CN1869287A - High temp corrosion inhibitor and its preparation method and application - Google Patents
High temp corrosion inhibitor and its preparation method and application Download PDFInfo
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- CN1869287A CN1869287A CN 200610018059 CN200610018059A CN1869287A CN 1869287 A CN1869287 A CN 1869287A CN 200610018059 CN200610018059 CN 200610018059 CN 200610018059 A CN200610018059 A CN 200610018059A CN 1869287 A CN1869287 A CN 1869287A
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- acid
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- temperature
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- 239000003112 inhibitor Substances 0.000 title claims abstract description 23
- 238000005260 corrosion Methods 0.000 title claims description 65
- 230000007797 corrosion Effects 0.000 title claims description 60
- 238000002360 preparation method Methods 0.000 title claims description 19
- 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 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 238000012545 processing Methods 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- -1 polyethylene Polymers 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 10
- 150000007524 organic acids Chemical class 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 claims description 4
- 238000005504 petroleum refining Methods 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 235000021353 Lignoceric acid Nutrition 0.000 claims description 3
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 229960004232 linoleic acid Drugs 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 claims description 2
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 claims description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 2
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 claims description 2
- 150000002462 imidazolines Chemical class 0.000 claims description 2
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 17
- 239000011593 sulfur Substances 0.000 abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 abstract description 14
- 239000003208 petroleum Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 11
- 238000009835 boiling Methods 0.000 description 11
- 230000005764 inhibitory process Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 208000016261 weight loss Diseases 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 230000000116 mitigating effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- 150000000211 1-dodecanols Chemical class 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000007518 monoprotic acids Chemical class 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- QZZGJDVWLFXDLK-UHFFFAOYSA-N tetracosanoic acid Chemical class CCCCCCCCCCCCCCCCCCCCCCCC(O)=O QZZGJDVWLFXDLK-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a manufacture method and application for high temperature inhibitor that is the compound has the structure general expression (1), and R1 is C4-C12 alkyl, R2 is C8-C30 alkyl or alkyl derivative, n is 2-5, A is SH or R10. The invention could effectively solve the naphthenic acid corruption and sulfur corruption generated by high temperature section in petroleum processing.
Description
Technical field
The invention belongs to the inhibition field of metallic substance, particularly relating to a kind of petroleum refining process that is used for has the dangerous equipment of corrosion and the preparation method and the application of the high-temperature corrosion inhibitor on the pipe surface and this inhibiter.
Background technology
In recent years, along with the continuous variation of processing crude quality, naphthenic acid corrosion and sulfur corrosion in various degree all taken place in many refineries water distilling apparatus, causes the equipment erosion to leak, and has a strong impact on the normal operation of device.
Contain a spot of acidic oxide in the crude oil, as lipid acid, naphthenic acid and phenols etc., these acidic oxides are referred to as petroleum acid, and naphthenic acid content accounts for about 90% of petroleum acid usually, so naphthenic acid is to cause device generation high-temperature acid corrosive major cause.Naphthenic acid mainly is the derivative of pentamethylene, it is similar to lipid acid, be typical monoprotic acid, have the whole chemical property of common organic acid, because of the molecular weight difference, naphthenic acid has different boiling points, and naphthenic acid is in the enrichment of equipment different sites in still-process, formation has corrosive nonaqueous electrolyte, thereby causes the corrosion at this position.Often initial ring alkanoic acid corrosive position is: the boiler tube of atmospheric pressure kiln and vacuum furnace, and the feed zone of atmospheric tower and vacuum distillation tower, the transfer line that comes out at the bottom of tower tray and tower wall and the tower etc. is located.
Sulphur in the crude oil generally is divided into active sulphur and inactive sulfur, elementary sulfur, hydrogen sulfide and low molecule mercaptan can both cause the corrosion of equipment with the direct effect of metal, therefore they are collectively referred to as active sulphur, and all the other can not be referred to as inactive sulfur with the direct acting sulfocompound of metal as thioether, disulphide, thiophene etc.Inactive sulfur can partly be decomposed into active sulphur under the effect of high temperature, high pressure and catalyzer.The corrosive environment of high temperature sulfocompound is meant by sulphur, hydrogen sulfide and mercaptan at the corrosive environment that forms more than 240 ℃.Typical high temperature sulfur corrosion environment is present in the bottom and the tower bottom tube road of ordinary decompression column, air distillation and underpressure distillation interchanger, the bottom of catalytic cracking main fractionating tower, the bottom of delayed coking main fractionating tower etc.
Naphthenic acid corrosion and sulfur corrosion at high temperature exist simultaneously, and can promote mutually, form corrosive cycle, the aggravation corrosion of metal.
Control naphthenic acid corrosion and sulfur corrosion at present is mainly by three kinds of approach:
One, improvement complete processing reduces the acid number of crude oil as adopting methods such as mediation, neutralization, extraction, change naphthenic acid form, and methods such as employing hydrogenating desulfurization, solvent desulfurization, biological desulphurization remove the S-contained substance in the crude oil;
Two, improve the anti-corrosion grade of equipment material, this is a kind of method of controlling high temperature corrosion of current the most normal use;
Three, adopt inhibiter to suppress high temperature corrosion.
Improving the anti-corrosion grade of complete processing and raising equipment material can not deal with problems fully, and investment is bigger.Use the inhibiter investment little, do not need to set up complex apparatus, easy to use flexible, can be according to corrosion situation decision filling position and consumption.
At present, the high-temperature corrosion inhibitor that report uses mainly contains 2 kinds, and a kind of is home-made GX-195 high-temperature corrosion inhibitor, and another kind is Nalco5180.These two kinds of inhibiter costs are higher, Nalco5180 especially, cost costliness.
Domestic high-temperature corrosion inhibitor aspect patent is less, is used for iron and steel inhibiter of high-temperature acidic medium and preparation method thereof, 03142259.4 1 kinds of inhibiter that are used for oil refining apparatus high temperature position equipment as 92109528.7 high temperature oil phase corrosion inhibitors, 02100697.0.Wherein 92109528.7 consumptions are few, efficient is high, but this inhibiter need be synthetic under pressure 0.2-0.4Mpa, and generated time is longer.02100697.0 be suitable as the acidification of oil gas well inhibiter.03142259.4 preparation is simple, consumption is few, but only selects the wherein composite inhibiter of certain several material, or restraining effect is relatively poor, or cost is higher.
The patent of external high-temperature corrosion inhibitor aspect is a lot, as patent USP5314643, USP5464525, USP5500107 etc. be with alkyl, fragrant alkyl phosphate as high-temperature corrosion inhibitor.These inhibiter can suppress naphthenic acid corrosion and sulfur corrosion simultaneously, but injection rate is very big, the injection rate foot 2000-3000ppm of pre-film phase; after forming, also wants protective membrane 100-1500ppm; cost of use is higher like this, and the corrosion inhibition rate of some product is on the low side in addition, and corrosion mitigating effect is undesirable.Patent USP5552085, USP5863415 with small molecule amine neutralization or not the neutral thiophosphatephosphorothioate experimental results show that as high-temperature corrosion inhibitor these inhibiter corrosion inhibition rates are not high.
Summary of the invention
The present invention is in order to solve high-temperature corrosion inhibitor unstable properties of the prior art, the shortcoming that corrosion mitigating effect is bad, and provide a kind of novel high-temperature corrosion inhibitor, with naphthenic acid corrosion and the sulfur corrosion that high temperature position was produced in effective solution petroleum refining process, the present invention also provides the preparation method and the application of this inhibiter.
The invention provides a kind of high-temperature corrosion inhibitor, it is characterized in that: be that a kind of general structure is the compound of formula (1):
R wherein
1Be C
4～C
12Alkyl, R
2Be C
8～C
30Alkyl or alkyl derivative, C preferably
12～C
24Alkyl or alkyl derivative, n is 2～5 integer, A is SH or R
1O.
High-temperature corrosion inhibitor of the present invention, its preparation method comprises the steps:
(i) thiophosphoric anhydride and Fatty Alcohol(C12-C14 and C12-C18) be in organic solvent, is that the generating structure formula is the thiophosphatephosphorothioate compounds of formula (2) under 100～170 ℃ the reaction conditions in normal pressure, temperature.
R wherein
1Be C
4～C
12Alkyl, A is SH or R
1O.
Described Fatty Alcohol(C12-C14 and C12-C18) is propyl carbinol, neopentyl alcohol, n-hexyl alcohol, isooctyl alcohol, nonylcarbinol or lauryl alcohol etc., preferred isooctyl alcohol.
(ii) organic acid and polyethylene polyamine be in organic solvent, under the normal pressure, temperature is that the generating structure formula is the imidazolines of formula (3) under 200～240 ℃ the reaction conditions.
Described R
2Be C
8～C
30Alkyl or alkyl derivative, C preferably
12～C
24Alkyl or alkyl derivative, described organic acid is C
13～C
25Thiazolinyl organic acid, dialkylene organic acid, alkyl organic acid or cycloalkyl organic acid, preferred oleic acid, linolic acid, stearic acid, naphthenic acid, dodecenylsuccinic acid or Lignoceric acid.
The general structure of described polyamines polyene is H
2N (CH
2CH
2NH)
nH, wherein n is 2～5 integer, the preferred diethylenetriamine of polyethylene polyamine, triethylene tetramine, tetraethylene pentamine or five ethene hexamines.
Described organic solvent is an aromatic hydrocarbon solvent, recommends to use benzene, toluene or dimethylbenzene.
(iii) the compound (3) that (ii) obtains of the compound (2) that step (i) is obtained and step reacted 20～40 minutes under 80～120 ℃, condition of normal pressure, then the solvent in the reaction product is steamed, drying promptly obtains the compound that general structure is formula (1) again, is high-temperature corrosion inhibitor of the present invention.
The present invention also provides a kind of described high-temperature corrosion inhibitor is used for equipment and the pipeline that petroleum refining process has corrosion danger; its application method is: high-temperature corrosion inhibitor is added to the above-mentioned course of processing is produced in the corrosive working fluid; form protective membrane at the use initial stage for having as early as possible on the wall that corrodes dangerous equipment and pipeline; should heavy dose ofly annotate; filling rate is that to make the content of inhibiter in the working fluid be 200～1000 μ g/g; preferably 300～500 μ g/g treat the Fe in the working fluid
2+Concentration is reduced to when requiring index, should reduce filling rate and make it maintain a suitable scope, and filling rate is that to make the content of inhibiter in the working fluid be 10～100 μ g/g, and best filling rate is 20～50 μ g/g.
Above-mentioned working fluid can be atmospheric pressure kiln charging, vacuum furnace charging, atmospheric tower charging, vacuum distillation tower charging, often reduce pressure the side line reflux material or the side line interchanger material that often reduces pressure, and also can be catalytic cracking fractionating tower side reflux material or delayed coker fractionator side reflux material etc.
High-temperature corrosion inhibitor provided by the invention, thus because can be adsorbed on the metallic surface, the polar group in its molecule changes double electrical layers, therefore can improve the activation energy of metal ion process; Non-polar group in its molecule becomes to align away from metal on the other hand, forms the hydrophobic protective membrane of one deck, can effectively stop naphthenic acid to contact with the metallic surface with sulfide, and corrosion is inhibited.The present invention compared with prior art because it is from multiple inhibition mechanism, both can form chemical films on the metal wall, can form the physical adsorption film again, had overcome that adsorption film comes off easily, the untight shortcoming of chemical films, and corrosion inhibition rate is greatly improved; Secondly high-temperature corrosion inhibitor stable performance provided by the invention, and because desired raw material is cheap and easy to get, so cost is lower.
Embodiment
Describe the present invention in detail with specific embodiment below, but embodiment does not limit the scope of the invention.
Embodiment 1:
The structure of novel cpd A1 and B1 and preparation method.
1, the structural formula of novel cpd A1 is formula (5), and the structural formula of B1 is formula (6):
2, preparation method
(1) earlier 260 gram isooctyl alcohol and 110 gram toluene are put into the 500ml four-hole boiling flask that agitator, thermometer, condenser are housed.Start the whipping appts water of condensation of open cold condenser simultaneously, add 110 gram thiophosphoric anhydrides again, when being warming up to 120 ℃, constant temperature 5 hours.
(2) 160 gram oleic acid, 90 gram triethylene tetramines, 60 gram dimethylbenzene are added in another 500ml four-hole boiling flask that agitator, thermometer, water trap, condenser are housed simultaneously.Be warmed up to 200 ℃ with 10 ℃/h, dehydration, desolventizing, constant temperature 8 hours, be cooled to 100 ℃, add the reaction product of step (1), constant temperature half an hour, be cooled to room temperature, then reaction product is poured in the matrass, with underpressure distillation solvent is steamed, drying promptly obtains the mixture of novel cpd A1 and novel cpd B1 again.
Embodiment 2:
The structure of novel cpd A2 and B2 and preparation method.
1, the structural formula of novel cpd A2 is formula (7), and the structural formula of B2 is formula (8):
2, preparation method
(1) earlier 150 gram propyl carbinols and 70 gram dimethylbenzene are put into the 500ml four-hole boiling flask that agitator, thermometer, condenser are housed.Start the whipping appts water of condensation of open cold condenser simultaneously, add 130 gram thiophosphoric anhydrides again, when being warming up to 160 ℃, constant temperature 8 hours.
(2) 140 gram stearic acid, 140 gram diethylenetriamines, 90 gram benzene are added in another 500ml four-hole boiling flask that agitator, thermometer, water trap, condenser are housed simultaneously.Be warmed up to 240 ℃ with 10 ℃/h, dehydration, desolventizing, constant temperature 6 hours, be cooled to 120 ℃, add the reaction product of step (1), constant temperature half an hour, be cooled to room temperature, then reaction product is poured in the matrass, with underpressure distillation solvent is steamed, drying promptly obtains the mixture of novel cpd A2 and novel cpd B2 again.
Embodiment 3:
The structure of novel cpd A3 and B3 and preparation method.
1, the structural formula of novel cpd A3 is formula (9), and the structural formula of B3 is formula (10):
2, preparation method
(1) 150 gram lauryl alcohols and 90 gram dimethylbenzene are put into the 500ml four-hole boiling flask that agitator, thermometer, condenser are housed.Start the whipping appts water of condensation of open cold condenser simultaneously, add 150 gram thiophosphoric anhydrides again, when being warming up to 150 ℃, constant temperature 6 hours.
(2) 240 gram dodecenylsuccinic acids, 50 grams, five ethene hexamines, 70 gram toluene are added in another 500ml four-hole boiling flask that agitator, thermometer, water trap, condenser are housed simultaneously.Be warmed up to 220 ℃ with 10 ℃/h, dehydration, desolventizing, constant temperature 5 hours, be cooled to 80 ℃, add the reaction product of step (1), constant temperature half an hour, the cooling room temperature, then reaction product is poured in the matrass, with underpressure distillation solvent is steamed, drying promptly obtains the mixture of novel cpd A3 and novel cpd B3 again.
Embodiment 4:
The structure of novel cpd A4 and B4 and preparation method.
1, the structural formula of novel cpd A4 is formula (11), and the structural formula of B4 is formula (12):
2, preparation method
(1) earlier 200 gram isooctyl alcohol and 110 gram benzene are put into the 500ml four-hole boiling flask that agitator, thermometer, condenser are housed.Start the whipping appts water of condensation of open cold condenser simultaneously, add 120 gram thiophosphoric anhydrides again, when being warming up to 130 ℃, constant temperature 7 hours.
(2) 120 gram Lignoceric acids, 150 gram triethylene tetramines, 80 gram toluene are added in another 500ml four-hole boiling flask that agitator, thermometer, water trap, condenser are housed simultaneously.Be warmed up to 240 ℃ with 10 ℃/h, dehydration, desolventizing, constant temperature 4 hours, be cooled to 120 ℃, add the reaction product of step (1), constant temperature half an hour, be cooled to room temperature, then reaction product is poured in the matrass, with underpressure distillation solvent is steamed, drying promptly obtains the mixture of novel cpd A4 and novel cpd B4 again.
Embodiment 5:
The structure of novel cpd A5 and B5 and preparation method.
1, the structural formula of novel cpd A5 is formula (13), and the structural formula of B5 is formula (14):
2, preparation method
(1) earlier 160 gram nonylcarbinols and 90 gram toluene are put into the 500ml four-hole boiling flask that agitator, thermometer, condenser are housed.Start the whipping appts water of condensation of open cold condenser simultaneously, add 110 gram thiophosphoric anhydrides again, when being warming up to 100 ℃, constant temperature 8 hours.
(2) 220 gram linolic acid, 70 gram tetraethylene pentamine, 100 gram dimethylbenzene are added in another 500ml four-hole boiling flask that agitator, thermometer, water trap, condenser are housed simultaneously.Be warmed up to 230 ℃ with 10 ℃/h, dehydration, desolventizing, constant temperature 7 hours, be cooled to 90 ℃, add the reaction product of step (1), constant temperature half an hour, the cooling room temperature, then reaction product is poured in the matrass, with underpressure distillation solvent is steamed, drying promptly obtains the mixture of novel cpd A5 and novel cpd B5 again.
Embodiment 6:
Adopt weight-loss method to estimate the inhibiter that embodiment 1-5 makes.
Test raw material: corrosive medium 1 and corrosive medium 2.Corrosive medium character is as shown in table 1.
Test temperature: 260～270 ℃
Test period: 6 hours
Filling rate: 50 μ g/g
Evaluation method: Fe ion content in the corrosive medium before and after the analytical test; The weight of test piece before and after the weighing test is according to the weight loss calculating corrosion rate and the corrosion inhibition rate of test piece.
Corrosion speed (mm/a) is calculated as follows:
In the formula: the C-computational constant, when being unit with mm/a, C=8.76 * 10
7,
The corrosion weight loss (g) of Δ W-test specimen,
Area (the cm of A-test specimen
2),
The T-corrosion test time (h);
Density (the kg/m of ρ-material for test
3).
Corrosion inhibition rate is calculated as follows:
Corrosion inhibition rate
F
oCorrosion rate when not adding inhibiter (blank);
F
kCorrosion rate when adding inhibiter.
Evaluation result is as shown in table 2.
Table 1 corrosive medium character
| Project | Medium 1 | Medium 2 |
| Acid number (mgKOH/g) | 5.0 | 5.0 |
| S(μg/g) | 6230 | 450 |
| Fe(μg/g) | 16.2 | 5.6 |
Table 2 inhibiter evaluation result
| Inhibiter | Filling rate μ g/g | Iron level (μ g/g) | Corrosion rate (mm/a) | Corrosion inhibition rate (%) | |||
| Medium 1 | Medium 2 | Medium 1 | Medium 2 | Medium 1 | Medium 2 | ||
| Blank | 0 | 107.3 | 33 | 1.159 | 1.452 | 0 | 0 |
| Triphenyl phosphite | 50 | 62 | 14.6 | 0.67 | 0.511 | 42.2 | 55.9 |
| The iso-octyl thiophosphatephosphorothioate | 50 | 51.9 | 12.4 | 0.561 | 0.437 | 51.6 | 62.3 |
| Embodiment 1 | 20 | 21.5 | 8.7 | 0.270 | 0.273 | 76.7 | 81.2 |
| Embodiment 1 | 50 | 17.6 | 7.1 | 0.182 | 0.059 | 84.3 | 95.9 |
| Embodiment 1 | 100 | 16.9 | 6.5 | 0.135 | 0.051 | 88.3 | 96.5 |
| Embodiment 2 | 50 | 19.8 | 6.9 | 0.222 | 0.078 | 80.8 | 94.6 |
| Embodiment 3 | 50 | 20.3 | 7.7 | 0.202 | 0.099 | 82.5 | 93.2 |
| Embodiment 4 | 50 | 19.2 | 8.1 | 0.197 | 0.119 | 83.0 | 91.8 |
| Embodiment 5 | 50 | 18.2 | 7.3 | 0.219 | 0.111 | 81.1 | 92.3 |
As shown in Table 2, inhibiter of the present invention all has good inhibitory effect to naphthenic acid corrosion and high-temperature sulfur corrosion, injection rate is 50 μ g/g, the high acid starting material corrosion inhibition rate of low-sulfur is reached more than 90%, the high acid starting material corrosion inhibition rate of high-sulfur is reached more than 80%, all apparently higher than triphenyl phosphite, iso-octyl thiophosphatephosphorothioate.
Claims (7)
1. high-temperature corrosion inhibitor, it is characterized in that: this inhibiter is that a kind of general structure is the compound of formula (1):
R wherein
1Be C
4～C
12Alkyl, R
2Be C
8～C
30Alkyl or alkyl derivative, n is 2～5 integer, A is SH or R
1O.
2. inhibiter according to claim 1 is characterized in that: described R
2Be C
12～C
24Alkyl or alkyl derivative.
3. the preparation method of the described inhibiter of claim 1 is characterized in that comprising the steps:
(i) thiophosphoric anhydride and Fatty Alcohol(C12-C14 and C12-C18) be in organic solvent, is that the generating structure formula is the thiophosphatephosphorothioate compounds of formula (2) under 100～170 ℃ the reaction conditions in normal pressure, temperature,
R wherein
1Be C
4～C
12Alkyl, A is SH or R
1O; Described Fatty Alcohol(C12-C14 and C12-C18) is propyl carbinol, neopentyl alcohol, n-hexyl alcohol, isooctyl alcohol, nonylcarbinol or lauryl alcohol;
(ii) organic acid and polyethylene polyamine be in organic solvent, is that the generating structure formula is the imidazolines of formula (3) under 200～240 ℃ the reaction conditions in normal pressure, temperature,
R wherein
2Be C
8～C
30Alkyl or alkyl derivative, organic acid is C
13～C
25Thiazolinyl organic acid, dialkylene organic acid, alkyl organic acid or cycloalkyl organic acid;
The general structure of described polyethylene polyamine is H
2N (CH
2CH
2NH)
nH, wherein n is 2～5 integer;
Described organic solvent is an aromatic hydrocarbon solvent;
(iii) the compound (3) that (ii) obtains of the compound (2) that step (i) is obtained and step reacted 20～40 minutes under 80～120 ℃, condition of normal pressure, then the solvent in the reaction product is steamed, drying promptly obtains the compound that general structure is the described formula of claim (1) again, is high-temperature corrosion inhibitor of the present invention.
4. preparation method according to claim 3 is characterized in that: the Fatty Alcohol(C12-C14 and C12-C18) described in the step (i) is an isooctyl alcohol; Step (ii) described in organic acid be oleic acid, linolic acid, stearic acid, naphthenic acid, dodecenylsuccinic acid or Lignoceric acid, polyethylene polyamine is diethylenetriamine, triethylene tetramine, tetraethylene pentamine or five ethene hexamines.
5. preparation method according to claim 3 is characterized in that: described organic solvent is benzene, toluene or dimethylbenzene.
6. the application of the described inhibiter of claim 1, it is characterized in that: this inhibiter is used for petroleum refining process corrosion dangerous equipment and pipeline, its application method is: high-temperature corrosion inhibitor is added to the above-mentioned course of processing is produced in the corrosive working fluid, using the initial stage filling rate is that to make the content of inhibiter in the working fluid be 200～1000 μ g/g, treats the Fe in the working fluid
2+Concentration is reduced to when requiring index, and filling rate is that to make the content of inhibiter in the working fluid be 10～100 μ g/g.
7. application according to claim 6 is characterized in that: using the initial stage filling rate is 300～500 μ g/g, the Fe in the working fluid
2+The filling rate that concentration is reduced to when requiring index is 20～50 μ g/g.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101868514A (en) * | 2007-09-14 | 2010-10-20 | 多尔夫凯塔尔化学制品（I）私人有限公司 | A novel additive for naphthenic acid corrosion inhibition and method of using the same |
| CN102220171A (en) * | 2010-04-13 | 2011-10-19 | 中国石油化工集团公司 | Corrosion inhibitor and preparation method thereof |
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| CN104762624A (en) * | 2015-04-08 | 2015-07-08 | 宜兴市中大凯化工有限公司 | High-temperature corrosion inhibitor for atmospheric and vacuum distillation unit |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101868514A (en) * | 2007-09-14 | 2010-10-20 | 多尔夫凯塔尔化学制品（I）私人有限公司 | A novel additive for naphthenic acid corrosion inhibition and method of using the same |
| CN101868514B (en) * | 2007-09-14 | 2015-03-25 | 多尔夫凯塔尔化学制品（I）私人有限公司 | A novel additive for naphthenic acid corrosion inhibition and method of using the same |
| CN102220171A (en) * | 2010-04-13 | 2011-10-19 | 中国石油化工集团公司 | Corrosion inhibitor and preparation method thereof |
| CN102650061A (en) * | 2012-05-07 | 2012-08-29 | 中国海洋石油总公司 | High-temperature corrosion inhibitor for restraining corrosion of high-acid value crude oil and application of high-temperature corrosion inhibitor |
| CN102650061B (en) * | 2012-05-07 | 2014-10-01 | 中国海洋石油总公司 | High-temperature corrosion inhibitor for restraining corrosion of high-acid value crude oil and application of high-temperature corrosion inhibitor |
| CN102965149A (en) * | 2012-12-11 | 2013-03-13 | 江苏汉光实业股份有限公司 | Preparation method of oil soluble corrosion inhibitor |
| CN102965149B (en) * | 2012-12-11 | 2014-06-25 | 江苏汉光实业股份有限公司 | Preparation method of oil soluble corrosion inhibitor |
| CN104762624A (en) * | 2015-04-08 | 2015-07-08 | 宜兴市中大凯化工有限公司 | High-temperature corrosion inhibitor for atmospheric and vacuum distillation unit |
| CN108165246A (en) * | 2016-12-08 | 2018-06-15 | 中国石油天然气股份有限公司 | Oil-water well protection liquid and preparation method thereof |
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