CN101316915A - Corrosion inhibitor - Google Patents
Corrosion inhibitor Download PDFInfo
- Publication number
- CN101316915A CN101316915A CNA2006800449048A CN200680044904A CN101316915A CN 101316915 A CN101316915 A CN 101316915A CN A2006800449048 A CNA2006800449048 A CN A2006800449048A CN 200680044904 A CN200680044904 A CN 200680044904A CN 101316915 A CN101316915 A CN 101316915A
- Authority
- CN
- China
- Prior art keywords
- carbon atom
- compound
- alkyl
- composition
- contain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 21
- 230000007797 corrosion Effects 0.000 title claims abstract description 21
- 239000003112 inhibitor Substances 0.000 title description 6
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 24
- 239000012530 fluid Substances 0.000 claims abstract description 20
- 239000010779 crude oil Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- -1 sulfo-phosphorus compound Chemical class 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 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 description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000002480 mineral oil Substances 0.000 claims description 5
- 235000010446 mineral oil Nutrition 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Chemical group 0.000 claims description 4
- 229910052760 oxygen Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims 20
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 239000002253 acid Substances 0.000 abstract description 10
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 230000002000 scavenging effect Effects 0.000 abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OTQJLBQYAAHCMS-UHFFFAOYSA-N P(O)(O)=O.S1CNCC1 Chemical class P(O)(O)=O.S1CNCC1 OTQJLBQYAAHCMS-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XMVQWNRDPAAMJB-UHFFFAOYSA-N (+)-13-Cyclopent-2-enyl-tridecansaeure Natural products OC(=O)CCCCCCCCCCCCC1CCC=C1 XMVQWNRDPAAMJB-UHFFFAOYSA-N 0.000 description 1
- XMVQWNRDPAAMJB-QGZVFWFLSA-N (S)-chaulmoogric acid Chemical compound OC(=O)CCCCCCCCCCCC[C@H]1CCC=C1 XMVQWNRDPAAMJB-QGZVFWFLSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- GTCZFOKUGWSLLG-UHFFFAOYSA-N OS([P])(=O)=O Chemical class OS([P])(=O)=O GTCZFOKUGWSLLG-UHFFFAOYSA-N 0.000 description 1
- 241000539618 Salma Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000001997 corrosion-resisting alloy Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G7/00—Distillation of hydrocarbon oils
- C10G7/10—Inhibiting corrosion during distillation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/02—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1033—Oil well production fluids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
- C10G2300/203—Naphthenic acids, TAN
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/80—Additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Lubricants (AREA)
Abstract
A composition and method of inhibiting corrosion caused by naphthepic acid in fluids includes using a combination of a thiophosphorus compound and a hydrogen sulfide scavenging compound. The hydrogen sulfide scavenging compound significantly enhances the performance of the thiophosphorus compound and may be included at relatively low levels in the composition. The treatment may be applied to fluids including crude oils and lighter fractions thereof.
Description
Technical field
The present invention relates to inhibiter.The invention particularly relates to the inhibiter of the application that can be used for wherein existing naphthenic acid.
Background technology
Be well known in the art, crude oil may cause the infringement on the ferrous metal surface of processing units with the processing of its various cut forms.In particular, this corrosion is often relevant with activity with the existence of naphthenic acid.When the amount of the naphthenic acid in the hydrocarbon reached certain threshold value by total acid value (" TAN ") expression, corrosion took place, during total acid value is expressed as and the sour required potassium hydroxide milligram quantities in the 1 gram sample.Document in the past it has been generally acknowledged that for causing naphthenic acid corrosion, and the TAN of crude oil must be greater than about 0.5, but nearer experience shows that threshold value can be worth thus significant the change taken place.When crude oil was applied the temperature of rising, such as 175 ℃ (～347)-about 400 ℃ temperature that (～752) are generally used for refining and distill the crude oil, etching problem was normally further aggravated.
Although multiple inhibiter known in the art, the usefulness of known any particular corrosion inhibitor all depends on the environment that uses it usually usually.Thereby various inhibiter have been developed and target is used to handle the burn into of selective crude, protection special metal, inhibition particular type and/or use under conditions such as specific temperature, environment.For example, U.S. patent 3,909,447 has been described some inhibiter can resist corrosion in cryogenic relatively containing in oxygen (oxygenated) Aquo System, such as water filling (water floods), cooling tower, drilling mud, pneumatic drill and automatization radiator system.
As normally used, naphthenic acid is to be referred to as about some organic acid that is present in the various crude oil.Though also can there be a spot of other organic acid, be appreciated that the most of acid in the cycloalkanes acidic group crude oil are naphthenic on characteristic, promptly have the saturated rings structure that meets such as one of following structural:
In the above-mentioned formula, m 1-2 and n typically can change.Be essentially any and encircle the hydroxy-acid groups that are connected with at least one saturated 5 or 6 yuan.A simplified example is a chaulmoogric acid.
The molecular weight of naphthenic acid can spread all over very big scope.Yet, after distillation, in light ends, found the most of naphthenic acid in the crude oil, comprise (for example) gas oil.Hydrocarbon contact ferrous metal when comprising above-mentioned naphthenic acid in the time of especially at elevated temperatures, serious etching problem occurs.
Various gate ring naphthenic acid induced corroding method comprise: neutralization and/or remove naphthenic acid from the crude oil of processing; With the crude oil of low acid number and bigger corrosive crude oil with high acid value blend to reduce whole neutralization value; With the relatively costly corrosion-resisting alloy of employing in the structure of CDU.These attempt usually requiring extra process and/or increase on the remarkable cost of crude Treatment that at it disadvantage is arranged.Optionally, U.S. patent 4,443,609 discloses some thiazolidine phosphonic acids and the effective additive that suppresses acid corrosion of ester conduct.Above-mentioned inhibitor can by make some 2,5-thiazoline and dialkyl phosphites reaction and preparing.Though these thiazolidine phosphonic acids or ester provide the good effect of corrosion inhibition, it tends to decompose under hot conditions.
Adopting phosphorio compound is that phosphorus has been concluded the effect that can weaken the various catalyzer that are used to handle crude oil as another shortcoming of inhibiter, such as in fixed bed hydrogenation treater and hydroeracking unit.Therefore, crude oil processor is often faced adverse conditions, because if do not suppress, corrosion itself can cause the gathering of the iron of catalyzer amount of attenuation in the hydrocarbon fluid, sometimes up to 10-20ppm.Regrettably, although many commercially available non-phosphorus base inhibitor are arranged, known they usually than phosphorio compound poor efficiency slightly.
The obvious progress of phosphorus basic ring naphthenic acid induced corrosion inhibitors is reported in U.S. patent 4,941,994.The metallic corrosion that wherein discloses in the hot acid liquid hydrocarbon is suppressed with optional thiazoline by dialkyl group and/or the trialkyl phosphite that has corrosion inhibition amount.Another patent, U.S. patent 5,863,415, the sulfo-phosphorus compound that discloses the ad hoc structure formula especially can be used for corrosion inhibition in the hot liquid hydrocarbon, and it uses with the finite concentration that joins in the fluid, and its catalyzer weakens phosphorus and is weaker than some previous phosphorus base inhibiter.These sulfo-phosphorus compounds have also presented the advantage that can be prepared by the starting raw material of relatively low cost.
In sum, find in the art to be used for to suppress or the burn into of controlling the crude oil naphthenic acid induced has better than other method and composition of prior art advantage and expects.
Summary of the invention
On the one hand, the present invention is the method that is used for suppressing at the fluid that contains the etching extent naphthenic acid naphthenic acid corrosion, this method comprises: add sulfo-phosphorus compound and hydrogen sulfide removing compound to this fluid or charging therefore, wherein sulfo-phosphorus compound and hydrogen sulfide are removed compound for can effectively suppress the corrosive amount.
On the other hand, the present invention is used in the composition that suppresses naphthenic acid corrosion in the fluid that contains the etching extent naphthenic acid, and said composition comprises the mixture of sulfo-phosphorus compound and hydrogen sulfide removing compound.
On the one hand, the present invention is the method that is used for suppressing at the fluid that contains the etching extent naphthenic acid naphthenic acid corrosion, and this method comprises to this fluid or the enough sulfo-phosphorus compound of corrosion inhibition amount and the hydrogen sulfide realized in this fluid of the interpolation of charging therefore removes compound.This fluid can be that for example, hydrocarbon is such as crude oil or its light ends.Can be used for sulfo-phosphorus compound of the present invention and comprise and be disclosed in U.S. patent No.5, those of 863,415 (Zetlmeisl), its full content is hereby incorporated by.For example, can be used for implementing salt, the alkyl ester of sulfo-phosphorus compound and the isomer of aryl ester and sulfo-phosphorus compound that sulfo-phosphorus compound of the present invention comprises the sulfo-phosphorus compound.Any inhibiting sulfo-phosphorus compound of naphthenic acid induced corrosion of can realizing in fluid can be applicable to the present invention.
In a non-limiting embodiments, can be used for of the present invention for having the sulfo-phosphorus compound of following general formula:
R wherein
1Be R
3(OCH
2CH
2)
n-or R
3(OCH
2CH
2)
nO-, R
2With R
1Identical or-XH, each X is sulphur or oxygen independently, is sulphur but condition is at least one X, R
3The alkyl and the n that are about 18 carbon atoms of about 6-are the integers of 0-about 12.
Can be used for hydrogen sulfide of the present invention and remove compound and comprise and be disclosed in U.S. patent Nos.5, those of 169,411 (Weers) and 6,663,841 (Salma etc.), its full content is hereby incorporated by.Comprise nonacid group with imine moiety in this compound, it is the condensation product of amine or polyamine and aldehyde, two aldehydes or ketones.For example, in non-limiting embodiments, it comprises those compounds with following general formula:
R
1(N=R
2)
xFormula 2
Wherein x is the integer of about 1-about 10; R
1Be independently selected from:
R
3O (CH
2)
n, formula 3
Contain about 7 carbon atoms of about 4-cycloalkyl, phenyl, benzyl, contain the alkyl of about 20 carbon atoms of 1-and contain the thiazolinyl of about 20 carbon atoms of 1-; R
3Be hydrogen, contain about 20 carbon atoms of 1-alkyl, contain the thiazolinyl or the aryl of about 20 carbon atoms of 1-; N is the integer of 1-6; R
4, R
5, and R
6Be selected from independently of one another the alkyl that contains about 20 carbon atoms of 1-and
R
7Be hydrogen or alkyl and and the R that contains about 20 carbon atoms of 1-
2Identical when condition be R only
4, R
5And R
6One of can be:
And R
2Be independently selected from=CH
2, cyclohexyl,
Contain the alkyl of about 20 carbon atoms of 1-and contain the thiazolinyl of about 20 carbon atoms of 1-.In formula 5 and 6, there is at least one sulphur atom in " S " representative ring, do not specify for its one or more positions.
Found inhibitor of the present invention not only effectively but also have store and application process in very the hydrogen sulfide of low levels emit.In some non-limiting embodiments, wish that the amount of sulfo-phosphorus compound accounts for the about 70 weight % of about 40-of the whole additives that comprise sulfo-phosphorus compound and hydrogen sulfide removing compound.In other embodiments, it can be 1-10 weight % that hydrogen sulfide is removed compound, and the about 6 weight % of preferably about 4-.The remainder of additive can be the inert substance with fluid compatible, such as (for example) mineral oil.In other non-limiting embodiments, the sulfo-phosphorus compound can account for the about 99 weight % of about 90-of whole additives, and in other non-limiting embodiments, it can account for the about 96 weight % of about 94-.
The compositions of additives that sulfo-phosphorus compound and hydrogen sulfide are removed compound can any corrosive amount that can effectively suppress to be caused by fluid/naphthenic acid be applied to this fluid (comprising the corrodibility naphthenic acid).These can be low relatively, and about 100ppm-is about 5,000ppm, but can adopt more or less amount, if this tittle is effective.In the embodiment of many expectations, found that about 500ppm-is about 2, the content of 000ppm is effectively, and in the embodiment of other expectation, can be the about 1250ppm of about 750ppm-.
Provide the following example for the present invention will be described.Embodiment does not represent to limit the scope of the invention and should so do not understood.Except as otherwise noted, measure and be weight part or weight %.
Embodiment 1
Test of the present invention is undertaken by at first determining level
Program comprises the step of adding 282 mineral oil that restrain to reaction flask.Under the continuously stirring, detection cell with nitrogen with the speed bubbling of 10-20mL/min 30-60 minute.With well heater be arranged on 288 ℃ and to the remainder of test with 1 mole of % H in nitrogen
2The S bubbling.Trace routine is carried out with the hydrogen sulfide in the nitrogen of total acid value 10mg KOH, 288 ℃ of temperature, experimental period 24 hours and 1 mole of %, employing C1018 carbon steel coupons.At first test " blank " (not having inhibiter) is to determine the etching extent of appearance.Lacing film inserts after the detection cell, and the naphthenic acid that is purchased that about 20 grams is had total acid value 151 injected 30 minutes.Then, first test of the present invention adopts another lacing film and same program to carry out, except comprising inhibiter of the present invention.Inhibiter is the mixture of sulfo-phosphorus compound and hydrogen sulfide scavenger compound, its content is by volume 1000ppm, wherein the sulfo-phosphorus compound exists with the amount of scavenging agent with 5 weight % with the amount of 55 weight % and exists, and the rest part of mixture is a mineral oil.In all cases lacing film was kept in detection cell after 24 hours its taking-up is estimated.In second test, adopt another lacing film also to finish check program of the present invention.
In first test, with when with " blank " when comparing, protection level provided by the present invention is measured as 94.2%.In second test of the present invention, the protection level is measured as 99.7%.
Comparative Examples 2
Repeat embodiment 1 substantially the samely, except not adopting hydrogen sulfide scavenger, but adopt the sulfo-phosphorus compound of same amount.In first test, the protection level is measured as 80.1%.In second test, the protection level is measured as 89.2%.
Claims (17)
1. method that is used for suppressing naphthenic acid corrosion at the fluid that contains the etching extent naphthenic acid, this method comprises to this fluid or the sulfo-phosphorus compound is added in charging therefore and hydrogen sulfide is removed compound, and wherein this sulfo-phosphorus compound and this hydrogen sulfide are removed compound for suppressing the corrosive amount.
2. the process of claim 1 wherein this sulfo-phosphorus compound and this hydrogen sulfide removing compound are added as mixture.
3. the process of claim 1 wherein that this sulfo-phosphorus compound has general formula:
R wherein
1Be R
3(OCH
2CH
2)
n-or R
3(OCH
2CH
2)
nO-, R
2With R
1Identical or-XH, each X is sulphur or oxygen independently, is sulphur but condition is at least one X, R
3Be the alkyl of 6-18 carbon atom and the integer that n is 0-12.
4. the process of claim 1 wherein that this hydrogen sulfide removing compound has general formula:
R
1(N＝R
2)
x
Wherein x is the integer of about 1-about 10; R
1Be independently selected from:
R
3O(CH
2)
n——、
Contain 4-7 carbon atom cycloalkyl, phenyl, benzyl, contain the alkyl of 1-20 carbon atom and contain the thiazolinyl of 1-20 carbon atom; R
3Be hydrogen, contain the alkyl of 1-20 carbon atom, the thiazolinyl that contains 1-20 carbon atom or aryl; N is the integer of 1-6; R
4, R
5, and R
6Be selected from independently of one another the alkyl that contains 1-20 carbon atom and
R
7Be hydrogen or the alkyl that contains 1-20 carbon atom and and R
2Identical when condition be R only
4, R
5With
R
6One of can be:
And R
2Be independently selected from=CH
2, cyclohexyl,
Contain the alkyl of 1-20 carbon atom and contain the thiazolinyl of 1-20 carbon atom; Wherein S represents the sulphur atom of at least one any position in this ring.
5. the process of claim 1 wherein that this fluid is crude oil or its cut.
6. the method for claim 2, wherein to remove the content of compound in this mixture be 1-10 weight % to this hydrogen sulfide.
7. the composition of claim 6, wherein to remove the content of compound in this mixture be 4-6 weight % to this hydrogen sulfide.
8. the composition of claim 2, wherein the content of this sulfo-phosphorus compound in mixture is 40-70 weight %.
9. the composition of claim 2, wherein this mixture further comprises mineral oil.
10. one kind is used in the composition that suppresses naphthenic acid corrosion in the fluid that contains the etching extent naphthenic acid, and said composition comprises following mixture: this mixture comprises sulfo-phosphorus compound and hydrogen sulfide removing compound.
11. the composition of claim 10, wherein this fluid is crude oil or its cut.
12. the composition of claim 10, wherein the content of this hydrogen sulfide removing compound in this mixture is 1-10 weight %.
13. the composition of claim 12, wherein the content of this hydrogen sulfide removing compound in this mixture is 4-6 weight %.
14. the composition of claim 10, wherein the content of this sulfo-phosphorus compound in mixture is 40-70 weight %.
15. the composition of claim 10, wherein this mixture further comprises mineral oil.
16. the composition of claim 10, wherein this sulfo-phosphorus compound has general formula:
R wherein
1Be R
3(OCH
2CH
2)
n-or R
3(OCH
2CH
2)
nO-, R
2With R
1Identical or-XH, each X is sulphur or oxygen independently, is sulphur but condition is at least one X, R
3Be the alkyl of 6-18 carbon atom and the integer that n is 0-12.
17. the composition of claim 10, wherein this hydrogen sulfide removing compound has general formula:
R
1(N＝R
2)
x
Wherein x is the integer of about 1-10; R
1Be independently selected from:
R
3O(CH
2)
n——、
Contain 4-7 carbon atom cycloalkyl, phenyl, benzyl, contain the alkyl of 1-20 carbon atom and contain the thiazolinyl of 1-20 carbon atom; R
3Be hydrogen, contain the alkyl of 1-20 carbon atom, the thiazolinyl that contains 1-20 carbon atom or aryl; N is the integer of 1-6; R
4, R
5, and R
6Be selected from independently of one another the alkyl that contains 1-20 carbon atom and
R
7Be hydrogen or the alkyl that contains 1-20 carbon atom and and R
2Identical when condition be R only
4, R
5With
R
6One of can be:
And R
2Be independently selected from=CH
2, cyclohexyl,
Contain the alkyl of 1-20 carbon atom and contain the thiazolinyl of 1-20 carbon atom; Wherein S represents the sulphur atom of at least one any position in this ring.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US74143005P | 2005-11-30 | 2005-11-30 | |
| US60/741,430 | 2005-11-30 | ||
| PCT/US2006/061101 WO2007065064A2 (en) | 2005-11-30 | 2006-11-20 | Corrosion inhibitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101316915A true CN101316915A (en) | 2008-12-03 |
| CN101316915B CN101316915B (en) | 2015-07-22 |
Family
ID=38092918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200680044904.8A Expired - Fee Related CN101316915B (en) | 2005-11-30 | 2006-11-20 | Corrosion inhibitor |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20070119747A1 (en) |
| EP (1) | EP1963462A4 (en) |
| KR (1) | KR101364325B1 (en) |
| CN (1) | CN101316915B (en) |
| BR (1) | BRPI0619195A2 (en) |
| CA (1) | CA2631572A1 (en) |
| WO (1) | WO2007065064A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101987973A (en) * | 2009-07-30 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Method for reducing corrosivity of acid-contained hydrocarbon oil |
| CN103459561A (en) * | 2011-03-24 | 2013-12-18 | 贝克休斯公司 | Synergistic H2S/mercaptan scavengers using glyoxal |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5713669B2 (en) * | 2007-03-30 | 2015-05-07 | ドルフ ケタール ケミカルズ （インディア）プライヴェート リミテッド | Prevention of high temperature naphthenic acid corrosion using organophosphorus sulfur compounds and combinations thereof |
| CN101688118B (en) * | 2007-04-04 | 2014-10-29 | 多尔夫凯塔尔化学制品（I）私人有限公司 | Naphthenic acid corrosion inhibition using new synergetic combination of phosphorus compounds |
| US20090061234A1 (en) * | 2007-09-04 | 2009-03-05 | Baker Hughes Incorporated | Method for Inhibiting Corrosion of Metal in Distillation Units Caused by Organic Acids |
| PL2193179T3 (en) * | 2007-09-14 | 2017-07-31 | Dorf Ketal Chemicals (I) Private Limited | A novel additive for naphthenic acid corrosion inhibition and method of using the same |
| PL2340296T3 (en) * | 2008-08-26 | 2015-03-31 | Dorf Ketal Chemicals I Private Ltd | A new additive for inhibiting acid corrosion and method of using the new additive |
| PE20110787A1 (en) * | 2008-08-26 | 2011-10-31 | Dorf Ketal Chemicals India Private Ltd | A NOVEL AND AFFECTIVE POLYMER ADDITIVE TO INHIBIT THE CORROSION OF NAPHENIC ACIDS AND METHODS FOR THE USE OF THE SAME |
| US9068128B2 (en) | 2011-10-18 | 2015-06-30 | Baker Hughes Incorporated | Method for reducing hydrogen sulfide evolution from asphalt and heavy fuel oils |
| US9140640B2 (en) * | 2012-11-06 | 2015-09-22 | Exxonmobil Research And Engineering Company | Method for identifying layers providing corrosion protection in crude oil fractions |
| US20160060520A1 (en) * | 2014-09-03 | 2016-03-03 | Baker Hughes Incorporated | Scavengers for sulfur species and/or phosphorus containing compounds |
| US10655232B2 (en) * | 2014-09-03 | 2020-05-19 | Baker Hughes, A Ge Company, Llc | Additives to control hydrogen sulfide release of sulfur containing and/or phosphorus containing corrosion inhibitors |
| CA3086018A1 (en) * | 2018-01-12 | 2019-07-18 | Baker Hughes Holdings Llc | Additives to control hydrogen sulfide release of sulfur containing and/or phosphorus containing corrosion inhibitors |
Family Cites Families (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2643227A (en) * | 1950-02-21 | 1953-06-23 | Cities Service Oil Co | Method of inhibiting corrosion of metals |
| US3595790A (en) * | 1969-10-22 | 1971-07-27 | Lubrizol Corp | Oil soluble highly basic metal salts of organic acids |
| US3711403A (en) * | 1971-01-18 | 1973-01-16 | Petrolite Corp | Corrosion inhibitors employing phosphate esters of cyclic amidines |
| US3909447A (en) * | 1972-07-17 | 1975-09-30 | Petrolite Corp | Mixtures of thiophosphates, oxygen phosphates and pyrophosphates |
| US4339349A (en) * | 1980-02-11 | 1982-07-13 | Petrolite Corporation | Corrosion inhibitors for limited oxygen systems |
| US4443609A (en) * | 1980-05-19 | 1984-04-17 | Petrolite Corporation | Tetrahydrothiazole phosphonic acids or esters thereof |
| US4511481A (en) * | 1983-08-31 | 1985-04-16 | Mobil Oil Corporation | Multifunctional additives |
| US4842716A (en) * | 1987-08-13 | 1989-06-27 | Nalco Chemical Company | Ethylene furnace antifoulants |
| US5169411A (en) * | 1989-03-03 | 1992-12-08 | Petrolite Corporation | Suppression of the evolution of hydrogen sulfide gases from crude oil, petroleum residua and fuels |
| GB8906406D0 (en) * | 1989-03-21 | 1989-05-04 | Bp Chem Int Ltd | Removal of sulphides |
| US4941994A (en) * | 1989-07-18 | 1990-07-17 | Petrolite Corporation | Corrosion inhibitors for use in hot hydrocarbons |
| CA2017047C (en) * | 1989-08-01 | 1999-08-17 | Jerry J. Weers | Method of scavenging hydrogen sulfide from hydrocarbons |
| US5266185A (en) * | 1990-09-10 | 1993-11-30 | Petrolite Corporation | Method of suppression of hydrogen sulfide with heterocyclic-amine aldehyde reaction products |
| MX9305120A (en) * | 1992-09-04 | 1994-03-31 | Lubrizol Corp | SULFURATED OVERBASED COMPOSITIONS. |
| US5500107A (en) * | 1994-03-15 | 1996-03-19 | Betz Laboratories, Inc. | High temperature corrosion inhibitor |
| US5552085A (en) * | 1994-08-31 | 1996-09-03 | Nalco Chemical Company | Phosphorus thioacid ester inhibitor for naphthenic acid corrosion |
| US5630964A (en) * | 1995-05-10 | 1997-05-20 | Nalco/Exxon Energy Chemicals, L.P. | Use of sulfiding agents for enhancing the efficacy of phosphorus in controlling high temperature corrosion attack |
| ES2192677T3 (en) * | 1996-05-30 | 2003-10-16 | Baker Hughes Inc | CORROSION CONTROL BY NAPTENIC ACID WITH THIOPHOSPHORUS COMPOUNDS. |
| US6267938B1 (en) * | 1996-11-04 | 2001-07-31 | Stanchem, Inc. | Scavengers for use in reducing sulfide impurities |
| US5712230A (en) * | 1997-03-10 | 1998-01-27 | The Lubrizol Corporation | Additive compositions having reduced sulfur contents for lubricants and functional fluids |
| US5863445A (en) * | 1997-03-27 | 1999-01-26 | Control Screening L.L.C. | Etched coil unibody digital detector |
| US6063346A (en) * | 1998-06-05 | 2000-05-16 | Intevep, S. A. | Process for scavenging hydrogen sulfide and mercaptan contaminants from a fluid |
| GB0031710D0 (en) * | 2000-12-27 | 2001-02-07 | Dyno Oil Field Chemicals | Process for the reduction or elimination of hydrogen sulphide |
| US7255796B2 (en) * | 2004-07-08 | 2007-08-14 | General Electric Company | Method of preventing hydrogen sulfide odor generation in an aqueous medium |
-
2006
- 2006-11-17 US US11/601,402 patent/US20070119747A1/en not_active Abandoned
- 2006-11-20 EP EP06846353A patent/EP1963462A4/en not_active Withdrawn
- 2006-11-20 CN CN200680044904.8A patent/CN101316915B/en not_active Expired - Fee Related
- 2006-11-20 BR BRPI0619195-9A patent/BRPI0619195A2/en not_active Application Discontinuation
- 2006-11-20 CA CA002631572A patent/CA2631572A1/en not_active Abandoned
- 2006-11-20 WO PCT/US2006/061101 patent/WO2007065064A2/en active Application Filing
- 2006-11-20 KR KR1020087012612A patent/KR101364325B1/en not_active IP Right Cessation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101987973A (en) * | 2009-07-30 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Method for reducing corrosivity of acid-contained hydrocarbon oil |
| CN101987973B (en) * | 2009-07-30 | 2015-04-29 | 中国石油化工股份有限公司 | Method for reducing corrosivity of acid-contained hydrocarbon oil |
| CN103459561A (en) * | 2011-03-24 | 2013-12-18 | 贝克休斯公司 | Synergistic H2S/mercaptan scavengers using glyoxal |
| US9260669B2 (en) | 2011-03-24 | 2016-02-16 | Baker Hughes Incorporated | Synergistic H2S/mercaptan scavengers using glyoxal |
| CN103459561B (en) * | 2011-03-24 | 2016-03-30 | 贝克休斯公司 | Use oxalic dialdehyde collaborative H 2s/ mercaptan scavenging agent |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0619195A2 (en) | 2011-09-20 |
| CN101316915B (en) | 2015-07-22 |
| EP1963462A4 (en) | 2012-01-04 |
| US20070119747A1 (en) | 2007-05-31 |
| WO2007065064A3 (en) | 2007-12-21 |
| EP1963462A2 (en) | 2008-09-03 |
| CA2631572A1 (en) | 2007-06-07 |
| WO2007065064A2 (en) | 2007-06-07 |
| KR101364325B1 (en) | 2014-02-18 |
| KR20080070833A (en) | 2008-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101316915B (en) | Corrosion inhibitor | |
| US9719035B2 (en) | Method and compositions for inhibition of naphthenic acid induced corrosion | |
| US5863415A (en) | Control of naphthenic acid corrosion with thiophosporus compounds | |
| JP5619601B2 (en) | Naphthenic acid corrosion inhibiting composition using a new synergistic combination of phosphorus compounds and method of use | |
| CA2682373C (en) | High temperature naphthenic acid corrosion inhibition using organophosphorous sulphur compounds and combinations thereof | |
| KR20100085916A (en) | A novel additive for naphthenic acid corrosion inhibition and method of using the same | |
| CA2672415C (en) | Novel mercaptan-based corrosion inhibitors | |
| JP2010539278A5 (en) | ||
| FR2857372A1 (en) | Protecting metal walls of refinery units from corrosion by naphthenic acids in crude oil or distillation fractions, involves adding a thiol-substituted carboxylic acid or derivative, e.g. thioglycolic acid, to the hydrocarbon feed stream | |
| CN1208499C (en) | Metal corrosion inhibitor | |
| US20160060520A1 (en) | Scavengers for sulfur species and/or phosphorus containing compounds | |
| EP0392896B1 (en) | Composition and process to reduce the corrosiveness of oxygenised salty solutions by bubbling with acid gases | |
| US11434413B1 (en) | Flourinated aromatic compound as refinery corrosion inhibitor | |
| US20210179926A1 (en) | Methods, products & uses relating to scavenging of acidic sulfide species | |
| FR2866030A1 (en) | Counteracting corrosion in metallic walls of refining units, by naphthenic acids, involves using tertiary alkyl mercaptans | |
| MXPA98010102A (en) | Control of corrosion by nafety acid concompuestos tiofosfori |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150722 Termination date: 20151120 |
|
| EXPY | Termination of patent right or utility model |