexes have been used as drag reducers. Reference is made to U.S. Patent No. 4,508,128 (1985).
Processes involving use of poly alpha-olefins suffer from ~_ . 2 the following drawbacks :
1. Shear stability of the polymers is poor.
In the pipe line transportation of fluids, there is drop in fluid pressure due to friction at pipe wall. Therefore, for a given pipe line, fluid must be transported with sufficient pressure to achieve the desired throughput. Since the pressure drops with the increase in flow rate, more pressure must be applied to increase the flow rate. There are design limitations for a given pipe line to withstand higher levels of pressure.
However, when the flow is turbulent in pipe lines, flow rate can be enhanced by the addition of high molecular weight polymeric additives. The role of these additives is to suppress the growth of turbulent eddies, which results in higher flow rate at a constant pumping pressure. The phenomenon is described as drag reduction and can be used to boost flows of crude oil and other hydrocarbon liquids in commercial pipe lines.
Use of polymeric additives for drag reduction is known.
Polymers based on alpha-olefins and other diene monomers have been reported to reduce drag in commercial pipe lines. For example reference is made to U.S. Patent Nos. 3,559,664 (1971), 3,827,447 (1974), 3,857,402 (1974) and 3,865,124 (1975). ~se of polymers based on vinyl monomers and co-monomers has also been reported. Reference is also made to Polymer Engineering And Science, Mid-May, 1980, Vol. 20, No. 7. Some reports are avail-able in which interpolymer complexes have been used as drag reducers. Reference is made to U.S. Patent No. 4,508,128 (1985).
Processes involving use of poly alpha-olefins suffer from ~_ . 2 the following drawbacks :
1. Shear stability of the polymers is poor.
2. Requires elaborate technique for the manufacture of polymers.
3. Cost of the polymeric additive is high.
Use of acrylate polymers, for pipe line transportation is not commercially attractive as they are required in higher con-centrations for effective drag reduction.
Polymers based on intermolecular complexes, are reported to perform at concentrations of 250 to 1000 ppm, which is quite high for commercial purposes. Moreover, such polymers are sensi-tive to the presence of any polar co-solvent i.e. they may lose their drag reduction activity in the presence of such solvents.
The primary advantage of the new polymer of the invention is that it reduces friction in the flow of a hydrocarbon fluid by a factor of around 5 at concentrations as low as 1 to 25 parts per million by weight, for instance, drag reduction of 76% in diesel at 25 parts per million by weight.
Another advantage is the simple method of producing the polymer i.e. by polymerisation technique which yields a linear and high molecular weight product.
Yet another advantage is the good solubility of the polymer in almost all the hydrocarbon liquids including benzene, toluene, xylene, diesel, kerosene, gasoline and crude oil.
A further advantage is the polymer's insensitivity to the presence of any other polar co-solvents e.g. n-butyl alcohol up to 10% by volume.
Yet a further advantage is that the polymer is shear stable even at high shear rates that is, the additive does not lose its drag reduction effectiveness at high shear rates.
The object of the invention is to provide a process for the preparation of a novel polymer useful for drag reduction in hydrocarbon fluids which overcomes the drawbacks hereinbefore outlined.
Accordingly, the present invention provides a process for the preparation of a polymer useful for drag reduction in a hydrocarbon fluid, said process comprising polymerizing monomers consisting essentially of a C-12 to C-18 acrylate or methacrylate monomer and an ionic monomer with or without other monomers acting as fillers or additives, which ionic monomer and other monomers do not substantially impair the usefulness of said polymer for said drag reduction, said ionic monomer being selected from the group consisting of sodium acrylate; sodium methacrylate, 4-vinyl sodium benzoate and 4-vinyl pyridinium salts of iodide, chloride and acetate and being present~in an amount of between about 0.05 to 0.1 moles per hundred grams of the polymer, said polymerization being effected at a temperature between 20~ and 30~ C. with constant stirring whereupon said monomers form a linear polymer which is soluble in said hydrocarbon fluid and useful for said drag reduction, said process further comprising recovering the resultant linear polymer.
The polymers prepared by this process are believed to be novel and form another aspect of the invention. Hydrocarbon fluids admixed with the novel polymers and a process for _ 4 transporting through a pipeline a hydrocarbon fluid admixed with the novel polymer constitute further aspects of the invention.
Any C-12 to C-18 acrylate or methacrylate ester individually or in combination can be used. The quantity of the ester monomer in the polymer should be more than 40%.
Concentration of the ionic monomer per hundred grams of the terpolymer can vary between 0.05 moles and 0.1 moles.
Monomers acting as fillers or additives may be selected from styrene monomers, acrylate monomers having less than 12 carbon atoms and vinyl monomers.
The process of the present invention can be effected by v~l~ional methods. For example, it can be effected by subject-ing the monomers in the presence of deionized water, a water soluble initiator and an emulsifier to the step of polymerization, at a temperature between 20~ and 30~ C. and at a pH between 4 and 6, with agitation.
The polymerisation may be affected in the presence of 0.2 to 0.6 % by weight of monomers of initiators such as potassium bromate/sodium sulphate, a combination of potassium persulphate with ferrous sulphate and sodium meta bisulphite and 4 to 12 ~ by weight of monomers of emulsifiers such as sodium lauryl sulphate, Triton X-100 .
The speed of agitation can be maintained between 250 and 400 rpm. The polymer can be isolated by known methods by either heating the emulsion at about 60 to 70~ C. under vacuum or by direct precipitation in a non-solvent such as methanol.
The coagulated polymer is filtered and dried at about 60~ C.
Trade-mark 4a " 27455-1 under vacuum. Such dried polymer is dissolved in a suitable hydrocarbon liquid in concentrations between 5 and 12 grams of polymer per 100 ml of hydrocarbon liquid.
The reduced viscosity of 0.5 % solution of the polymer should be more than 22 dl/g as determined by Cannon - Ubblehode dilution viscometer, using toluene as solvent at 25~ C.
The required concentration of polymer in hydrocarbon liquid for effective drag reduction can be between 1 and 25 parts per million by weight of the polymer.
The extent of drag reduction by the polymer is evaluated in a pipe loop by measuring pressure drops due to the flow of hydrocarbon liquid and due to that of 1.0 to 25 ppm solution of Trade-mark -polymer in hydrocarbon liquid.
The invention is described with reference to the following examples which should not be construed to limit the scope of the invention :
45 gram dodecyl methacrylate 50 gram styrene 5 gram sodium methacrylate 275 ml. distilled water 12 gram Triton X - 100 0.2 gram potassium persulphate 0.2 gram sodium meta bisulphite 0.001 gram FeSO4 To a clean 500 ml reactor, all the above ingredients were charged (except the initiator system) under the positive pressure of nitrogen. After an hour of nitrogen bubbling, the initiator system was introduced to the reactor under agitation. The reaction was continued for 6 hours, maintaining the temperature at 25~C. After the reaction was complete, the polymer was precipitated from the emulsion in cold methanol. The resulting polymer was filtered and dried under vacuum at 60~C for 4 hours.
Yield of isolated polymer was more than 98%.
The polymer yielded is Poly (dodecyl methacrylate -styrene - sodium methacrylate). The polymer was dissolved in toluene in concentration of about 10 gram polymer per 100 ml. of toluene by allowing the polymer to swell in the solvent for 7 days.
Figure - 1 of the drawings accompanying the specifica-tions gives the relative performance of drag reduction of a 10 ~_ . 6 ppm solution of the terpolymer in kerosene. It can be seen from the figure that the polymer retains about 60~ of its performance even after ten passes in a 50 cm. long capillary of 3 mm diameter at a typical wall shear rate of 10,500 per second.
The performance of the polymer was evaluated by pumping a solution of known concentration of the polymer of this invention in a hydrocarbon fluid through a 9.3 mm. pipe loop. Pressure drops were monitored across 30 cm. straight segment of the pipe by means of differential pressure transmitter. Flow rates were measured by means of a mechanical vane type of flow meter.
Percent drag reduction was calculated using the following equation :
Pressure drop Pressure drop with solvent - with solution % Drag Reduction = ------------------------------------ X 100 Pressure drop with solvent Pressure drop is measured at a constant volumetric flow rate. The results are tabulated in Table 1.
Table - 1 Drag reduction data at various additive concentrations.
Polymer Reynolds Liquid Drag Reduction concentration number ( ppm ) 01 27,000 xylene 28 11,000 kerosene 53 11,000 kerosene 34 05 28,000 diesel/kerosene 30 28,000 diesel/kerosene 76 -41.75 gram dodecyl methacrylate 50 gram styrene 8.25 gram vinyl pyridinium acetate 275 ml distilled water 12 gram Triton X - 100 0.2 gram potassium persulphate 0.2 gram sodium meta bisulphite 0.001 gram FeS04 The polymer yielded is Poly (dodecyl methacrylate -styrene - vinyl pyridinium acetate).
The procedure for the preparation of the polymer is essentially the same as described in Example - 1.
Drag reduction characteristics of the polymer were studied by the method explained in Example - 1 and the results are tabulated in Table - 2.
Drag reduction data at various additive concentrations.
Polymer Reynolds Liquid Drag Reduction concentration number ( ppm ) 05 28,000 diesel/kerosene 34 27,000 xylene 38 11,000 kerosene 34
Use of acrylate polymers, for pipe line transportation is not commercially attractive as they are required in higher con-centrations for effective drag reduction.
Polymers based on intermolecular complexes, are reported to perform at concentrations of 250 to 1000 ppm, which is quite high for commercial purposes. Moreover, such polymers are sensi-tive to the presence of any polar co-solvent i.e. they may lose their drag reduction activity in the presence of such solvents.
The primary advantage of the new polymer of the invention is that it reduces friction in the flow of a hydrocarbon fluid by a factor of around 5 at concentrations as low as 1 to 25 parts per million by weight, for instance, drag reduction of 76% in diesel at 25 parts per million by weight.
Another advantage is the simple method of producing the polymer i.e. by polymerisation technique which yields a linear and high molecular weight product.
Yet another advantage is the good solubility of the polymer in almost all the hydrocarbon liquids including benzene, toluene, xylene, diesel, kerosene, gasoline and crude oil.
A further advantage is the polymer's insensitivity to the presence of any other polar co-solvents e.g. n-butyl alcohol up to 10% by volume.
Yet a further advantage is that the polymer is shear stable even at high shear rates that is, the additive does not lose its drag reduction effectiveness at high shear rates.
The object of the invention is to provide a process for the preparation of a novel polymer useful for drag reduction in hydrocarbon fluids which overcomes the drawbacks hereinbefore outlined.
Accordingly, the present invention provides a process for the preparation of a polymer useful for drag reduction in a hydrocarbon fluid, said process comprising polymerizing monomers consisting essentially of a C-12 to C-18 acrylate or methacrylate monomer and an ionic monomer with or without other monomers acting as fillers or additives, which ionic monomer and other monomers do not substantially impair the usefulness of said polymer for said drag reduction, said ionic monomer being selected from the group consisting of sodium acrylate; sodium methacrylate, 4-vinyl sodium benzoate and 4-vinyl pyridinium salts of iodide, chloride and acetate and being present~in an amount of between about 0.05 to 0.1 moles per hundred grams of the polymer, said polymerization being effected at a temperature between 20~ and 30~ C. with constant stirring whereupon said monomers form a linear polymer which is soluble in said hydrocarbon fluid and useful for said drag reduction, said process further comprising recovering the resultant linear polymer.
The polymers prepared by this process are believed to be novel and form another aspect of the invention. Hydrocarbon fluids admixed with the novel polymers and a process for _ 4 transporting through a pipeline a hydrocarbon fluid admixed with the novel polymer constitute further aspects of the invention.
Any C-12 to C-18 acrylate or methacrylate ester individually or in combination can be used. The quantity of the ester monomer in the polymer should be more than 40%.
Concentration of the ionic monomer per hundred grams of the terpolymer can vary between 0.05 moles and 0.1 moles.
Monomers acting as fillers or additives may be selected from styrene monomers, acrylate monomers having less than 12 carbon atoms and vinyl monomers.
The process of the present invention can be effected by v~l~ional methods. For example, it can be effected by subject-ing the monomers in the presence of deionized water, a water soluble initiator and an emulsifier to the step of polymerization, at a temperature between 20~ and 30~ C. and at a pH between 4 and 6, with agitation.
The polymerisation may be affected in the presence of 0.2 to 0.6 % by weight of monomers of initiators such as potassium bromate/sodium sulphate, a combination of potassium persulphate with ferrous sulphate and sodium meta bisulphite and 4 to 12 ~ by weight of monomers of emulsifiers such as sodium lauryl sulphate, Triton X-100 .
The speed of agitation can be maintained between 250 and 400 rpm. The polymer can be isolated by known methods by either heating the emulsion at about 60 to 70~ C. under vacuum or by direct precipitation in a non-solvent such as methanol.
The coagulated polymer is filtered and dried at about 60~ C.
Trade-mark 4a " 27455-1 under vacuum. Such dried polymer is dissolved in a suitable hydrocarbon liquid in concentrations between 5 and 12 grams of polymer per 100 ml of hydrocarbon liquid.
The reduced viscosity of 0.5 % solution of the polymer should be more than 22 dl/g as determined by Cannon - Ubblehode dilution viscometer, using toluene as solvent at 25~ C.
The required concentration of polymer in hydrocarbon liquid for effective drag reduction can be between 1 and 25 parts per million by weight of the polymer.
The extent of drag reduction by the polymer is evaluated in a pipe loop by measuring pressure drops due to the flow of hydrocarbon liquid and due to that of 1.0 to 25 ppm solution of Trade-mark -polymer in hydrocarbon liquid.
The invention is described with reference to the following examples which should not be construed to limit the scope of the invention :
45 gram dodecyl methacrylate 50 gram styrene 5 gram sodium methacrylate 275 ml. distilled water 12 gram Triton X - 100 0.2 gram potassium persulphate 0.2 gram sodium meta bisulphite 0.001 gram FeSO4 To a clean 500 ml reactor, all the above ingredients were charged (except the initiator system) under the positive pressure of nitrogen. After an hour of nitrogen bubbling, the initiator system was introduced to the reactor under agitation. The reaction was continued for 6 hours, maintaining the temperature at 25~C. After the reaction was complete, the polymer was precipitated from the emulsion in cold methanol. The resulting polymer was filtered and dried under vacuum at 60~C for 4 hours.
Yield of isolated polymer was more than 98%.
The polymer yielded is Poly (dodecyl methacrylate -styrene - sodium methacrylate). The polymer was dissolved in toluene in concentration of about 10 gram polymer per 100 ml. of toluene by allowing the polymer to swell in the solvent for 7 days.
Figure - 1 of the drawings accompanying the specifica-tions gives the relative performance of drag reduction of a 10 ~_ . 6 ppm solution of the terpolymer in kerosene. It can be seen from the figure that the polymer retains about 60~ of its performance even after ten passes in a 50 cm. long capillary of 3 mm diameter at a typical wall shear rate of 10,500 per second.
The performance of the polymer was evaluated by pumping a solution of known concentration of the polymer of this invention in a hydrocarbon fluid through a 9.3 mm. pipe loop. Pressure drops were monitored across 30 cm. straight segment of the pipe by means of differential pressure transmitter. Flow rates were measured by means of a mechanical vane type of flow meter.
Percent drag reduction was calculated using the following equation :
Pressure drop Pressure drop with solvent - with solution % Drag Reduction = ------------------------------------ X 100 Pressure drop with solvent Pressure drop is measured at a constant volumetric flow rate. The results are tabulated in Table 1.
Table - 1 Drag reduction data at various additive concentrations.
Polymer Reynolds Liquid Drag Reduction concentration number ( ppm ) 01 27,000 xylene 28 11,000 kerosene 53 11,000 kerosene 34 05 28,000 diesel/kerosene 30 28,000 diesel/kerosene 76 -41.75 gram dodecyl methacrylate 50 gram styrene 8.25 gram vinyl pyridinium acetate 275 ml distilled water 12 gram Triton X - 100 0.2 gram potassium persulphate 0.2 gram sodium meta bisulphite 0.001 gram FeS04 The polymer yielded is Poly (dodecyl methacrylate -styrene - vinyl pyridinium acetate).
The procedure for the preparation of the polymer is essentially the same as described in Example - 1.
Drag reduction characteristics of the polymer were studied by the method explained in Example - 1 and the results are tabulated in Table - 2.
Drag reduction data at various additive concentrations.
Polymer Reynolds Liquid Drag Reduction concentration number ( ppm ) 05 28,000 diesel/kerosene 34 27,000 xylene 38 11,000 kerosene 34
Claims (22)
1. A process for the preparation of a polymer useful for drag reduction in a hydrocarbon fluid, said process comprising polymerizing monomers consisting essentially of a C-12 to C-18 acrylate or methacrylate monomer and an ionic monomer with or without other monomers acting as fillers or additives, which ionic monomer and other monomers do not substantially impair the usefulness of said polymer for said drag reduction, said ionic monomer being selected from the group consisting of sodium acrylate; sodium methacrylate; 4-vinyl sodium benzoate and 4-vinyl pyridinium salts of iodide, chloride and acetate and being present in an amount of between about 0.05 to 0.1 moles per hundred grams of the polymer, said polymerization being effected at a temperature between 20° and 30° C. with constant stirring whereupon said monomers form a linear polymer which is soluble in said hydrocarbon fluid and useful for said drag reduction, said process further comprising recovering the resultant linear polymer.
2. The process as claimed in claim 1, wherein the amount of acrylate or methacrylate monomer in the polymer is more than 40 % by weight.
3. The process as claimed in claim 1, wherein the polymerization is effected using a water-soluble Redox system as initiator.
4. The process as claimed in claim 1, wherein the polymerization is effected using initiators selected from a combination of potassium persulphate, ferrous sulphate, and sodium meta bisulphite or a combination of potassium bromate, sodium sulphate and potassium persulphate.
5. The process as claimed in claim 1, wherein the polymerization is effected using a water-soluble non-ionic emulsifier.
6. The process as claimed in claim 1, wherein the polymerization is effected using sodium lauryl sulphate as emulsifier.
7. The process as claimed in claim 3, wherein the amount of initiator ranges from 0.2 to 0.6 % by weight of monomer.
8. The process as claimed in claim 4, wherein the amount of emulsifier ranges from 4 to 12 % by weight of monomer.
9. The process as claimed in claim 1, wherein the polymerization is effected at a pH of 4 to 6.
10. The process as claimed in claim 1, wherein the monomers acting as fillers or additives are selected from styrene monomers, acrylate monomers having less than 12 carbon atoms and vinyl monomers.
11. A polymer produced by the process of claim 1.
12. A polymer produced by the process of claim 2.
13. A process for the preparation of an agent which reduces drag in a hydrocarbon fluid, said process consisting essentially of (a) polymerizing monomers consisting essentially of a C-12 to C-18 acrylate or methacrylate monomer and an ionic monomer with or without other monomers acting as fillers are additives, said ionic and other monomers being such that they do not substantially impair the usefulness of said polymer for drag reduction, said ionic monomer being selected from the group consisting of sodium acrylate, sodium methacrylate, 4-vinyl sodium benzoate and 4-vinyl pyridinium salts of iodide, chloride and acetate and being present in an amount of between about 0.05 to 0.1 moles per hundred grams of the polymer, said polymeriza-tion being effected at a temperature between 20° and 30° C. with constant stirring whereupon said monomers form a linear polymer which is soluble in said hydrocarbon fluid and useful for said drag reduction, and (b) recovering the resultant linear polymer.
14. The process as in claim 13, wherein the hydrocarbon fluid is benzene, toluene, xylene, diesel, kerosene, gasoline, or crude oil.
15. A polymer produced by the process of claim 13.
16. A process for reducing friction in the flow of a hydrocarbon fluid by adding a polymer of high molecular weight to the fluid, the process comprising forming said polymer by polymerizing a C-12 to C-18 acrylate or methacrylate monomer and an ionic monomer to form a resultant polymer which is linear and soluble in said fluid, said ionic monomer being selected from the group consisting of sodium acrylate, sodium methacrylate, 4-vinyl sodium benzoate and 4-vinyl pyridinium salts of iodide, chloride and acetate and being present in an amount of between about 0.05 to 0.1 mole per hundred grams of the resultant polymer, said polymerization being effected at a temperature between 20° and 30° C. with constant stirring, recovering the resultant polymer, and dissolving the resultant polymer in said hydrocarbon fluid thereby to reduce friction in the flow of said fluid.
17. The process as claimed in claim 16, wherein said acrylate or methacrylate monomer is present in said resultant polymer in an amount of more than 40 % by weight.
18. The process as claimed in claim 17, wherein the polymerization of the acrylate or methacrylate monomer and the ionic monomer is carried out in the presence of a monomer acting as a filler or additive which does not substantially impair the ability of said resultant polymer to reduce friction in the flow of said fluid, such that the polymerization results in the formation of a terpolymer which includes said filler or additive.
19. The process as claimed in claim 18, wherein the resultant polymer is dissolved in said hydrocarbon fluid at a concentration of between 1 to 25 parts per million.
20. The process as claimed in claim 19, wherein said solvent further comprises a polar co-solvent in an amount of up to 10 % by volume.
21. A hydrocarbon fluid admixed with a polymer as claimed in claim 11, 12 or 15, the polymer being present in an amount of 1 to 25 parts per million parts of hydrocarbon fluid.
22. A process which comprises transporting a hydrocarbon fluid through a pipeline, wherein there is present in the hydrocarbon fluid being transported from 1 to 25 parts per million of a polymer as claimed in claim 11, 12 or 15.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN160DE1990 IN176862B (en) | 1990-02-22 | 1990-02-22 | |
| IN160/DEL/90 | 1990-02-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2023298A1 CA2023298A1 (en) | 1991-08-23 |
| CA2023298C true CA2023298C (en) | 1997-04-29 |
Family
ID=11088513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002023298A Expired - Lifetime CA2023298C (en) | 1990-02-22 | 1990-08-15 | Process for the preparation of a new polymer useful for drag reduction in hydrocarbon fluids in exceptionally dilute polymer solutions |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA2023298C (en) |
| IN (1) | IN176862B (en) |
-
1990
- 1990-02-22 IN IN160DE1990 patent/IN176862B/en unknown
- 1990-08-15 CA CA002023298A patent/CA2023298C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CA2023298A1 (en) | 1991-08-23 |
| IN176862B (en) | 1996-09-21 |
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| MKLA | Lapsed | ||
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Effective date: 20121202 |