CN102660744A - Corrosion inhibitor for treating oilfield produced water and preparation method thereof - Google Patents
Corrosion inhibitor for treating oilfield produced water and preparation method thereof Download PDFInfo
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- CN102660744A CN102660744A CN2012101173441A CN201210117344A CN102660744A CN 102660744 A CN102660744 A CN 102660744A CN 2012101173441 A CN2012101173441 A CN 2012101173441A CN 201210117344 A CN201210117344 A CN 201210117344A CN 102660744 A CN102660744 A CN 102660744A
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- imidazoline
- corrosion inhibitor
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 7
- 230000007797 corrosion Effects 0.000 title abstract description 47
- 238000005260 corrosion Methods 0.000 title abstract description 47
- 239000003112 inhibitor Substances 0.000 title abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 24
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 23
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 15
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005642 Oleic acid Substances 0.000 claims abstract description 15
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002636 imidazolinyl group Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 17
- -1 oleic imidazolinones Chemical class 0.000 claims description 10
- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical compound O=C1CNC=N1 CAAMSDWKXXPUJR-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 125000005499 phosphonyl group Chemical group 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 4
- 230000005764 inhibitory process Effects 0.000 abstract description 43
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 5
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
- 239000011964 heteropoly acid Substances 0.000 abstract description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 12
- 238000011160 research Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 150000002462 imidazolines Chemical class 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 208000016261 weight loss Diseases 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 239000011973 solid acid Substances 0.000 description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000009671 shengli Substances 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- BJLRVFDWAOVFCI-UHFFFAOYSA-N 1h-imidazole;quinoline Chemical compound C1=CNC=N1.N1=CC=CC2=CC=CC=C21 BJLRVFDWAOVFCI-UHFFFAOYSA-N 0.000 description 2
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- 229910000926 A-3 tool steel Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000009435 amidation Effects 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
- 229940113162 oleylamide Drugs 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002461 imidazolidines Chemical class 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002332 oil field water Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Lubricants (AREA)
Abstract
The invention provides a corrosion inhibitor for treating oilfield produced water, which comprises an imidazoline group and a phosphonic acid group. 350 to 450 parts of diethylene triamine, 650 to 750 parts of oleic acid, 15 to 25 parts of heteropolyacid serving as a catalyst and 950 to 1100 parts of dimethyl benzene serving as a water-carrying agent are added to a reactor by weight, stirred and heated to a temperature of 150 DEG C, the reaction temperature is kept at 140 to 220 DEG C, and after a reaction product flows back for 5 to 8 hours, oleic acid imidazoline is obtained. Under a normal temperature condition, 350 to 450 parts of oleic acid imidazoline, 20 to 30 parts of hydrochloric acid serving as a catalyst and 55 to 65 parts of formaldehyde are added to the reactor and stirred for 0.5 to 4 hours, 65 to 75 parts of isopropyl alcohol solutions of phosphorous acid is added to the reactor and stirred for 1 to 2 hours, then pH value of a reaction product is regulated to 6 by using hydrochloric acid, and a finished product of the corrosion inhibitor with for treating the oilfield produced water, which has a concentration of 90 percent, is obtained. The corrosion inhibitor has a high corrosion inhibition rate, is easy to be dissolved in water and is modified by using cheap raw materials; and the cost for preparing the corrosion inhibitor is low.
Description
Technical field
The present invention relates to the oilfield chemistry agent that a kind of oil field produced water treatment is used, particularly relate to a kind of oil field produced water treatment with inhibiter and preparation method thereof.
Background technology
The duration of service of oil transportation, water supply and waterflood-transmission line and equipment has been shortened in the corrosion of oil field extracted water, has caused great waste.The main at present method of the chemical inhibiter of interpolation that adopts is carried out protection against corrosion, and inhibiter is divided into inorganic inhibitor and organic inhibitor, mainly uses organic inhibitor according to the oil field characteristics.Cause the corrosive principal element that carbonic acid gas, hydrogen sulfide, cl ions, various salt, dissolved oxygen and bacterium etc. are arranged in the oil field extracted water; Prevent that at present the corrosion that these factors cause from mainly adopting the imidazolines organic inhibitor; In neutral water, film forming properties is good in the metallic surface for the imidazolines inhibiter, and corrosion inhibition rate is high; Can reach the requirement of SY/T6301-1997 " oil field extracted water is used the inhibiter general technical specifications "; Through retrieval, domestic bibliographical information about imidazoline inhibitor is more, comprehensively as follows:
1, fine chemistry industry, 2006,23 (9): 930-932 has reported Xi'an University of Architecture and Technology; The Yin of China National Petroleum Corporation (CNPC) becomes earlier, Feng Yaorong, Lanzhou-Xinjiang wise man etc.; A kind of synthetic and performance of novel solid inhibiter; This article is a raw material with dimerization oleic acid and diethylenetriamine, and Mono Chloro Acetic Acid is a reaction medium, has synthesized the novel imidazole quinoline through amidation, cyclisation and quaterisation.Through orthogonal experiment research, confirm optimum synthesis condition.
2, oilfield chemistry; 2004,21 (3): 230-233,236 have introduced department of chemistry of the Central China University of Science and Technology; The two factory gold battalion of recovering the oil of Sinopec Zhongyuan Oil Field branch office; Wei Huifang, Zhang Liqiang etc., the synthetic and corrosion inhibition [J] in oil gas well output liquid of tetrahydroglyoxaline oleylamide. this article by oleic acid and diethylenetriamine synthesized imidazoline amide YIM also with infrared spectrum characterization chemical structure.The weight-loss method test result shows, 60 ℃ of temperature, when adding dosage 50 mg/L, and in the oil field extracted water of the middle original text east of salinity 1.24 * 105 mg/L, YIM is respectively 81.7%, 75.6% and 74.6% to the corrosion inhibition rate of Q235, N80, the test piece of J55 steel; Corrosion inhibition rate is with CO
2Dividing potential drop increases (0.2～1.0 MPa) and reduces.
3, oil and gas chemical industry; 2004; 33 (5): 359-361 has reported the Ma Tao of petroleum engineering institute of Petroleum Univ. (East China); Zhang Guicai, Ge Jijiang. " the synthetic and evaluation [J] of modified imidazoline inhibiter ". this article is that raw material has synthesized tetrahydroglyoxaline with oleic acid, diethylenetriamine, and it is carried out the water-soluble modified imidazoline type inhibiter that obtained.Use testing method such as polarization curve, static steel and estimated the corrosion inhibition and the inhibition mechanism of this inhibiter.Experimental result shows: the corrosion in saturated carbonic acid gas simulation brine system has the obvious suppression effect to this inhibiter to the A3 carbon steel, dosage 5 mg/l, and corrosion inhibition rate can reach more than 95%, is applicable to the corrosion that suppresses high salinity, carbonated oil-field water.
4, Speciality Petrochemicals progress; 2009,10 (10): 9-12 has introduced chemical institute of Southwest Petrol University, the Yan Jie of COSL; Li Qianlu; Yang Honglie etc., this article is a main raw material with oleic acid, diethylenetriamine and quaternizing agent, has synthesized the Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor that is applicable to the oil field.Confirmed the optimum synthesis condition of this inhibiter.
5, Treatment of Industrial Water, 2003,23 (6): 42-44 has introduced Shengli Oil Tiandong County hot oil recovery history of factory foot China, Zhang Liping, the synthetic and rig-site utilization [J] of yellow quick efficient tetrahydroglyoxaline sewage water corrosion inhibitor.This article is with the synthetic under certain condition imidazolines MB inhibiter of rosin, Viscotrol C and diethylenetriamine; Because the chemical structure and the relative molecular mass of colophony type tetrahydroglyoxaline and caster oil type tetrahydroglyoxaline are different; Both replenish each other, can form compact protective film in the metallic surface.
6, Wuhan: the Central China University of Science and Technology; 2009 have reported the synthetic and corrosion inhibition research [D] of the rosinyl imidazoline quaternary ammonium salt that Wang Qian writes. this article is with rosin; Diethylenetriamine, alkylating reagent are that raw material has synthesized four kinds of different rosinyl imidazolidine derivatives.Through to water-soluble and evaluation corrosion inhibition, finally select rosin, diethylenetriamine, the rosinyl imidazoline quaternary ammonium salt RIA of the synthetic gained of sodium chloroacetate three is a research object.Utilize ir spectra that the structure of rosinyl imidazoline quaternary ammonium salt RIA is characterized, proved the generation of title product.At CO
2In saturated 3% the sodium chloride solution, adopt weight-loss method, polarization curve, testing method such as alternating-current impedance are estimated the corrosion inhibition of inhibiter.The erosion profile on Q235 steel disc surface of having used scanning electron microscopic observation.According to the weight-loss method test result analysis influence the principal element of corrosion inhibition.Also inquired into inhibiter simultaneously at the adsorption mechanism of metallic surface and the dynamic characteristic of corrosion reaction.
7, refining of petroleum and chemical industry; 2006; 37 (4): 60-63 has introduced Shengli Oil Field triumph engineering design Advisory Co., Ltd scientific research institution; Wu Lu is peaceful for petroleum engineering institute of China University Of Petroleum Beijing, and by " the synthetic and corrosion inhibition research of imidazoline type inhibiter " [J] of celebrating, the document is the synthetic tetrahydroglyoxaline of raw material with palmitinic acid, diethylenetriamine; And it is carried out the water-soluble modified imidazoline type inhibiter YG-1 that prepared; Obtain composite inhibition system YG-2. and use the corrosion inhibition that static steel weight-loss method, electrochemical process have been estimated this composite inhibition system YG-2 with the auxiliary agent thiocarbamide is composite, studied inhibition mechanism, and with scanning electron microscope analysis the surface topography of A3 steel after corroding front and back and adding composite inhibition system YG-2.
8, corrosion science and guard technology; 2006; 18 (5): 317-320 has introduced China University Of Petroleum Beijing, Shengli Oil Field mud company of China Petrochemical Industry, hot love deep pool, hot oil recovery factory, China Petrochemical Industry Shengli Oil Tiandong County; Zhu Xiaoming; The corrosion inhibition of the composite imidazoline type slow-releasing agent system " research " [J] that Luan Yong fortunately writes. this article is that raw material has synthesized tetrahydroglyoxaline with palmitinic acid, diethylenetriamine, and with MALEIC ANHYDRIDE its modification has been obtained imidazoline type inhibiter YQ-01, obtains composite inhibition system YQ-03 with auxiliary agent YQ-02 is composite.Use static steel weight-loss method, electrochemical process and ESEM method and studied the corrosion inhibition of this composite inhibition system YQ-03.
9, University Of Science and Technology Of Hunan's journal (natural science edition), 2007,22 (2): 94-97 has reported Shi Shuncun; Jiang Huapeng; Sweet potato (University Of Science and Technology Of Hunan) is eaten by the side, " the synthetic and corrosion inhibition research of amphoteric imidazoline " [J]. and this article has synthesized the midbody tetrahydroglyoxaline with high-purity naphthenic acid and diethylenetriamine reaction, is solvent again with the deionized water; With sodium chloroacetate this midbody is carried out amphoterisation, made the soluble amphoteric imidazoline inhibitor.Inquired into of the influence of factors such as reactant ratio, temperature of reaction, pH, drawn best synthesis condition product.
10, corrosion and protection; 2006; 27 (3): 122-125 has introduced by celebrating, Wang Yefei, Wei Yongzhou; Deng (petroleum engineering institute of China University Of Petroleum Beijing). the research [J] of the synthetic and inhibition mechanism of imidazoline type inhibiter. this article is that raw material has synthesized a kind of imidazoline type inhibiter YQ-01 with palmitinic acid, diethylenetriamine, maleic anhydride, obtains effectively suppressing the inhibition system YQ-03 of carbon dioxide corrosion after composite with YQ-02.Application static steel weight-loss method, electrochemical tests, X-ray photoelectron spectroscopic analysis have been studied the electrochemical characteristic of YQ-03 inhibition carbon dioxide corrosion; Analyzed and corroded forward and backward and add the surperficial product of A3 steel behind the inhibition system YQ-03, inquired into the inhibition mechanism of YQ-03.
Show through literature search in the above-mentioned scope; Domestic bibliographical information about imidazoline inhibitor is more; As: a kind of synthetic and performance of novel solid inhibiter; With dimerization oleic acid and diethylenetriamine is raw material, and Mono Chloro Acetic Acid is a reaction medium, has synthesized the novel imidazole quinoline through amidation, cyclisation and quaterisation
[1]Synthetic and the corrosion inhibition in oil gas well output liquid of tetrahydroglyoxaline oleylamide, by oleic acid and diethylenetriamine synthesized imidazoline amide YIM also with infrared spectrum characterization chemical structure
[2]Synthetic and the evaluation of modified imidazoline inhibiter; With oleic acid, diethylenetriamine is that raw material has synthesized tetrahydroglyoxaline; And it is carried out the water-soluble modified imidazoline type inhibiter that obtained, use corrosion inhibition and inhibition mechanism that testing method such as polarization curve, static steel have been estimated this inhibiter
[3]Synthetic and the rig-site utilization of efficient tetrahydroglyoxaline sewage water corrosion inhibitor; With the synthetic under certain condition imidazolines MB inhibiter of rosin, Viscotrol C and diethylenetriamine; Because the chemical structure and the relative molecular mass of colophony type tetrahydroglyoxaline and caster oil type tetrahydroglyoxaline are different; Both replenish each other, can form compact protective film in the metallic surface
[5]The corrosion inhibition research of composite imidazoline type slow-releasing agent system is that raw material has synthesized tetrahydroglyoxaline with palmitinic acid, diethylenetriamine, and with MALEIC ANHYDRIDE its modification has been obtained imidazoles
Quinoline type inhibiter YQ-01 obtains composite inhibition system YQ-03 with auxiliary agent YQ-02 is composite
[8]Synthetic and the corrosion inhibition research of amphoteric imidazoline has been synthesized the midbody tetrahydroglyoxaline with high-purity naphthenic acid and diethylenetriamine reaction, is solvent again with the deionized water, with sodium chloroacetate this midbody is carried out amphoterisation, has made the soluble amphoteric imidazoline inhibitor
[9]Deng.
The synthetic of various oleic imidazolinones of the prior art all uses aluminium sesquioxide as catalyzer, and the reaction times needs 24h; Synthesising reacting time is long, and corrosion inhibition rate is lower and cost is higher.
Summary of the invention:
The synthetic use aluminium sesquioxide that goal of the invention of the present invention is to the county technological oleic imidazolinone to be arranged is as catalyzer; Synthesising reacting time is long; The deficiency that corrosion inhibition rate is lower and cost is higher, the same form provide a kind of corrosion inhibition rate high, and inhibiter is used in oil field produced water treatment soluble in water; Two to provide a kind of compound method simple, and the cheap oil field produced water treatment of cost is with the preparation method of inhibiter.
Realize that the foregoing invention purpose adopts following technical scheme:
Inhibiter is used in a kind of oil field produced water treatment, and described inhibiter contains imidazoline group and phosphonyl group.
A kind of oil field produced water treatment is with the preparation method of inhibiter, and it is synthetic that this method was divided into for two steps, may further comprise the steps:
A. by weight, in reactor drum, add 350～450 parts of diethylenetriamines, 650～750 parts of oleic acid; 15～25 parts of catalyzer heteropolyacids, 950～1100 parts of azeotropic agent YLENE are heated with stirring to 150 ℃; Keeping temperature of reaction is 140～220 ℃, refluxes 5～8 hours, obtains oleic imidazolinone;
B. under the normal temperature condition, in reactor drum, add 350～450 parts of oleic imidazolinones, 20～30 parts of catalyzer hydrochloric acid; 55～65 parts in formaldehyde; Stir 0.5～4h, 65～75 parts of the aqueous isopropanols of continuation adding phosphorous acid in reactor drum are behind stirring 1～2h; Using hydrochloric acid to regulate pH is 6, obtains concentration and is 90% oil field extracted water and use the inhibiter finished product.
Adopt technique scheme; Compare with existing other general type inhibiter; Remarkable advantage of the present invention is: use the solid acid heteropolyacid as the synthetic oleic imidazolinone of catalyzer, if adopt aluminium sesquioxide to need 24 h approximately as the catalyst reaction time, with solid acid as catalyzer; Reaction times only needs 5～8 h, uses solid acid catalyst to shorten 16～19h than aluminium sesquioxide as the catalyst reaction time; At normal temperatures, under hydrochloric acid catalysis, with formolite reaction, add the aqueous isopropanol of phosphorous acid again by oleic imidazolinone, tetrahydroglyoxaline continues and the phosphorous acid reaction, inserts phosphorus-containing groups, again with the pH value to 6 of hydrochloric acid conditioned reaction product.Through above-mentioned reaction, except containing imidazoline group, also contain phosphonyl group in the inhibiter, strengthened adsorption, improved corrosion inhibition rate; The synthetic inhibiter is soluble in water, uses comparatively cheap starting material to carry out
Modification has greatly reduced the cost of inhibiter.
Embodiment:
Below in conjunction with embodiment the present invention is done further description.
Present embodiment is that inhibiter is used in a kind of oil field produced water treatment; It is synthetic that this inhibiter was divided into for two steps; Midbody by diethylenetriamine, oleic acid under the catalysis of solid acid; Adopt YLENE to do azeotropic agent, cyclic condensation under the condition that refluxes is processed the aqueous isopropanol and the hydrochloric acid reaction of midbody and formaldehyde, phosphorous acid again.This inhibiter contains imidazoline group and phosphonyl group.
Oil field produced water treatment may further comprise the steps with the preparation method of inhibiter:
Under the catalysis of solid acid heteropolyacid, adopt YLENE to make azeotropic agent by diethylenetriamine and oleic acid, generate oleic imidazolinone in the condensation reaction in 5～8 hours of 140～220 degree condition refluxed;
Under the normal temperature, under the catalysis of hydrochloric acid, with formolite reaction after 0.5～4 hour, add the aqueous isopropanol of phosphorous acid again by oleic imidazolinone, tetrahydroglyoxaline continues and the phosphorous acid reaction, inserts phosphorus-containing groups, and the pH value of using hydrochloric acid conditioned reaction product again is 6.
Through behind the above-mentioned two-step reaction, except containing imidazoline group, also contain phosphonyl group in the inhibiter that obtains, strengthened adsorption.
Preparing method's specific embodiment
Embodiment 1 (raw material by weight)
In reactor drum, add diethylenetriamine 400kg, oleic acid 700kg, catalyzer heteropolyacid 20kg, azeotropic agent YLENE 1000kg is heated to 150 ℃ at continuous stir following, and keeping temperature of reaction is 140～220 ℃, refluxes 5～8 hours, obtains oleic imidazolinone.
Under the normal temperature condition, in reactor drum, add oleic imidazolinone 400kg, catalyzer hydrochloric acid 25kg; Formaldehyde 60kg; Stir 0.5～4h, continue in reactor drum, to add the aqueous isopropanol 70kg of phosphorous acid, stir 1～2h; It is 6 that the back uses hydrochloric acid to regulate pH, obtains 600kg concentration and is 90% oil field extracted water and use inhibiter.
The test of embodiment 2 inhibiter corrosion inhibition rates
The corrosion inhibition rate test is carried out according to normal pressure static etch rate and corrosion inhibition rate measuring method in SY/T 5273-2000 " oil field extracted water the is used the inhibiter method of evaluating performance " standard; The test water sample adopts Ji Dong oil field high one and master mausoleum recovered water; Test temperature is 50 ℃; Adding consistency is 100mg/L, and test-results is seen table 1
Table 1 inhibiter corrosion inhibition rate test-results
| Water sample | Sample | Erosion rate/mm/a | Corrosion inhibition rate/% |
| A high recovered water | / | 0.05364 | / |
| ? | 1 kind of example | 0.01386 | 74.2 |
| ? | Phosphoric acid hydroxyl acid type | 0.04629 | 13.7 |
| ? | Double quaternary ammonium salt type | 0.03031 | 43.5 |
| ? | The alkyl phosphate type | 0.02989 | 44.3 |
| ? | The Mannich base type | 0.03899 | 27.3 |
| Master mausoleum recovered water | / | 0.07056 | / |
| ? | 1 kind of example | 0.01373 | 80.5 |
| ? | Phosphoric acid hydroxyl acid type | 0.06374 | 9.7 |
| ? | Double quaternary ammonium salt type | 0.02358 | 66.6 |
| ? | The alkyl phosphate type | 0.02086 | 70.4 |
| ? | The Mannich base type | 0.03705 | 47.5 |
More than disclosedly be merely specific embodiment of the present invention; Though the present invention discloses as above with preferred embodiment; But the present invention is not limited thereto, any those skilled in the art can think variation, in not breaking away from design philosophy of the present invention and scope; The present invention is carried out various changes and retouching, all should drop within protection scope of the present invention.
Claims (2)
1. inhibiter is used in an oil field produced water treatment, it is characterized in that described inhibiter contains imidazoline group and phosphonyl group.
2. an oil field produced water treatment is characterized in that with the preparation method of inhibiter, and it is synthetic that this method was divided into for two steps, may further comprise the steps:
A. by weight, in reactor drum, add 350～450 parts of diethylenetriamines, 650～750 parts of oleic acid; 15～25 parts of catalyzer heteropolyacids, 950～1100 parts of azeotropic agent YLENE are heated with stirring to 150 ℃; Keeping temperature of reaction is 140～220 ℃, refluxes 5～8 hours, obtains oleic imidazolinone;
B. under the normal temperature condition, in reactor drum, add 350～450 parts of oleic imidazolinones, 20～30 parts of catalyzer hydrochloric acid; 55～65 parts in formaldehyde; Stir 0.5～4h, 65～75 parts of the aqueous isopropanols of continuation adding phosphorous acid in reactor drum are behind stirring 1～2h; Using hydrochloric acid to regulate pH is 6, obtains concentration and is 90% oil field extracted water and use the inhibiter finished product.
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