CN111304659B - Compound polyisobutenyl phosphite corrosion inhibitor - Google Patents
Compound polyisobutenyl phosphite corrosion inhibitor Download PDFInfo
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- CN111304659B CN111304659B CN201911101602.5A CN201911101602A CN111304659B CN 111304659 B CN111304659 B CN 111304659B CN 201911101602 A CN201911101602 A CN 201911101602A CN 111304659 B CN111304659 B CN 111304659B
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- Prior art keywords
- imidazoline
- compound
- polyisobutenyl
- solvent
- corrosion inhibitor
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- 230000007797 corrosion Effects 0.000 title claims abstract description 74
- 238000005260 corrosion Methods 0.000 title claims abstract description 74
- 239000003112 inhibitor Substances 0.000 title claims abstract description 44
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 150000001875 compounds Chemical class 0.000 title claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 27
- -1 thiazoline compound Chemical class 0.000 claims abstract description 26
- 229920002367 Polyisobutene Polymers 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000008096 xylene Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- FZOZFDAMVVEZSJ-UHFFFAOYSA-N 2-Acetyl-4,5-dihydrothiazole Chemical compound CC(=O)C1=NCCS1 FZOZFDAMVVEZSJ-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- GOHZKUSWWGUUNR-UHFFFAOYSA-N 2-(4,5-dihydroimidazol-1-yl)ethanol Chemical compound OCCN1CCN=C1 GOHZKUSWWGUUNR-UHFFFAOYSA-N 0.000 claims description 6
- REGFWZVTTFGQOJ-UHFFFAOYSA-N 4,5-dihydro-1,3-thiazol-2-amine Chemical compound NC1=NCCS1 REGFWZVTTFGQOJ-UHFFFAOYSA-N 0.000 claims description 6
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 6
- WGTDLPBPQKAPMN-KTKRTIGZSA-N 2-[2-[(z)-heptadec-8-enyl]-4,5-dihydroimidazol-1-yl]ethanol Chemical compound CCCCCCCC\C=C/CCCCCCCC1=NCCN1CCO WGTDLPBPQKAPMN-KTKRTIGZSA-N 0.000 claims description 5
- QNDGQRJVVZJMJO-UHFFFAOYSA-N 2-(2-undecyl-4,5-dihydroimidazol-1-yl)ethanol Chemical compound CCCCCCCCCCCC1=NCCN1CCO QNDGQRJVVZJMJO-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- 239000002283 diesel fuel Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003784 tall oil Substances 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 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- YGPLZBDXFXBLMZ-UHFFFAOYSA-N 1,1-dichloro-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)C(O)(Cl)Cl YGPLZBDXFXBLMZ-UHFFFAOYSA-N 0.000 claims description 2
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 claims description 2
- RDBONSWKYPUHCS-UHFFFAOYSA-N 1-undecyl-4,5-dihydroimidazole Chemical compound CCCCCCCCCCCN1CCN=C1 RDBONSWKYPUHCS-UHFFFAOYSA-N 0.000 claims description 2
- WOHLSTOWRAOMSG-UHFFFAOYSA-N 2,3-dihydro-1,3-benzothiazole Chemical compound C1=CC=C2SCNC2=C1 WOHLSTOWRAOMSG-UHFFFAOYSA-N 0.000 claims description 2
- QJEBJKXTNSYBGE-UHFFFAOYSA-N 2-(2-heptadecyl-4,5-dihydroimidazol-1-yl)ethanol Chemical compound CCCCCCCCCCCCCCCCCC1=NCCN1CCO QJEBJKXTNSYBGE-UHFFFAOYSA-N 0.000 claims description 2
- FLLNQHCNHPZJOY-UHFFFAOYSA-N 2-(2-octyl-4,5-dihydroimidazol-1-yl)ethanol Chemical compound CCCCCCCCC1=NCCN1CCO FLLNQHCNHPZJOY-UHFFFAOYSA-N 0.000 claims description 2
- JUIQOABNSLTJSW-UHFFFAOYSA-N 2-Methyl-4,5-dihydro-1,3-thiazole Chemical compound CC1=NCCS1 JUIQOABNSLTJSW-UHFFFAOYSA-N 0.000 claims description 2
- MFQABLFJUQNPAC-UHFFFAOYSA-N 2-Propionyl-2-thiazoline Chemical compound CCC(=O)C1=NCCS1 MFQABLFJUQNPAC-UHFFFAOYSA-N 0.000 claims description 2
- QUPKCFBHJFNUEW-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1h-imidazole Chemical compound CCC1=NCCN1 QUPKCFBHJFNUEW-UHFFFAOYSA-N 0.000 claims description 2
- ZJULPBMTEMGRNC-UHFFFAOYSA-N 2-methoxy-4,5-dihydro-1h-imidazole Chemical compound COC1=NCCN1 ZJULPBMTEMGRNC-UHFFFAOYSA-N 0.000 claims description 2
- VWSLLSXLURJCDF-UHFFFAOYSA-N 2-methyl-4,5-dihydro-1h-imidazole Chemical compound CC1=NCCN1 VWSLLSXLURJCDF-UHFFFAOYSA-N 0.000 claims description 2
- BKCCAYLNRIRKDJ-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1h-imidazole Chemical compound N1CCN=C1C1=CC=CC=C1 BKCCAYLNRIRKDJ-UHFFFAOYSA-N 0.000 claims description 2
- HXRQZPPTNIMZNK-UHFFFAOYSA-N 2-prop-1-enylsulfanyl-4,5-dihydro-1,3-thiazole Chemical compound C(=CC)SC=1SCCN=1 HXRQZPPTNIMZNK-UHFFFAOYSA-N 0.000 claims description 2
- LFCYHAXVBWPGQR-UHFFFAOYSA-N 2-propyl-4,5-dihydro-1h-imidazole Chemical compound CCCC1=NCCN1 LFCYHAXVBWPGQR-UHFFFAOYSA-N 0.000 claims description 2
- LENVRVUQOXYSDH-UHFFFAOYSA-N 4-ethyl-2-methyl-4,5-dihydro-1,3-thiazole Chemical compound CCC1CSC(C)=N1 LENVRVUQOXYSDH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 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 abstract description 23
- 229910052751 metal Inorganic materials 0.000 abstract description 21
- 239000002184 metal Substances 0.000 abstract description 21
- 230000005764 inhibitory process Effects 0.000 abstract description 12
- 238000007670 refining Methods 0.000 abstract description 7
- 150000001412 amines Chemical class 0.000 abstract description 4
- 239000012530 fluid Substances 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 abstract 1
- 230000002452 interceptive effect Effects 0.000 abstract 1
- 239000010779 crude oil Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000003502 gasoline Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- 239000010962 carbon steel Substances 0.000 description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 3
- 150000008301 phosphite esters Chemical class 0.000 description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention mainly aims at the problem of naphthenic acid corrosion of high-temperature parts of oil refining equipment and provides a compound polyisobutenyl phosphite inhibitor and a preparation method thereof. The corrosion inhibitor consists of 10-40% of polyisobutenyl phosphite, not more than 20% of thiazoline compound, not more than 20% of imidazoline compound, 5-20% of organic amine compound and 30-70% of solvent by weight of the total weight of the corrosion inhibitor. The polyisobutenyl phosphite contained in the composite material has high boiling point and excellent oil solubility, is more firmly adsorbed on the metal surface, is more difficult to fall off in fluid, has large steric hindrance, and is favorable for increasing the coverage area on the metal surface. The polyisobutene group has excellent hydrophobicity and is effective in preventing corrosive media from contacting with metal surfaces. The compound imidazoline and thiazoline compound can effectively fill up gaps of the film layer, form an interactive hydrogen bond to compact the film layer, improve the corrosion inhibition performance, and the organic amine can appropriately neutralize naphthenic acid. The corrosion inhibitor contains few phosphorus elements and does not influence subsequent processing devices.
Description
Technical Field
The invention relates to inhibition of iron corrosion on the surface of high-temperature metal equipment in the field of oil refining, in particular to corrosion caused by naphthenic acid, and particularly relates to a compound polyisobutenyl phosphite corrosion inhibitor.
Background
Crude oil is continuously mined, and the crude oil gradually becomes heavy and inferior, and the acid value is also continuously improved. The crude oil with high acid value has few light components, high residual oil yield, high acid value and other contents, but has low cost and abundant reserves, and the processing of the crude oil with high acid value becomes the choice of most oil refining enterprises at present.
The acidic substance in crude oil is mainly naphthenic acid, which is an organic acid with a saturated cyclic structure and is a viscous liquid which is relatively difficult to volatilize and is expressed as R (CH2)nCOOH, R is a five-membered or six-membered saturated monocyclic or polycyclic cycloalkyl group, and n is about 10-35. Generally, when the acid value of the crude oil exceeds 0.5mgKOH/g, naphthenic acid corrosion is caused in the range of 210 to 420 ℃.
Naphthenic acid corrosion mostly occurs in liquid phase, generates oil-soluble iron naphthenate with iron in the surface of metal equipment, simultaneously, naphthenic acid reacts with a protective film FeS to generate iron naphthenate and hydrogen sulfide, and a fluid medium takes away the iron naphthenate and exposes a new surface to be corroded, so that metal corrosion is continuously performed.
Naphthenic acid has its corrosive properties related to its molecular weight, with low molecular weight naphthenic acids being the most corrosive. Also in relation to the temperature of the corrosive environment: below 210 ℃, basically no corrosion; the corrosivity is gradually enhanced along with the temperature rise, and is strongest at 270-280 ℃; when the temperature is increased again, the naphthenic acid is partially gasified but not condensed, and the concentration of the naphthenic acid in the liquid phase is reduced, so the corrosivity is reduced; the naphthenic acid is gasified at 350 ℃, the gas phase speed is increased, and the corrosion is aggravated; when the temperature is about 420 ℃, the naphthenic acid is basically completely gasified or decomposed, and the high-temperature part of the equipment is not corroded any more.
The corrosion of high acid value crude oil mainly occurs on equipment in the raw material heating section of an atmospheric and vacuum distillation, delayed coking and hydrocracking unit. During the processing of crude oil containing naphthenic acid, severe corrosion of the refinery equipment and pipelines is usually caused, and the normal production of the refinery and the output of downstream products are affected.
The measures taken by the oil refining industry to inhibit naphthenic acid corrosion are: blending crude oil, namely mixing the crude oil with high acid value and the crude oil with low acid value to obtain the crude oil with the total acid value of less than 0.5 mgKOH/g; removing naphthenic acid, which is developed mainly aiming at distillate oil with more concentrated distribution of the naphthenic acid; refining, namely amine refining (i.e. the naphthenic acid reacts with organic amine under certain conditions to generate amide with low acid value and low corrosivity) and hydrorefining; upgrading equipment materials by using corrosion-resistant alloy materials; adjusting the process and equipment structure, such as avoiding local high temperature, overhigh flow speed, multi-turn turning head and the like; adding corrosion inhibitor to react with naphthenic acid to obtain non-corrosive oil soluble product or forming protecting film on the surface of equipment.
At present, the corrosion inhibitor can be directly used for protecting corroded parts, and is an economic and effective control measure.
The common corrosion inhibitor has the defects of poor high temperature resistance, weak metal surface adhesion capability, poor oil solubility and the like.
The corrosion inhibitor contains compounds with lone pair electrons, such as N, O, S, P central atom of polar group, and has the best effect of inhibiting naphthenic acid corrosion. The unpaired electrons of the central atom are coordinated with the empty d orbit of the metal surface to form bonds to generate chemical adsorption, and the chemical adsorption is attached to the metal surface. If the corrosion inhibitor contains a plurality of electron donors and pi electrons, p-pi conjugation is formed and is firmly adsorbed on the metal surface in a plane mode, so that the corrosion inhibition rate is greatly improved. The great steric hindrance of the molecules is beneficial to increasing the coverage rate of the metal surface, thereby increasing the corrosion inhibition rate.
If the corrosion inhibitor molecule contains long-chain alkyl, the long-chain alkyl can be directionally arranged on the metal surface to form a hydrophobic protective film, so that the corrosion inhibitor molecule can block the contact of a corrosion medium and the metal surface and greatly inhibit the corrosion of the corrosion medium to the metal surface.
Disclosure of Invention
Aiming at the defects that the traditional corrosion inhibitor has poor film forming property, low corrosion inhibition rate and easy decomposition at high temperature, the naphthenic acid corrosion inhibitor with the double P structure provided by the invention has firmer adsorption with the metal surface, a polyisobutylene base chain has excellent hydrophobic function, and phosphite ester components also have the functions of resisting oxidation and the like. Has important significance for improving the economic benefit of the oil refinery and prolonging the production period of the device.
The invention provides a compound polyisobutenyl phosphite ester corrosion inhibitor, which comprises the following components in percentage by weight: 10-40% of polyisobutenyl phosphite, not more than 20% of thiazoline compound, not more than 20% of imidazoline compound, 5-20% of organic amine compound and 30-70% of solvent.
Preferably, the polyisobutenyl phosphite has the formula:
wherein PIB is a polyisobutenyl group; the molecular weight is 500-1000.
Preferably, R1Is polyisobutenyl phenyl, or C2~C20And (3) one of alkyl, cycloalkyl and aryl.
Preferably, R1Isooctyl is preferred.
Preferably, the polyisobutenyl phosphite is prepared in the following manner, in three steps:
step (1): preparation of polyisobutylene phenol:
dissolving high-activity polyisobutylene (alpha-terminal olefin is more than or equal to 85%) in a solvent according to the mass ratio of 1: 0.5-1, dissolving phenol in the solvent according to the mass ratio of 1: 1.1-1.5, wherein the solvent is a mixed solvent of normal hexane and xylene, and introducing nitrogen into a nitrogen displacement reaction system; adding boron trifluoride diethyl etherate into the polyisobutene solution as a catalyst, wherein the molar ratio of polyisobutene to the catalyst to phenol is 1: 0.01-0.4: 1.1-2; dropwise adding a phenol solution into the mixed solution by using a dropping funnel for reaction, reacting for 2-6 hours at the reaction temperature of 50-80 ℃, washing with hot water for 2-4 times, drying with anhydrous sodium sulfate, and distilling under reduced pressure to remove the solvent and excessive phenol to obtain polyisobutene phenol;
step (2): synthesis of dichloropentaerythritol diphosphite:
dissolving 0.2mol of pentaerythritol in a xylene solvent, wherein the mass ratio of the pentaerythritol to the solvent is 1: 1.1-1.5, introducing nitrogen into a nitrogen displacement reaction system, and adding a proper amount of catalyst. Slowly dripping a proper amount of phosphorus trichloride by using a dropping funnel, and reacting for 3-6 hours at 50-80 ℃. And (3) carrying out reduced pressure distillation to remove excessive phosphorus trichloride and a byproduct hydrogen chloride, and filtering to obtain a xylene solution of a target product.
And (3): preparation of Polyisobutenylphosphites
Introducing a nitrogen replacement reaction system, dissolving the polyisobutene phenol in a xylene solvent with the mass ratio of 1: 0.8-1.2, and then dropwise adding equivalent isooctanol and stirring; dropwise adding the solution into a xylene solution of the target product in the step (2), and reacting for 2-5 hours at 60-120 ℃ to generate a final target product; and (4) decompressing and evaporating the solvent and the excessive isooctanol, and performing vacuum drying to obtain the final target product.
Preferably, the polyisobutene phenol catalyst is one or a mixture of more than two of sulfuric acid, phosphoric acid, aluminum trichloride, trifluoromethanesulfonic acid and boron trifluoride diethyl etherate solution.
Preferably, the thiazoline compound is one or a mixture of two or more of benzothiazoline, 2-mercaptothiazoline, 2-methyl-4-ethylthiazoline, 2-amino-2-thiazoline, 2-methyl-2-thiazoline, 2-propenylthio-2-thiazoline, 2-acetyl-2-thiazoline, and 2-propionyl-2-thiazoline.
Preferably, the imidazoline compound is one or a mixture of two or more of oleyl hydroxyethyl imidazoline, octyl hydroxyethyl imidazoline, coco hydroxyethyl imidazoline, lauryl hydroxyethyl imidazoline, tall oil hydroxyethyl imidazoline, stearyl hydroxyethyl imidazoline, 2-phenyl imidazoline, 2-methyl imidazoline, 2-methoxy imidazoline, 2-ethyl-2-imidazoline, 2-propyl imidazoline, and undecyl imidazoline.
Preferably, the organic amine compound is C7~C18The monoamine, the diamine and the triamine are one or a mixture of more than two of the monoamine, the diamine and the triamine.
Preferably, the solvent is one or a mixture of more than two of crude gasoline, kerosene, diesel oil or heavy benzene aromatic hydrocarbon.
The invention provides a preparation method of a compound polyisobutenyl phosphite inhibitor, which comprises the following steps: and (3) uniformly stirring the polyisobutenyl phosphite, the thiazoline compound, the imidazoline compound, the organic amine compound and the solvent prepared in the step (3) at the temperature of 50-100 ℃, and standing to room temperature to obtain the coating.
The corrosion inhibitor provided by the invention can be used for inhibiting iron corrosion on the surface of high-temperature metal equipment in the field of oil refining, and the addition amount is 10-200 mu g/g.
The polyisobutenyl phosphite provided by the invention has excellent high-temperature thermal stability and oil solubility, O, P atom lone pair electrons in molecules can form coordinate bonds with Fe atom empty-d orbitals to be more firmly adsorbed on the metal surface, the polyisobutenyl phosphite is less prone to fall off in fluid after film forming, and the p-pi and pi-pi conjugation in the molecules improves the film forming stability of the polyisobutenyl phosphite on the surface of metal equipment. Meanwhile, the polyisobutenyl phosphite ester has larger steric hindrance, which is beneficial to increasing the coverage area on the metal surface, thereby improving the corrosion inhibition rate of the corrosion inhibitor.
The polyisobutenyl contained in the polyisobutenyl phosphite provided by the invention has excellent hydrophobicity, and can effectively prevent corrosive media from contacting with metal surfaces, so that the corrosion speed is reduced.
Imidazoline compounds and thiazoline compounds in the corrosion inhibitor provided by the invention contain N, S atoms, can form coordinate bonds with Fe atoms and be adsorbed on the metal surface, can effectively fill gaps of a film layer to enable the film layer to be compact, organic amine appropriately neutralizes naphthenic acid, and the corrosion inhibition efficiency of the corrosion inhibitor is greatly improved.
The corrosion inhibitor provided by the invention contains few phosphorus elements and does not influence subsequent processing devices.
The polyisobutenyl phosphite contained in the corrosion inhibitor provided by the invention also has an antioxidant property.
The specific implementation mode is as follows:
the polyisobutenyl phosphites according to the invention and the process for their preparation are illustrated below by means of specific examples, which are not intended to limit the scope of the invention.
The polyisobutenyl phosphites in the following examples were prepared as follows:
(1) 200g of high-activity polyisobutene with molecular weight of 1000 are dissolved in 200ml of N-hexane and added into a three-neck flask, and N is introduced2And (3) adding a catalyst of boron trifluoride diethyl etherate solution 14.0ml into a displacement system, dissolving 36g of phenol in 60ml of dimethylbenzene, then dropwise adding the solution, reacting at the reaction temperature of 80 ℃ for 4 hours, washing with hot water for 3 times, drying with anhydrous sodium sulfate, filtering, and distilling under reduced pressure to remove the solvent and excessive phenol to obtain the polyisobutene phenol.
(2) 27.2g of pentaerythritol were dissolved in a solvent and N was added2The reaction system was replaced, 36.6ml of phosphorus trichloride was slowly dropped into the reaction system through a dropping funnel, and the reaction was carried out at 50 ℃ for 4 hours. And (4) removing the byproduct hydrogen chloride by reduced pressure distillation to obtain a xylene solution of the target product.
(3) 219g of polyisobutene phenol is dissolved by using a proper amount of dimethylbenzene as a solvent, and 28g of isooctanol is added and stirred. Dropwise adding the mixture into a xylene solution of the target product in the step (2), and reacting at 80 ℃ for 4 hours. The solvent is distilled out under reduced pressure, and the final target product is obtained after vacuum drying.
Example 1
Respectively weighing 30g of synthesized polyisobutenyl phosphite, 10g of 2-amino-2-thiazoline, 10g of oleyl hydroxyethyl imidazoline, 10g of n-dodecylamine and 140g of crude gasoline, respectively adding the obtained mixture into a three-neck flask with a condenser tube, heating and stirring the obtained mixture uniformly under normal pressure, and standing the obtained product to room temperature to obtain the corrosion inhibitor 1.
Example 2
Respectively weighing 40g of synthesized polyisobutenyl phosphite, 20g of 2-amino-2-thiazoline, 10g of lauryl hydroxyethyl imidazoline, 10g of n-octylamine and 120g of crude gasoline, respectively adding the obtained mixture into a three-neck flask with a condenser, heating and stirring the mixture uniformly under normal pressure, and standing the mixture to room temperature to obtain the corrosion inhibitor 2.
Example 3
60g of synthesized polyisobutenyl phosphite, 10g of 2-amino-2-thiazoline, 10g of tall oil hydroxyethyl imidazoline, 20g of di-n-butylamine and 100g of crude gasoline are respectively weighed and added into a three-neck flask with a condenser tube, heated and stirred uniformly under normal pressure, and placed to room temperature to obtain the corrosion inhibitor 3.
Example 4
70g of synthesized polyisobutenyl phosphite, 20g of 2-acetyl-2-thiazoline, 20g of oleyl hydroxyethyl imidazoline, 10g of n-dodecylamine and 80g of crude gasoline are respectively weighed and added into a three-neck flask with a condenser tube, heated and stirred uniformly under normal pressure, and placed to room temperature to obtain the corrosion inhibitor 4.
Example 5
Respectively weighing 50g of synthesized polyisobutenyl phosphite, 10g of 2-acetyl-2-thiazoline, 20g of lauryl hydroxyethyl imidazoline, 20g of n-octylamine and 100g of heavy benzene aromatic hydrocarbon, respectively adding the materials into a three-neck flask with a condenser tube, heating and stirring the materials uniformly under normal pressure, and standing the mixture to room temperature to obtain the corrosion inhibitor 5.
Example 6
Respectively weighing 50g of synthesized polyisobutenyl phosphite, 20g of 2-acetyl-2-thiazoline, 10g of tall oil-based hydroxyethyl imidazoline, 10g of di-n-butylamine and 110g of heavy benzene aromatic hydrocarbon, respectively adding into a three-neck flask with a condenser tube, heating and stirring uniformly under normal pressure, and standing to room temperature to obtain the corrosion inhibitor 6.
Example 7
60g of synthesized polyisobutenyl phosphite, 30g of 2-amino-2-thiazoline, 10g of n-dodecylamine and 100g of diesel oil are respectively weighed and added into a three-neck flask with a condenser tube, heated and stirred uniformly under normal pressure, and placed to room temperature to obtain the corrosion inhibitor 7.
Example 8
Respectively weighing 30g of synthesized polyisobutenyl phosphite, 30g of oleyl hydroxyethyl imidazoline, 20g of n-octylamine and 140g of diesel oil, respectively adding into a three-neck flask with a condenser tube, heating and stirring uniformly under normal pressure, and standing to room temperature to obtain the corrosion inhibitor 8.
Examples of the experiments
In order to evaluate the corrosion inhibition effect of the corrosion inhibitor on naphthenic acid, the polyisobutenyl phosphites of examples 1 to 8 were evaluated by a coupon weight loss method.
Corrosion medium: blending a normal-three-wire oil product with commercial naphthenic acid by an atmospheric and vacuum device (TAN is 14.2 mgKOH/g);
adding 500g of corrosive medium into a 1L magnetic stirring high-pressure reaction kettle, polishing a No. 20 carbon steel test piece by using sand paper, cleaning by using acetone, wiping by using absorbent cotton, soaking in absolute ethyl alcohol for 20 minutes, drying, weighing, and adding the corrosion inhibitor and the corrosion inhibitor which are not added into the test piece2The etching medium was heated to a reaction kettle at 280 ℃ under protection and stirred at 300 rpm. The corrosion time is 72 hours, and finally the test piece is taken out, washed by acetone, diluted hydrochloric acid liquid and absolute ethyl alcohol respectively, dried and weighed. And calculating the corrosion inhibition effect in the corrosion medium at 280 ℃ when the corrosion inhibitor is added according to the mass loss of the test piece.
The corrosion inhibition rate calculation formula is as follows:
in the formula: eta is corrosion inhibition rate (%);
Δm0mass loss of the carbon steel test piece in the blank test, g;
Δm1the mass loss g of the carbon steel test piece in the corrosion inhibitor adding experiment is shown.
Table 1 shows the results of the corrosion inhibition experiments of examples 1 to 6.
TABLE 1
Claims (8)
1. A compound polyisobutenyl phosphite corrosion inhibitor is characterized in that: the corrosion inhibitor comprises the following components in percentage by weight: 10-40% of polyisobutenyl phosphite, not more than 20% of thiazoline compound, not more than 20% of imidazoline compound, 5-20% of organic amine compound and 30-70% of solvent;
the structural formula of the polyisobutenyl phosphite is as follows:
wherein PIB is polyisobutenyl and has a molecular weight of 500-2000;
R1is polyisobutenyl phenyl, or C2~C20And (3) one of alkyl, cycloalkyl and aryl.
2. The corrosion inhibitor according to claim 1, wherein the thiazoline compound is one or a mixture of two or more selected from the group consisting of benzothiazoline, 2-mercaptothiazoline, 2-methyl-4-ethylthiazoline, 2-amino-2-thiazoline, 2-methyl-2-thiazoline, 2-propenylthio-2-thiazoline, 2-acetyl-2-thiazoline, and 2-propionyl-2-thiazoline.
3. The corrosion inhibitor of claim 1, wherein the imidazoline compound is selected from one or a mixture of two or more of oleyl hydroxyethyl imidazoline, octyl hydroxyethyl imidazoline, coco hydroxyethyl imidazoline, lauryl hydroxyethyl imidazoline, tall oil hydroxyethyl imidazoline, stearyl hydroxyethyl imidazoline, 2-phenyl imidazoline, 2-methyl imidazoline, 2-methoxy imidazoline, 2-ethyl-2-imidazoline, 2-propyl imidazoline, and undecyl imidazoline.
4. Corrosion inhibitor according to claim 1, characterized in that said organic amine compound is selected from C7~C18The monoamine, the diamine and the triamine are one or a mixture of more than two of the monoamine, the diamine and the triamine.
5. The corrosion inhibitor of claim 1, wherein the solvent is one or a mixture of two or more of naphtha, kerosene, diesel oil, or heavy benzene aromatics.
6. A process for the preparation of a corrosion inhibitor according to any of claims 1 to 5, characterized in that the process comprises the following steps: and (2) uniformly stirring the polyisobutenyl phosphite, the thiazoline compound, the imidazoline compound, the organic amine compound and the solvent at a temperature of 50-100 ℃ in proportion, and standing to room temperature to obtain the composite material.
7. The process according to claim 6, wherein the process for the preparation of polyisobutenyl phosphite comprises the steps of:
step (1): preparation of polyisobutylene phenol:
dissolving high-activity polyisobutylene with alpha-terminal olefin content being more than or equal to 85% in a solvent, wherein the mass ratio of the polyisobutylene is 1: 0.5-1, dissolving phenol in the solvent, the mass ratio of the polyisobutylene to the phenol is 1: 1.1-1.5, the solvent is a mixed solvent of n-hexane and xylene, introducing a nitrogen displacement reaction system, adding boron trifluoride diethyl etherate into the polyisobutylene solution as a catalyst, the molar ratio of the polyisobutylene to the catalyst to the phenol is 1: 0.01-0.4: 1.1-2, dropwise adding the phenol solution into the mixed solution by using a dropping funnel for reaction, reacting at the reaction temperature of 50-80 ℃ for 2-6 hours, washing with hot water for 2-4 times, drying with anhydrous sodium sulfate, and removing the solvent and excessive phenol by reduced pressure distillation to obtain polyisobutylene phenol;
step (2): preparation of dichloropentaerythritol diphosphite:
dissolving pentaerythritol in a xylene solvent, wherein the mass ratio of the pentaerythritol to the solvent is 1: 1.1-1.5, introducing a nitrogen displacement reaction system, adding a proper amount of catalyst, slowly dropwise adding a proper amount of phosphorus trichloride by using a dropping funnel, reacting at 50-80 ℃ for 3-6 hours, carrying out reduced pressure distillation to remove excessive phosphorus trichloride and a byproduct hydrogen chloride, and filtering to obtain a xylene solution of a target product;
and (3): preparation of Polyisobutenylphosphites
Introducing a nitrogen displacement reaction system, dissolving polyisobutylene phenol in a xylene solvent at a mass ratio of 1: 0.8-1.2, dropwise adding equivalent isooctanol, stirring, dropwise adding the solution into the xylene solution of the target product in the step (2), and reacting at 60-120 ℃ for 2-6 hours to generate a final target product; and (4) decompressing and evaporating the solvent and the excessive isooctanol, and performing vacuum drying to obtain the final target product.
8. The method of claim 7, wherein the molar ratio of pentaerythritol, phosphorus trichloride, polyisobutylene phenol, isooctanol is: 1: 2-2.2: 1-1.1: 1-1.5.
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