CN1865172A - Oil displacement agent - Google Patents
Oil displacement agent Download PDFInfo
- Publication number
- CN1865172A CN1865172A CN 200510070800 CN200510070800A CN1865172A CN 1865172 A CN1865172 A CN 1865172A CN 200510070800 CN200510070800 CN 200510070800 CN 200510070800 A CN200510070800 A CN 200510070800A CN 1865172 A CN1865172 A CN 1865172A
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- China
- Prior art keywords
- oil
- water
- displacing agent
- agent
- salt
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- 238000006073 displacement reaction Methods 0.000 title abstract description 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 134
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011575 calcium Substances 0.000 claims abstract description 11
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 229940077388 benzenesulfonate Drugs 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims abstract description 4
- 159000000011 group IA salts Chemical class 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 12
- 235000011152 sodium sulphate Nutrition 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000012747 synergistic agent Substances 0.000 claims description 8
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 230000003750 conditioning effect Effects 0.000 claims description 4
- -1 phospho Chemical class 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 239000012745 toughening agent Substances 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 3
- 239000003352 sequestering agent Substances 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 114
- 239000000498 cooling water Substances 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 6
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 4
- 239000002738 chelating agent Substances 0.000 abstract description 2
- 239000002455 scale inhibitor Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 2
- 238000006065 biodegradation reaction Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 89
- 239000002699 waste material Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 20
- 238000012544 monitoring process Methods 0.000 description 15
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 230000005764 inhibitory process Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 7
- 239000003814 drug Substances 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 229910000926 A-3 tool steel Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000002826 coolant Substances 0.000 description 4
- 239000008235 industrial water Substances 0.000 description 4
- 230000000149 penetrating effect Effects 0.000 description 4
- CCVYRRGZDBSHFU-UHFFFAOYSA-N (2-hydroxyphenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC=C1O CCVYRRGZDBSHFU-UHFFFAOYSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000010962 carbon steel Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 3
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- AJVIQNYVMGYYOL-UHFFFAOYSA-M sodium;2-decylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O AJVIQNYVMGYYOL-UHFFFAOYSA-M 0.000 description 2
- ZIGVUIYVPLQEAL-UHFFFAOYSA-M sodium;2-tetradecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O ZIGVUIYVPLQEAL-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010729 system oil Substances 0.000 description 2
- 238000000207 volumetry Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000037358 bacterial metabolism Effects 0.000 description 1
- LOGBRYZYTBQBTB-UHFFFAOYSA-N butane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CC(O)=O LOGBRYZYTBQBTB-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000008935 nutritious Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- ZNRSXPDDVNZGEN-UHFFFAOYSA-K trisodium;chloride;sulfate Chemical compound [Na+].[Na+].[Na+].[Cl-].[O-]S([O-])(=O)=O ZNRSXPDDVNZGEN-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Lubricants (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention relates to an oil displacement agent suitable for oil-containing industrial circulating water and oil-containing wastewater, which comprises 38-62% of main agent and N-alkyl C based on 100% of the total weight of the composition8～24P-imido benzene sulfonate anionic surfactant; 0-12% of pH value regulator which is alkaline salt or alkali; contains 7 to 21 percent of synergist which is a chelating agent of calcium and magnesium ions; contains 18-30% of intensifier and is neutral salt. When the composite oil displacement agent is applied to an oil-containing industrial circulating cooling water system and oil-containing wastewater, the composite oil displacement agent has the characteristics of small dosage, good oil displacement effect, no toxicity, environmental friendliness and easiness in biodegradation, and has good synergistic effect on water treatment corrosion and scale inhibitors.
Description
Technical field
The present invention relates to a kind of oil-displacing agent, particularly a kind of oil-displacing agent that is mainly used in oil-containing industrial circulating water and the oily(waste)water system.
Background technology
The oil product that leakage is often arranged with waste water in the refinery industrial circulating water, the oil product of leakage make equipment commentaries on classics thermo-efficiency decline or blowdown be difficult for up to standard attached to the hardware surface; Oil film covers the recirculated water surface, and oxygen concn descends in the water body, and the anerobe reproduction speed increases, and total heterotrophic bacteria count is higher, and bacterial metabolism causes deteriorating water quality, and the equipment corrosion rate raises; Oil product and the sulfide that contains thereof lost efficacy the effective constituent of the biocide that adds in the industrial circulating water and corrosion-mitigation scale-inhibition medicament.
Do not use oil-displacing agent in refinery recirculated water and the waste water at present, after oil leak is gone into system, circulating water system needs the large excretion and large complement displacement, cause a large amount of wastes of water resources and water treatment agent, and, so only can replace the part of leak oil sludge in the recirculated water, also have a considerable amount of greasy dirts, be difficult to drive away attached to equipment, pipeline surface.Existing its host of Phenylsulfonic acid salt oil-displacing agent patent (as CN1281025A, CN1394935A, CN1337439A, CN1352224A, CN1426833A, CN1417284A, CN1373172A) mainly is with alkylsulfonate, is that auxiliary agent is composited with polymkeric substance (polyacrylamide), alkali or compound alkali, solubilizing agent and synergistic agent (alcohols).They all only are used for the displacement of reservoir oil of underground oil recovery, be applicable to the field that oil-contg is quite high, and oil-contg is all lower in oil-containing industrial circulating water or the industrial oily waste water, after they are applied to this field, oil displacement efficiency is all not remarkable, and because the singularity of industrial circulating water, the inhibition, Scale inhibitors and the biocide that require to be added in oil-displacing agent and the water treatment have good consistency (best and water treating corrosion, scale inhibition agent have synergistic effect).All reckon without this Application for Field in the existing displacement of reservoir oil medicament, nature can't be realized the effective application in oil-containing industrial circulating cooling water and the oil-containing industrial water, and a large amount of experiments also proves this point.
Summary of the invention
The object of the present invention is to provide a kind of oil-displacing agent that is particularly suitable for being applied to oil-containing industrial circulating cooling water and oil-containing industrial water.
Oil-displacing agent of the present invention is 100% in the constituent gross weight, and containing host in the composition is N-alkyl C
8～24To imido grpup benzene sulfonate anion surfactant, account for 38%～62%; PH value conditioning agent is alkaline salt or alkali, as sodium bicarbonate, saleratus, sodium hydroxide etc., can be one or more, accounts for 0～12%; Contain synergistic agent, it is the sequestrant of calcium, magnesium ion, can be in polyphosphoric acid or its salt, organic phospho acid or its salt, polyacrylic acid or its salt one or more, accounts for 7%～21%; Containing toughener is neutral salt, as sodium-chlor, Repone K, sodium sulfate etc., can be one or more, accounts for 18%～30%.
Principal feature of the present invention is to have used N-alkyl C
8～24To the host of imido grpup benzene sulfonate anion surfactant as oil-displacing agent, N-alkyl C
8～24Molecular formula to the imido grpup benzene sulfonic acid sodium salt is
R is identical or different C
8～C24In alkyl.Because N-alkyl C
8～24Molecular structure to imido grpup Phenylsulfonic acid salt has more singularity than alkyl sulfonates, and after using in oil-containing recirculated water and oily(waste)water system, the surfactivity flooding system can make between water and the greasy dirt and form 10
-3MN/m～10
-4MN/m ultra low interfacial tension, and improve wetting, the penetrating power of water reduces the bonding strength of irreducible oil in equipment surface effectively, make irreducible oil easily deformable, peel off, move, coalescence, make the oil product that is bled into water system be easy to expeling; Simultaneously, can effectively alleviate in the water quality that the system leak oil product causes nutritious, aggravation of bacterium algae propagation and equipment corrosion quickening, and this oil-displacing agent and Treatment of Industrial Water inhibition, scale inhibition agent have good synergetic property, strengthened inhibition, the scale-inhibiting properties of medicament.To be preferably alkyl be C to alkyl in the host
8-C
24
The adding of bases salt pH value conditioning agent among the present invention, make oil-displacing agent oil displacement efficiency under alkaline environment better, suitable pH value scope is 7.5～10.2, also operation (being generally 7.5～9.2) in this scope of the pH value of industrial circulating cooling water simultaneously, so, when this oil-displacing agent prescription was used in the oil-containing industrial circulating cooling water, bases salt can not add or add on a small quantity and can reach same oil displacement efficiency; In other non-alkaline oily(waste)water, should suitably add a certain amount of alkali according to the particular case of pH value in the water.
Employed synergistic agent is the sequestrant of calcium in the water, magnesium ion among the present invention, its adding is in order to reduce in the water metal ion such as calcium, magnesium to the influence of surfactivity host, especially in industrial circulating water, increase along with the recirculated water cycles of concentration, calcium, magnesium ion concentration sum can reach 600mg/l (in lime carbonate) in the water, this will make the activity of host descend, and oil-displacement capacity reduces.Employed synergistic agent can be polyphosphoric acid, organic phospho acid, polyacrylic acid and their salt or the like, its consumption should be determined according to the content of metal ions such as calcium, magnesium in the actual treatment oil-containing water system, calcium in the water quality, when magnesium ion content is high, can increase its consumption.If the synergistic agent consumption is too little, concentration of metal ions such as the calcium in the water, magnesium are too high, will influence the oil displacement efficiency of oil-displacing agent, otherwise then for causing the waste of synergistic agent, reagent cost increases.
Toughener is neutral salts such as sodium-chlor, sodium sulfate, after itself and host are compound, can further reduce the interfacial tension of profit, strengthens micellar cohesive force.These single agent also have an outstanding feature to be: it all perhaps has synergistic effect mutually with Treatment of Industrial Water medicament commonly used, be after compound oil displacement agent adds the oil-containing industrial circulating water, added inhibition in the recirculated water, scale inhibition agent performance are reduced, and the inhibition of original medicament, scale inhibition ability are strengthened.
Characteristics of the present invention are: a large amount of emphasis of existing chemical oil displacement agent is applied to underground oil recovery, and oil-displacing agent of the present invention is mainly used in the displacement of reservoir oil of oil-containing industrial circulating water and oily(waste)water, so the oil-displacing agent of its design according to theory is: the interfacial tension that reduces profit, make oil film and poly-, this is a factor that realizes the displacement of reservoir oil, but not topmost factor, because, after greasy dirt is bled in the water system, a large amount of greasy dirts is attached to hardware and pipe surface, therefore must improve wetting, the penetrating power of water, greasy dirt slave unit surface replacement is got off; In addition, owing to recycling of industrial circulating water, metal ion in the water quality (especially calcium, magnesium ion) concentration quite high (can reach 600mg/l sometimes) must add a certain amount of metal ion chelation agent, and the oil-displacement capacity of host is strengthened; Moreover, in order to prevent burn into fouling and bacterium algae propagation, added a certain amount of water treatment agent in the industrial circulating water, the adding of oil-displacing agent can not weaken inhibition, scale inhibition and the sterilization effect of original medicament, and preferably oil-displacing agent and original water treatment agent have synergy.According to such theory, the N-alkyl C that contains of the present invention
8～24To imido grpup benzene sulfonate compound oil displacement agent, pay attention to oil displacement efficiency and with the synergistic effect of water treatment agent.This oil-displacing agent should have the character of certain reduction oil water interfacial tension, and the wettability of the water that also will improve and perviousness reach compatible (or collaborative) character with water treatment agent, and crucial is the structure and the character of used active substance.
Its oil-displacement mechanism is:
1, the oil-displacing agent system can effectively reduce the interfacial tension between equipment surface and the irreducible oil, makes remaining oil in equipment surface be easy to peel off, and reaches the requirement effect.
2, the oil-displacing agent system can effectively reduce the interfacial tension between water and the irreducible oil, reduces alternate surface energy, helps the migration of elaioleucite.
3, in being bordering on neutral slight alkalinity water surrounding, because phenyl ring is a rigid radical, the phenyl ring both sides are NH in the host
2 +And SO
3 -, the NH of a host molecule
2 +SO with another host molecule
3 -Have intermolecular light current adsorption, this effect is that the irreducible oil particulate is migrated in water and the power of coalescence, helps improving oil displacement efficiency.
4, the oil-displacing agent system can effectively be improved the resistance to flow of viscous crude.
Oil-displacing agent of the present invention can reduce oil water interfacial tension, and it has extremely strong surfactivity and penetrating power; By its adding, the oil film that is dispersed in oil-containing water quality surface is easy to gather; The a large amount of greasy dirts that are adsorbed on equipment and pipe surface are easy to peel off, also gather, and help final expeling.
Practical application effect shows in industrial oil-containing recirculated water and oily(waste)water, and its oil displacement efficiency of oil-displacing agent of the present invention is higher than other present known oil-displacing agent product far away.This high-efficient oil-displacing agent uses effectively simple, its good water solubility, oil soluble is moderate, extremely strong surfactivity and penetrating power are arranged, oil displacement efficiency is good, and synergistic function is arranged with water treatment agent, after this oil-displacing agent adds oil-containing industrial cycle water system, water quality significantly descends to the corrosion rate of metal (especially carbon steel), the dirt deposition speed of equipment surface significantly reduces, and this oil-displacing agent is nontoxic, environmentally friendly, readily biodegradable, the displacement of reservoir oil of particularly suitable oil-containing industrial circulating water and oily(waste)water is particularly useful for the low oil-containing water system displacement of reservoir oil of greasy dirt content at 50mg/l～1000mg/l.
Embodiment
Use the oil-displacing agent that the present invention obtains, when greasy dirt content is higher than 50mg/l in the water system, carries out impact and add, carry out the oil displacement efficiency test, monitor its oil-displacement capacity and the influence of circulating water quality.Measure the method for oil-contg in the recirculated water, carry out according to China Petrochemical Industry's " water coolant analysis and test method " (93 years versions) (130) " mensuration of oil-contg " method (by the several times dilution).The calculating of displacement of reservoir oil rate is carried out as follows:
In the formula: B is smeary content in the water before the adding oil-displacing agent, mg/l;
C is smeary content in the water after the adding oil-displacing agent, mg/l.
It is foundation with the field monitoring interchanger that circulating cooling water quality sticks speed to corrosion of Carbon Steel rate and dirt.Test is carried out according to China Petrochemical Industry's " water coolant analysis and test method " (93 years versions) (409) " monitoring heat exchanger method of testing " method.Monitoring heat exchanger can insert three test tubes (I type) for self-control at every turn, and the average corrosion rate F of carbon steel heat-transfer surface is calculated as follows:
In the formula: the C-computational constant, when F unit is (millimeter/year), C=8.76 * 10
7
W
0The weight of test tube before the-test, gram/root;
W
2The weight of-test back test tube, gram/root;
The internal surface area of test tube before the A-test, centimetre 2/;
The T-test period, hour;
ρ-test tube material density, kg/m
3
Stick the lip-deep adhesion speed of thing in vitro, be calculated as follows:
In the formula: W
1-test back test tube weight, mg;
W
2-test is back with test tube weight after the pickling, mg;
A-is surface-area in vitro, centimetre
2/ root;
The T-test period, month.
Measurement of surface tension, laboratory apparatus are U.S. Texas500 type interfacial tensimeter.
Calcium, magnesium ion are measured in the water quality, and test is carried out according to China Petrochemical Industry's " water coolant analysis and test method " (93 years versions) (111) " EDTA volumetry " and (112) " minusing " method.(mg/l is with CaCO for calcium ion content X in the water sample
3Meter), be calculated as follows:
In the formula: the V-titration consumes the volume of EDTA standardized solution, ml;
The concentration of M-EDTA standardized solution, mol/l;
The Vw-volume of water sample, ml;
100.08-the lime carbonate molar mass, g/mol.
(mg/l is with CaCO for magnesium ion content X in the water sample
3Meter) mensuration is calculated as follows:
X＝Y-Z
In the formula: total hardness content and the calcium ion content measured simultaneously in Y, the Z-water sample, mg/l is with CaCO
3Meter.Total hard measuring method is carried out according to China Petrochemical Industry's " water coolant analysis and test method " (93 years versions) (110) " EDTA volumetry ", and total hard method of calculation are with " calcium ion concn method of calculation ".
Embodiment 1
Prepare oil-displacing agent by following proportioning:
The N-octyl is host 400Kg to the imido grpup benzene sulfonic acid sodium salt, sodium bicarbonate 0Kg (handle pH value is 8.9 in the water quality), polyacrylic acid 120kg, sodium sulfate 200kg, deionized water 280Kg.The oil-displacing agent total amount is 1000Kg.
Cooling water system greasy dirt content is 200mg/l.Add this oil-displacing agent 100mg/l in cooling water system, use the field monitoring interchanger, monitor the corrosion of A3 steel heat exchange test tube and stick rate behavior, the result is as shown in table 1:
The adding of table 1 oil-displacing agent is to the A3 steel corrosion and stick the speed impact effect
| Erosion rate (mm/a) | Stick speed (mcm) | Displacement of reservoir oil rate % | |
| Do not add oil-displacing agent | 0.08261 | 18.32 | |
| Add oil-displacing agent | 0.07187 | 13.37 | 82.5 |
Embodiment 2
Prepare oil-displacing agent by following proportioning:
The N-dodecyl is to imido grpup benzene sulfonic acid sodium salt 550Kg, yellow soda ash 60Kg, tripoly phosphate sodium STPP 150kg, sodium sulfate 220kg, deionized water 20Kg.The oil-displacing agent total amount is 1000Kg.
Greasy dirt content is 800mg/l in the industrial treatment waste water.Add this oil-displacing agent 100mg/l in cooling water system, the oil displacement efficiency analytical results is as shown in table 2:
The adding of table 2 oil-displacing agent influences the oily(waste)water oil displacement efficiency
| Sump oil content (mg/l) | Greasy dirt clearance % | |
| Before adding oil-displacing agent | 800 | |
| After adding oil-displacing agent | 75.3 | 90.63 |
Embodiment 3
Prepare oil-displacing agent by following proportioning:
The N-octadecyl is 420Kg to the imido grpup benzene sulfonic acid sodium salt, sodium bicarbonate 50Kg (circulating water system PH=7.2 need add a certain amount of alkali), hydroxy ethylene diphosphonic acid 180kg, sodium sulfate 260kg, deionized water 90Kg.The oil-displacing agent total amount is 1000Kg.
Refinery one follows the cooling water system oil leak, and greasy dirt content is 320mg/l.Add this oil-displacing agent 100mg/l in cooling water system, use the field monitoring interchanger, monitor the corrosion of A3 steel heat exchange test tube and stick rate behavior, the result is as shown in table 3:
The adding of table 3 oil-displacing agent is to the influence of water quality
| Erosion rate (mm/a) | Stick speed (mcm) | Displacement of reservoir oil rate % | |
| Do not add oil-displacing agent | 0.08261 | 18.32 | |
| Add oil-displacing agent | 0.07187 | 13.37 | 86.9 |
Embodiment 4
Prepare oil-displacing agent by following proportioning:
The N-tetracosyl is host 590Kg to the imido grpup benzene sulfonic acid sodium salt, potassium hydroxide 80Kg, 2-phosphonic acids butane 1,2,4-tricarboxylic acid 90kg, sodium-chlor 230kg, deionized water 10Kg.The oil-displacing agent total amount is 1000Kg.
Greasy dirt content is 80mg/l in refinery's waste discharge.In water, add this oil-displacing agent 100mg/l, its oil displacement efficiency of field monitoring, the result is as shown in table 4:
The adding of table 4 oil-displacing agent influences the oily(waste)water oil displacement efficiency
| Sump oil content (mg/l) | Greasy dirt clearance % | |
| Do not add oil-displacing agent | 80 | |
| After adding oil-displacing agent | 28.2 | 64.75 |
Embodiment 5
Prepare oil-displacing agent by following proportioning:
The N-hexadecyl is 420Kg to the imido grpup benzene sulfonic acid sodium salt, sodium bicarbonate 0Kg (circulating water system PH=8.6), hydroxy ethylene diphosphonic acid acid 180kg, sodium sulfate 260kg, deionized water 140Kg.The oil-displacing agent total amount is 1000Kg.
Refinery one follows the cooling water system oil leak, and greasy dirt content is 320mg/l.Add this oil-displacing agent 100mg/l in cooling water system, use the field monitoring interchanger, monitor the corrosion of A3 steel heat exchange test tube and stick rate behavior, the result is as shown in table 5:
The adding of table 5 oil-displacing agent is to the influence of water quality
| Erosion rate (mm/a) | Stick speed (mcm) | Displacement of reservoir oil rate % | |
| Do not add oil-displacing agent | 0.08261 | 18.32 | |
| Add oil-displacing agent | 0.07187 | 13.37 | 86.9 |
Embodiment 6
Prepare oil-displacing agent by following proportioning:
The N-tetracosyl is host 390Kg to the imido grpup benzene sulfonic acid sodium salt, sodium hydroxide 80Kg, sodium polyacrylate 75kg, sodium-chlor 230kg, deionized water 225Kg.The oil-displacing agent total amount is 1000Kg.
Greasy dirt content is 150mg/l in refinery's waste discharge.In water, add this oil-displacing agent 100mg/l, its oil displacement efficiency of field monitoring, the result is as shown in table 6:
The adding of table 6 oil-displacing agent influences the oily(waste)water oil displacement efficiency
| Sump oil content (mg/l) | Greasy dirt clearance % | |
| Do not add oil-displacing agent | 150 | |
| After adding oil-displacing agent | 32.2 | 78.53 |
Embodiment 7
Prepare oil-displacing agent by following proportioning:
The N-tetradecyl is host 600Kg to the imido grpup benzene sulfonic acid sodium salt, sodium hydroxide 100Kg (PH=6.1 in the water quality that handles), Sodium hexametaphosphate 99 80kg, sodium sulfate 220kg.The oil-displacing agent total amount is 1000Kg.
Greasy dirt content is 1000mg/l in refinery's waste discharge.In water, add this oil-displacing agent 100mg/l, its oil displacement efficiency of field monitoring, the result is as shown in table 7:
The adding of table 7 oil-displacing agent influences the oily(waste)water oil displacement efficiency
| Sump oil content (mg/l) | Greasy dirt clearance % | |
| Do not add oil-displacing agent | 1000 | |
| After adding oil-displacing agent | 82.7 | 91.73 |
Embodiment 8
Prepare oil-displacing agent by following proportioning:
The N-decyl is host 580Kg to the imido grpup benzene sulfonic acid sodium salt, sodium bicarbonate 50Kg, 2-HPAA 90kg, sodium sulfate 180kg, deionized water 100kg.The oil-displacing agent total amount is 1000Kg.
Greasy dirt content is 120mg/l in refinery's recirculated water.In water, add oil-displacing agent 100mg/l, its oil displacement efficiency of field monitoring, the result is as shown in table 8:
The adding of table 8 oil-displacing agent is to oil-containing industrial circulating water water quality impact
| Erosion rate (mm/a) | Stick speed (mcm) | Displacement of reservoir oil rate % | |
| Do not add oil-displacing agent | 0.09561 | 20.75 | |
| Add oil-displacing agent | 0.07187 | 13.37 | 77.8 |
Comparative Examples 1
Host N-decyl is replaced with the decyl benzene sulfonic acid sodium salt to the imido grpup benzene sulfonic acid sodium salt, and other presses embodiment 8 conditions preparation oil-displacing agent:
The decyl benzene sulfonic acid sodium salt is host 580Kg, sodium bicarbonate 50Kg, 2-HPAA 90kg, sodium sulfate 180kg, deionized water 100kg.The oil-displacing agent total amount is 1000Kg.
Greasy dirt content is 120mg/l in refinery's recirculated water.In water, add oil-displacing agent 100mg/l, its oil displacement efficiency of field monitoring, the result is as shown in table 9:
The adding of table 9 oil-displacing agent is to oil-containing industrial circulating water water quality impact
| Erosion rate (mm/a) | Stick speed (mcm) | Displacement of reservoir oil rate % | |
| Do not add oil-displacing agent | 0.09561 | 20.75 | |
| Add oil-displacing agent | 0.09235 | 19.20 | 6.92 |
Comparative Examples 2
Host N-tetradecyl is replaced with the tetradecyl benzene sulfonic acid sodium salt to the imido grpup benzene sulfonic acid sodium salt, and other presses embodiment 7 conditions preparation oil-displacing agent:
Tetradecyl benzene sulfonic acid sodium salt host 600Kg, sodium hydroxide 100Kg, Sodium hexametaphosphate 99 80kg, sodium sulfate 220kg.The oil-displacing agent total amount is 1000Kg.
Greasy dirt content is 1000mg/l in refinery's waste discharge.In water, add this oil-displacing agent 100mg/l, its oil displacement efficiency of field monitoring, the result is as shown in table 10:
The adding of table 10 oil-displacing agent influences the oily(waste)water oil displacement efficiency
| Sump oil content (mg/l) | Greasy dirt clearance % | |
| Do not add oil-displacing agent | 1000 | |
| After adding oil-displacing agent | 756.9 | 24.31 |
Comparative Examples 3
Prepare oil-displacing agent by following proportioning:
The N-tetracosyl is host 390Kg to the imido grpup benzene sulfonic acid sodium salt, sodium hydroxide 80Kg, sodium polyacrylate 75kg, sodium-chlor 0kg (other is with embodiment 6 conditions), deionized water 455Kg.The oil-displacing agent total amount is 1000Kg.
Greasy dirt content is 150mg/l in refinery's waste discharge.In water, add this oil-displacing agent 100mg/l, its oil displacement efficiency of field monitoring, the result is as shown in table 11:
The adding of table 11 oil-displacing agent influences the oily(waste)water oil displacement efficiency
| Sump oil content (mg/l) | Greasy dirt clearance % | |
| Do not add oil-displacing agent | 150 | |
| After adding oil-displacing agent | 72.6 | 51.6 |
Comparative Examples 4
Prepare oil-displacing agent by following proportioning:
The N-tetradecyl is host 600Kg to the imido grpup benzene sulfonic acid sodium salt, sodium hydroxide 0Kg (other is with embodiment 7 conditions), Sodium hexametaphosphate 99 80kg, sodium sulfate 220kg, deionized water 100kg.The oil-displacing agent total amount is 1000Kg.
Greasy dirt content is 1000mg/l in refinery's waste discharge, PH=6.1 in the water quality.In water, add this oil-displacing agent 100mg/l, its oil displacement efficiency of field monitoring, the result is as shown in table 12:
The adding of table 7 oil-displacing agent influences the oily(waste)water oil displacement efficiency
| Sump oil content (mg/l) | Greasy dirt clearance % | |
| Do not add oil-displacing agent | 1000 | |
| After adding oil-displacing agent | 436.9 | 56.31 |
Comparative Examples 5
Prepare oil-displacing agent by following proportioning:
The N-decyl is host 580Kg to the imido grpup benzene sulfonic acid sodium salt, sodium bicarbonate 50Kg, 2-HPAA 0kg (other is with embodiment 8 conditions), sodium sulfate 180kg, deionized water 190kg.The oil-displacing agent total amount is 1000Kg.
Greasy dirt content is 120mg/l in refinery's recirculated water.In water, add oil-displacing agent 100mg/l, its oil displacement efficiency of field monitoring, the result is as shown in table 13:
The adding of table 13 oil-displacing agent is to oil-containing industrial circulating water water quality impact
| Erosion rate (mm/a) | Stick speed (mcm) | Displacement of reservoir oil rate % | |
| Do not add oil-displacing agent | 0.09561 | 20.75 | |
| Add oil-displacing agent | 0.08229 | 17.35 | 45.2 |
Claims (5)
1. an oil-displacing agent is characterized in that in the constituent gross weight be 100%, contains host 38%～62% in the composition, is N-alkyl C
8～24To imido grpup benzene sulfonate anion surfactant; PH value conditioning agent 0～12% is alkaline salt or alkali; Contain synergistic agent 7%～21%, be the sequestrant of calcium, magnesium ion; Contain toughener 18%～30%, be neutral salt.
2. oil-displacing agent according to claim 1 is characterized in that pH value conditioning agent is one or more in sodium bicarbonate, saleratus, the sodium hydroxide.
3. oil-displacing agent according to claim 1 is characterized in that synergistic agent is one or more in polyphosphoric acid or its salt, organic phospho acid or its salt, polyacrylic acid or its salt.
4. oil-displacing agent according to claim 1 is characterized in that toughener is one or more in sodium-chlor, Repone K, the sodium sulfate.
5. oil-displacing agent according to claim 1, the alkyl that it is characterized in that host is C
8～C
24
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103351857A (en) * | 2013-07-18 | 2013-10-16 | 中国石油大学(华东) | Salt-tolerant wormlike micellar system, preparation method and application thereof in flooding oil |
| CN105860949A (en) * | 2016-04-11 | 2016-08-17 | 中国石油天然气股份有限公司 | Imbibition agent composition and preparation thereof |
| CN106433591A (en) * | 2016-08-30 | 2017-02-22 | 陕西海山能源发展有限公司 | Binary-gel-reconstruction-oily-sludge combined with microorganisms profile control and displacement technology |
| CN109574343A (en) * | 2019-01-21 | 2019-04-05 | 东北石油大学 | The demulsification processing method of oily wastewater solar energy STEP |
| CN113429954A (en) * | 2021-07-30 | 2021-09-24 | 南华大学 | Oil-displacing surfactant system, and preparation method and application thereof |
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| US5973195A (en) * | 1998-03-19 | 1999-10-26 | Energy Biosystems Corporation | Surfactants derived from 2-(2-hydroxyphenyl)benzenesulfinate and alkyl-substituted derivatives |
| CN1131293C (en) * | 2001-02-28 | 2003-12-17 | 大庆高新区鑫诺精细化工有限公司 | Oil-displacing surfactant system for increasing recovery ratio of crude |
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| CN1215145C (en) * | 2001-07-06 | 2005-08-17 | 赵景瑞 | Oil-displacing agent |
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| CN1184276C (en) * | 2001-10-29 | 2005-01-12 | 大庆油田有限责任公司 | Application of alkylbenzene sulfonate as main surfactant in ternary composite oil-displacing agent |
| CN1439690A (en) * | 2002-02-19 | 2003-09-03 | 秦立君 | Alkali(salt)-mixed surfactant-polymer oil composite displacement system and application thereof |
| CN1219017C (en) * | 2002-12-30 | 2005-09-14 | 中国科学院理化技术研究所 | Use of alkyl naphthalene sulfonate as oil displacement agent |
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2005
- 2005-05-20 CN CNB2005100708001A patent/CN100404439C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351857A (en) * | 2013-07-18 | 2013-10-16 | 中国石油大学(华东) | Salt-tolerant wormlike micellar system, preparation method and application thereof in flooding oil |
| CN103351857B (en) * | 2013-07-18 | 2016-04-06 | 中国石油大学(华东) | A kind of salt tolerant worm-like micelle systems, its preparation method and the purposes in the displacement of reservoir oil thereof |
| CN105860949A (en) * | 2016-04-11 | 2016-08-17 | 中国石油天然气股份有限公司 | Imbibition agent composition and preparation thereof |
| CN105860949B (en) * | 2016-04-11 | 2018-07-13 | 中国石油天然气股份有限公司 | Imbibition agent composition and preparation thereof |
| CN106433591A (en) * | 2016-08-30 | 2017-02-22 | 陕西海山能源发展有限公司 | Binary-gel-reconstruction-oily-sludge combined with microorganisms profile control and displacement technology |
| CN109574343A (en) * | 2019-01-21 | 2019-04-05 | 东北石油大学 | The demulsification processing method of oily wastewater solar energy STEP |
| CN113429954A (en) * | 2021-07-30 | 2021-09-24 | 南华大学 | Oil-displacing surfactant system, and preparation method and application thereof |
| CN113429954B (en) * | 2021-07-30 | 2022-07-12 | 南华大学 | Oil-displacing surfactant system, and preparation method and application thereof |
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