CN101316915B - Corrosion inhibitor - Google Patents
Corrosion inhibitor Download PDFInfo
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- CN101316915B CN101316915B CN200680044904.8A CN200680044904A CN101316915B CN 101316915 B CN101316915 B CN 101316915B CN 200680044904 A CN200680044904 A CN 200680044904A CN 101316915 B CN101316915 B CN 101316915B
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- Prior art keywords
- compound
- carbon atom
- composition
- hydrogen sulfide
- thiosphosphorus
- Prior art date
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- 238000005260 corrosion Methods 0.000 title claims abstract description 23
- 230000007797 corrosion Effects 0.000 title claims abstract description 23
- 239000003112 inhibitor Substances 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 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 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 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
- 239000005864 Sulphur Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- -1 hydrogen Chemical class 0.000 claims description 5
- 239000002480 mineral oil Substances 0.000 claims description 5
- 235000010446 mineral oil Nutrition 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 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
- 125000000753 cycloalkyl group Chemical group 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
- 239000002253 acid Substances 0.000 abstract description 11
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 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
- 230000000670 limiting effect Effects 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005764 inhibitory process 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
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000005587 bubbling Effects 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 group 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
- 241000539618 Salma Species 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
- 238000006243 chemical reaction Methods 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
- 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
- 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
- 230000006698 induction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 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
- 230000000717 retained 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 that can be used for the application that wherein there is 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 form.In particular, this corrosion is often relevant with activity with the existence of naphthenic acid.When the amount of the naphthenic acid in hydrocarbon reaches certain threshold value represented by total acid value (" TAN "), corrosion occurs, the potassium hydroxide milligram quantities needed for acid during total acid value is expressed as and in 1 gram of sample.Document in the past it has been generally acknowledged that the TAN of crude oil must be greater than about 0.5 for causing for naphthenic acid corrosion, but nearer experience shows that threshold value can be worth thus, and significant change occurs.When elevated temperatures are applied to the crude, the temperature that such as 175 DEG C (~ 347 ℉)-about 400 DEG C (~ 752 ℉) is generally used for refining and distills the crude oil, etching problem is normally typically further exacerbated.
Although multiple inhibiter known in the art, the usefulness of usual known any particular corrosion inhibitor all depends on the environment using it usually.Thus, various inhibiter be developed and target for the treatment of selective crude, protection special metal, suppress particular type burn into and/or use under the conditions such as specific temperature, environment.Such as, U.S. patent 3,909,447 describe some inhibiter can resist corrosion, such as water filling (water floods), cooling tower, drilling mud, pneumatic drill and automatization radiator system in containing in oxygen (oxygenated) Aquo System of relative low temperature.
As normally used, naphthenic acid is that the organic acid be present in various crude oil about some is referred to as.Although other a small amount of organic acid also can be there is, be appreciated that the most of acid in naphthenic acid based crude are characteristically naphthenic, namely there is the saturated rings structure meeting such as one of following structural:
In above-mentioned formula, m is 1-2 typically, and n alterable.Be essentially any hydroxy-acid group be connected with at least one saturated 5 or 6 ring.A simplified example is chaulmoogric acid.
The molecular weight of naphthenic acid can spread all over very large scope.But, after distillation, in light ends, find the most of naphthenic acid in crude oil, comprise (such as) gas oil.When comprising the hydrocarbon contact ferrous metal of above-mentioned naphthenic acid, time especially at elevated temperatures, there is serious etching problem.
The method of various control naphthenic acid induced corrosion comprises: neutralization and/or removing naphthenic acid from the crude oil carrying out processing; By blended to reduce overall neutralization value to the crude oil of low acid number and larger corrosive crude oil with high acid value; Relatively costly corrosion-resisting alloy is adopted with in the structure of CDU.These attempt usually requiring extra process and/or increase on the remarkable cost of crude Treatment have disadvantage at it.Optionally, U.S. patent 4,443,609 disclose some thiazolidine phosphonic acids and ester as the additive effectively suppressing acid corrosion.Above-mentioned inhibitor can react by making some 2,5-thiazoline and dialkyl phosphites and prepare.Although these thiazolidine phosphonic acids or ester provide the good effect of corrosion inhibition, it tends to decompose under the high temperature conditions.
Phosphorio compound is adopted to be that phosphorus is concluded the effect of the various catalyzer that can weaken for the treatment of crude oil, such as in fixed bed hydrogenation treater and hydroeracking unit as another shortcoming of inhibiter.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 hydrocarbon fluid, sometimes up to 10-20ppm.Regrettably, although there are many commercially available non-phosphorus-based inhibitors, known they usually than phosphorio compound poor efficiency slightly.
The obvious progress of phosphorus-based naphthenic acid induction inhibiter is reported in U.S. patent 4,941,994.It is disclosed that metallic corrosion in hot acid liquid hydrocarbon is suppressed by there is the dialkyl group of corrosion inhibiting amount and/or trialkyl phosphite and optional thiazoline.Another patent, U.S. patent 5,863,415, it is corrosion inhibition that the thiosphosphorus compound disclosing ad hoc structure formula especially can be used in hot liquid hydrocarbon, and it uses with the finite concentration joined in fluid, and its catalyzer weakens phosphorus and is weaker than some previous phosphorus base inhibiter.These thiosphosphorus compound also present the advantage that can be prepared by the starting raw material of relatively low cost.
In sum, find in the art for suppress or control the burn into of naphthenic acid induced in crude oil have other method and composition surpassing prior art advantage be expect.
Summary of the invention
On the one hand, the present invention is the method for suppressing naphthenic acid corrosion in the fluid containing etching extent naphthenic acid, the method comprises: add thiosphosphorus compound and hydrogen sulfide removing compound to this fluid or charging therefore, and wherein thiosphosphorus compound and hydrogen sulfide remove compound is the amount that can effectively suppress to corrode.
On the other hand, the present invention is used in the composition suppressing naphthenic acid corrosion in the fluid containing etching extent naphthenic acid, and said composition comprises the mixture of thiosphosphorus compound and hydrogen sulfide removing compound.
On the one hand, the present invention is the method for suppressing naphthenic acid corrosion in the fluid containing etching extent naphthenic acid, and the method comprises adds to this fluid or charging therefore in this fluid, enough realize corrosion inhibition amount thiosphosphorus compound and hydrogen sulfide removing compound.This fluid can be, such as, and hydrocarbon such as crude oil or its light ends.Thiosphosphorus compound used in the present invention comprises and is disclosed in U.S. patent No.5,863, those of 415 (Zetlmeisl), and its full content is hereby incorporated by.Such as, can be used for implementing the isomer that thiosphosphorus compound of the present invention comprises the salt of thiosphosphorus compound, the alkyl ester of thiosphosphorus compound and aryl ester and thiosphosphorus compound.Any inhibiting thiosphosphorus compound that can realize naphthenic acid induced corrosion in a fluid can be applicable to the present invention.
In one non-limiting embodiment, the thiosphosphorus compound for having following general formula used in the present invention:
Wherein R
1r
3(OCH
2cH
2)
n-or R
3(OCH
2cH
2)
no-, R
2with R
1identical or-XH, each X are sulphur or oxygen independently, but condition is at least one X is sulphur, R
3be the alkyl of about 6-about 18 carbon atoms, and n is the integer of 0-about 12.
Hydrogen sulfide used in the present invention is removed compound and is comprised and be disclosed in U.S. patent Nos.5,169,411 (Weers) and 6,663, those of 841 (Salma etc.), and its full content is hereby incorporated by.This compound comprises nonacid group with imine moiety, and it is the condensation product of amine or polyamine and aldehyde, two aldehydes or ketones.Such as, in a not limiting embodiment, 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
1independently selected from:
R
3o (CH
2)
n, formula 3
Contain the cycloalkyl of about 4-about 7 carbon atoms, phenyl, benzyl, the alkyl containing 1-about 20 carbon atoms and the thiazolinyl containing 1-about 20 carbon atoms; R
3hydrogen, the alkyl containing 1-about 20 carbon atoms, the thiazolinyl containing 1-about 20 carbon atoms or aryl; N is the integer of 1-6; R
4, R
5, and R
6be selected from independently of one another containing 1-about 20 carbon atoms alkyl and
R
7hydrogen or containing the alkyl of 1-about 20 carbon atoms, and with R
2identical when condition be only R
4, R
5and R
6one of can be:
And R
2independently selected from=CH
2, cyclohexyl,
Alkyl containing 1-about 20 carbon atoms and the thiazolinyl containing 1-about 20 carbon atoms.In formula 5 and 6, there is at least one sulphur atom in " S " representative ring, the one or more positions for it are not specified.
Find that inhibitor of the present invention not only effectively but also have and storing and the hydrogen sulfide releasing of unusual low levels in application process.In certain non-limiting embodiments, wish that the amount of thiosphosphorus compound accounts for the about 40-about 70 % by weight of the whole additives comprising thiosphosphorus compound and hydrogen sulfide removing compound.In other embodiments, it can be 1-10 % by weight that hydrogen sulfide removes compound, and preferred about 4-about 6 % by weight.The remainder of additive can be the inert substance with fluid compatible, than such as (e.g.) mineral oil.In other non-limiting embodiments, thiosphosphorus compound can account for the about 90-about 99 % by weight of whole additive, and in a further non-limiting embodiment, it can account for about 94-about 96 % by weight.
The compositions of additives that thiosphosphorus compound and hydrogen sulfide remove compound can anyly can effectively suppress the amount of the corrosion caused by fluid/naphthenic acid to be applied to this fluid (comprising corrosive naphthenic acid).These can be relatively low, about 100ppm-about 5,000ppm, but can adopt more or less amount, if this tittle is effective.In the embodiment of many expectations, find that the content of about 500ppm-about 2,000ppm is effective, and in other embodiment expected, can be that about 750ppm-is about 1250ppm.
The following example is provided in order to the present invention will be described.Embodiment does not represent and limits the scope of the invention and should so do not understood.Except as otherwise noted, measure as weight part or % by weight.
Embodiment 1
First test of the present invention by determining that level is carried out
Program comprises the step of the mineral oil of 282 grams being added to reaction flask.Under continuously stirring, detection cell nitrogen is with the speed bubbling 30-60 minute of 10-20mL/min.Well heater is arranged on 288 DEG C and remainder 1 % by mole of H in nitrogen to test
2s bubbling.Hydrogen sulfide in the nitrogen of trace routine total acid value 10mg KOH, temperature 288 DEG C, experimental period 24 hours and 1 % by mole, C1018 carbon steel coupons is adopted to carry out.First " blank " (not having inhibiter) is tested to determine the etching extent occurred.After lacing film inserts detection cell, the naphthenic acid that is purchased about 20 grams with total acid value 151 injects 30 minutes.Then, the 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 thiosphosphorus compound and hydrogen sulfide scavenger compound, its content is 1000ppm by volume, wherein thiosphosphorus compound with 55 % by weight amount exist and scavenging agent with 5 % by weight amount existence, and the rest part of mixture is mineral oil.Taken out after in all cases lacing film being retained 24 hours in detection cell and evaluated.In the second test, adopt another lacing film also to complete inspection program of the present invention.
In the first test, with when compared with " blank ", level of protection provided by the present invention is measured as 94.2%.In the second test of the present invention, level of protection is measured as 99.7%.
Comparative example 2
Repeating embodiment 1 substantially the samely, except not adopting hydrogen sulfide scavenger, but adopting the thiosphosphorus compound of identical amount.In the first test, level of protection is measured as 80.1%.In the second test, level of protection is measured as 89.2%.
Claims (15)
1. one kind for suppressing the method for naphthenic acid corrosion in containing the fluid of etching extent naphthenic acid, the method comprises adds thiosphosphorus compound and hydrogen sulfide removing compound to this fluid or charging therefore, and wherein this thiosphosphorus compound and this hydrogen sulfide remove compound is the amount suppressing corrosion; And wherein this hydrogen sulfide removing compound has general formula:
R
1(N＝R
2)
x
Wherein x is the integer of 1-10; R
1independently selected from:
Containing the cycloalkyl of 4-7 carbon atom, phenyl, benzyl, the alkyl containing 1-20 carbon atom and the thiazolinyl containing 1-20 carbon atom; R
3hydrogen, the alkyl containing 1-20 carbon atom, the thiazolinyl containing 1-20 carbon atom or aryl; N is the integer of 1-6; R
4, R
5, and R
6be selected from the alkyl containing 1-20 carbon atom independently of one another, and
R
7hydrogen or the alkyl containing 1-20 carbon atom, and
With R
2identical, condition is only R
4, R
5and R
6one of can be:
And R
2independently selected from=CH
2, cyclohexyl,
Alkyl containing 1-20 carbon atom and the thiazolinyl containing 1-20 carbon atom; Wherein S represents the sulphur atom of at least one any position in this ring.
2. the process of claim 1 wherein that this thiosphosphorus compound and this hydrogen sulfide are removed compound to be added as mixture.
3. the process of claim 1 wherein that this thiosphosphorus compound has general formula:
Wherein R
1r
3(OCH
2cH
2)
n-or R
3(OCH
2cH
2)
no-, R
2with R
1identical or-XH, each X are sulphur or oxygen independently, but condition is at least one X is sulphur, R
3be the alkyl of 6-18 carbon atom, and n is the integer of 0-12.
4. the process of claim 1 wherein that this fluid is crude oil or its cut.
5. the method for claim 2, wherein this hydrogen sulfide removes compound content is in the mixture 1-10 % by weight.
6. the composition of claim 5, wherein this hydrogen sulfide removes compound content is in the mixture 4-6 % by weight.
7. the composition of claim 2, wherein this thiosphosphorus compound content is in the mixture 40-70 % by weight.
8. the composition of claim 2, wherein this mixture comprises mineral oil further.
9. be used in the composition suppressing naphthenic acid corrosion in the fluid containing etching extent naphthenic acid, said composition comprises following mixture: this mixture comprises thiosphosphorus compound and hydrogen sulfide removes compound, and wherein this hydrogen sulfide removing compound has general formula:
R
1(N＝R
2)
x
Wherein x is the integer of 1-10; R
1independently selected from:
Containing the cycloalkyl of 4-7 carbon atom, phenyl, benzyl, the alkyl containing 1-20 carbon atom and the thiazolinyl containing 1-20 carbon atom; R
3hydrogen, the alkyl containing 1-20 carbon atom, the thiazolinyl containing 1-20 carbon atom or aryl; N is the integer of 1-6; R
4, R
5, and R
6be selected from the alkyl containing 1-20 carbon atom independently of one another, and
R
7hydrogen or the alkyl containing 1-20 carbon atom, and
With R
2identical, condition is only R
4, R
5and R
6one of can be:
And R
2independently selected from=CH
2, cyclohexyl,
Alkyl containing 1-20 carbon atom and the thiazolinyl containing 1-20 carbon atom; Wherein S represents the sulphur atom of at least one any position in this ring.
10. the composition of claim 9, wherein this fluid is crude oil or its cut.
The composition of 11. claims 9, wherein this hydrogen sulfide removes compound content is in the mixture 1-10 % by weight.
The composition of 12. claims 11, wherein this hydrogen sulfide removes compound content is in the mixture 4-6 % by weight.
The composition of 13. claims 9, wherein this thiosphosphorus compound content is in the mixture 40-70 % by weight.
The composition of 14. claims 9, wherein this mixture comprises mineral oil further.
The composition of 15. claims 9, wherein this thiosphosphorus compound has general formula:
Wherein R
1r
3(OCH
2cH
2)
n-or R
3(OCH
2cH
2)
no-, R
2with R
1identical or-XH, each X are sulphur or oxygen independently, but condition is at least one X is sulphur, R
3be the alkyl of 6-18 carbon atom, and n is the integer of 0-12.
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 CN101316915A (en) | 2008-12-03 |
| CN101316915B true 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) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY155018A (en) * | 2007-03-30 | 2015-08-28 | Dorf Ketal Chemicals I Private Ltd | High temperature naphthenic acid corrosion inhibition using organophosphorous sulphur compounds and combinations thereof |
| WO2008122989A2 (en) * | 2007-04-04 | 2008-10-16 | Dorf Ketal Chemicals (I) Private Limited | 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 |
| HUE031481T2 (en) | 2007-09-14 | 2017-07-28 | Dorf Ketal Chemicals (I) Private Ltd | A novel additive for naphthenic acid corrosion inhibition and method of using the same |
| MX349928B (en) * | 2008-08-26 | 2017-08-21 | Dorf Ketal Chemicals I Pvt Ltd | An effective novel polymeric additive for inhibiting napthenic acid corrosion and method of using the same. |
| CN102197163B (en) * | 2008-08-26 | 2014-03-05 | 多尔夫凯塔尔化学制品（I）私人有限公司 | New additive for inhibiting acid corrosion and method of using new additive |
| 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 |
| US9260669B2 (en) | 2011-03-24 | 2016-02-16 | Baker Hughes Incorporated | Synergistic H2S/mercaptan scavengers using glyoxal |
| 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 |
| 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 |
| US20160060520A1 (en) * | 2014-09-03 | 2016-03-03 | Baker Hughes Incorporated | Scavengers for sulfur species and/or phosphorus containing compounds |
| 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 |
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| US5712230A (en) * | 1997-03-10 | 1998-01-27 | The Lubrizol Corporation | Additive compositions having reduced sulfur contents for lubricants and functional fluids |
| US5863415A (en) * | 1996-05-30 | 1999-01-26 | Baker Hughes Incorporated | Control of naphthenic acid corrosion with thiophosporus compounds |
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| 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 |
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- 2006-11-20 CA CA002631572A patent/CA2631572A1/en not_active Abandoned
- 2006-11-20 CN CN200680044904.8A patent/CN101316915B/en not_active Expired - Fee Related
- 2006-11-20 EP EP06846353A patent/EP1963462A4/en not_active Withdrawn
- 2006-11-20 KR KR1020087012612A patent/KR101364325B1/en not_active IP Right Cessation
- 2006-11-20 WO PCT/US2006/061101 patent/WO2007065064A2/en active Application Filing
- 2006-11-20 BR BRPI0619195-9A patent/BRPI0619195A2/en not_active Application Discontinuation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084552A (en) * | 1992-09-04 | 1994-03-30 | 鲁布里佐尔公司 | Sulfurized overbased compositions |
| US5863415A (en) * | 1996-05-30 | 1999-01-26 | Baker Hughes Incorporated | Control of naphthenic acid corrosion with thiophosporus compounds |
| US5712230A (en) * | 1997-03-10 | 1998-01-27 | The Lubrizol Corporation | Additive compositions having reduced sulfur contents for lubricants and functional fluids |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101364325B1 (en) | 2014-02-18 |
| WO2007065064A2 (en) | 2007-06-07 |
| EP1963462A4 (en) | 2012-01-04 |
| CA2631572A1 (en) | 2007-06-07 |
| BRPI0619195A2 (en) | 2011-09-20 |
| KR20080070833A (en) | 2008-07-31 |
| EP1963462A2 (en) | 2008-09-03 |
| WO2007065064A3 (en) | 2007-12-21 |
| US20070119747A1 (en) | 2007-05-31 |
| CN101316915A (en) | 2008-12-03 |
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