BRPI0619195A2 - corrosion inhibitor - Google Patents
corrosion inhibitor Download PDFInfo
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- BRPI0619195A2 BRPI0619195A2 BRPI0619195-9A BRPI0619195A BRPI0619195A2 BR PI0619195 A2 BRPI0619195 A2 BR PI0619195A2 BR PI0619195 A BRPI0619195 A BR PI0619195A BR PI0619195 A2 BRPI0619195 A2 BR PI0619195A2
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- carbon atoms
- formula
- compound
- composition
- hydrogen sulfide
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- 238000005260 corrosion Methods 0.000 title claims abstract description 43
- 230000007797 corrosion Effects 0.000 title claims abstract description 43
- 239000003112 inhibitor Substances 0.000 title abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract 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 abstract description 25
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 23
- 239000012530 fluid Substances 0.000 claims abstract description 19
- 239000010779 crude oil Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000002480 mineral oil Substances 0.000 claims description 5
- 235000010446 mineral oil Nutrition 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 229910052760 oxygen Chemical group 0.000 claims description 3
- 239000001301 oxygen Chemical group 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
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 125000005608 naphthenic acid group Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical class C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- -1 thiophosphate compound Chemical class 0.000 description 2
- JLPUISACQXFVRC-UHFFFAOYSA-N 2,5-dihydro-1,3-thiazole Chemical class C1SCN=C1 JLPUISACQXFVRC-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical group OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
INIBIDOR DE CORROSãO. Uma composição e método de inibir corrosão causada por ácido naftênico em fluidos incluem usar uma combinação de um composto de tiofósforo e um composto de remoção de sulfeto de hidrogênio. O composto de remoção de sulfeto de hidrogénio intensifica o desempenho do composto de tiofósforo e pode ser incluído em níveis relativamente baixos na composição. O tratamento pode ser aplicado a fluidos incluindo óleos brutos e frações mais leves destes.Corrosion inhibitor. A composition and method of inhibiting corrosion caused by naphthenic acid in fluids includes using a combination of a thiophosphorus compound and a hydrogen sulfide removal compound. The hydrogen sulfide removal compound enhances the performance of the thiophosphorus compound and can be included at relatively low levels in the composition. The treatment can be applied to fluids including crude oils and lighter fractions thereof.
Description
Relatório Descritivo da Patente de Invenção para "INIBIDOR DE CORROSÃO".Patent Descriptive Report for "CORROSION INHIBITOR".
A presente invenção refere-se a inibidores de corrosão. A pre- sente invenção está particularmente direcionada a inibidores de corrosão úteis para aplicações, nas quais ácido naftênico está presente.The present invention relates to corrosion inhibitors. The present invention is particularly directed to corrosion inhibitors useful for applications in which naphthenic acid is present.
É de amplo conhecimento na técnica que o processamento de óleo bruto em suas várias frações pode danificar as superfícies metálicas contendo ferro do equipamento de processamento. Essa corrosão é freqüen- temente associada, em particular, à presença e atividade do ácido naftênico.It is well known in the art that processing crude oil in its various fractions can damage the iron containing metal surfaces of the processing equipment. This corrosion is often associated, in particular, with the presence and activity of naphthenic acid.
A corrosão ocorre quando a quantidade de ácidos naftênicos no hidrocarbo- neto atinge algum valor crítico indicado pelo índice de acidez total ("IA"), ex- presso como miligramas de hidróxido de potássio requeridos para neutralizar os ácidos em uma amostra de um grama. Literatura mais antiga sustenta, em geral, que um IA maior que cerca de 0,5 é requerido para um óleo bruto causar corrosão por ácido naftênico, mas experiência mais recente indica que o valor crítico pode variar consideravelmente desse valor. Quando tem- peraturas elevadas são aplicadas ao óleo bruto, tais como as temperaturas de 175°C (-347°F) a cerca de 400°C (-752°F) comumente usadas para refi- nar e destilar o óleo, o problema de corrosão é tipicamente mais exacerba- do.Corrosion occurs when the amount of naphthenic acids in the hydrocarbon reaches some critical value indicated by the total acidity index ("IA"), expressed as milligrams of potassium hydroxide required to neutralize acids in a one gram sample. Older literature generally holds that an AI greater than about 0.5 is required for a crude oil to cause naphthenic acid corrosion, but more recent experience indicates that the critical value may vary considerably from this value. When high temperatures are applied to crude oil, such as temperatures from 175 ° C (-347 ° F) to about 400 ° C (-752 ° F) commonly used to refine and distill the oil, the problem corrosion is typically more exacerbated.
Embora vários inibidores de corrosão sejam conhecidos da téc- nica, a eficácia de qualquer inibidor de corrosão particular é geralmente co- nhecida como sendo dependente das circunstâncias sob as quais ele é usa- do. Como resultado, uma variedade de inibidores de corrosão foi desenvol- vida e marcada para uso no tratamento particular de óleos brutos, para pro- teger metais particulares, para inibir tipos específicos de corrosão, e/ou para uso sob condições particulares de temperatura, ambiente, e similares. Por exemplo, a Patente US 3.909.447 descreve certos inibidores de corrosão como úteis contra corrosão em sistemas aquosos oxigenados, em tempera- turas relativamente baixas, tais como inundações de água, torres de refrige- ração, lamas de perfuração, perfuração a ar e sistemas auto-radiadores.Although various corrosion inhibitors are known in the art, the effectiveness of any particular corrosion inhibitor is generally known to be dependent upon the circumstances under which it is used. As a result, a variety of corrosion inhibitors have been developed and marked for use in the particular treatment of crude oils, to protect particular metals, to inhibit specific types of corrosion, and / or for use under particular temperature, ambient conditions. , and the like. For example, US 3,909,447 describes certain corrosion inhibitors as useful against corrosion in oxygenated aqueous systems at relatively low temperatures, such as water flooding, cooling towers, drilling muds, air drilling and auto-radiator systems.
Como comumente usado, o ácido naftênico é um termo coletivo para certos ácidos orgânicos presentes em vários óleos brutos. Embora quantidades menores de outros ácidos orgânicos podem também estar pre- sentes, é entendido que a maioria dos ácidos em um óleo bruto com base em ácido naftênico seja de caráter naftênico, isto é, com uma estrutura de anel saturado que se conforma a uma fórmula tal como uma das seguintes:As commonly used, naphthenic acid is a collective term for certain organic acids present in various crude oils. Although smaller amounts of other organic acids may also be present, it is understood that most acids in a naphthenic acid-based crude oil are naphthenic in character, that is, with a saturated ring structure that conforms to a formula. such as one of the following:
Nas fórmulas acima, m é tipicamente 1-2, e η varia. Ele é basi- camente qualquer grupo de ácido carboxílico com pelo menos um anel de 5 ou 6 membros, saturado, ligado. Um exemplo simples é o ácido ciclopenta- nóico.In the above formulas, m is typically 1-2, and η varies. It is basically any carboxylic acid group with at least one saturated, 5- or 6-membered ring attached. A simple example is cyclopentaenoic acid.
O peso molecular do ácido naftênico pode se estender por uma faixa ampla. Contudo, a maior parte do ácido naftênico em óleos brutos é encontrada, depois da destilação, nas frações mais leves, incluindo, por e- xemplo, óleo diesel. Quando hidrocarbonetos contendo tal ácido naftênico contatam metais que contêm ferro, especialmente em temperaturas eleva- das, surgem vários problemas de corrosão.The molecular weight of naphthenic acid can extend over a wide range. However, most naphthenic acid in crude oils is found after distillation in the lightest fractions, including, for example, diesel oil. When hydrocarbons containing such naphthenic acid contact iron-containing metals, especially at elevated temperatures, various corrosion problems arise.
Várias abordagens para controlar a corrosão induzida por ácido naftênico incluíram neutralizar e/ou remover os ácidos naftênicos do óleo bruto que está sendo processado; combinar óleos com baixo índice de aci- dez com óleos com índice de acidez alto, mais corrosivos, para reduzir o índice de neutralização total; e usar ligas resistentes à corrosão relativamen- te dispendiosas na construção do aparelho de processamento de óleo bruto. Essas tentativas são geralmente desvantajosas em que elas requerem pro- cessamento adicional e/ou aumentam substancialmente o custo do trata- mento do óleo bruto. Alternativamente, a Patente US 4.443.609 descreve certos ácidos e ésteres tetraidrotiazol fosfônicos como sendo aditivos úteis para inibir a corrosão ácida. Tais inibidores podem ser preparados por rea- ção de certos 2,5-diidrotiazóis com um fosfito de dialquila. Embora esses ácidos e ésteres tetraidrotiazol fosfônicos ofereçam boa inibição de corrosão, eles tendem à ruptura sob condições de altas temperaturas.Several approaches to controlling naphthenic acid-induced corrosion have included neutralizing and / or removing naphthenic acids from the crude oil being processed; combine low acidity oils with more corrosive high acidity oils to reduce the total neutralization index; and use relatively expensive corrosion resistant alloys in the construction of the crude oil processing apparatus. Such attempts are generally disadvantageous in that they require additional processing and / or substantially increase the cost of treating crude oil. Alternatively, US Patent 4,443,609 describes certain phosphonic acids and tetrahydrothiazole esters as useful additives for inhibiting acid corrosion. Such inhibitors may be prepared by reaction of certain 2,5-dihydrothiazoles with a dialkyl phosphite. Although these phosphonic tetrahydrothiazole acids and esters offer good corrosion inhibition, they tend to rupture under high temperature conditions.
Uma outra desvantagem de usar compostos com base em fósfo- ro é que se alega que o fósforo prejudica a função de vários catalisadores usados para tratar óleos brutos, tais como hidrotratadores de leito fixo e uni- dades de hidrocraqueamento. Assim, processadores de óleo bruto são fre- qüentemente confrontados com um dilema, já que a própria corrosão, senão inibida, pode resultar em acúmulo no fluido de hidrocarboneto de uma quan- tidade prejudicial a catalisador de ferro, tão alta quanto de 10 a 20 ppm, em alguns casos. Infelizmente, embora existam numerosos inibidores com base em não-fósforo comercialmente disponíveis, eles são conhecidos como sen- do geralmente um pouco menos eficazes que os compostos com base em fósforo.Another disadvantage of using phosphorus-based compounds is that it is claimed that phosphorus impairs the function of various catalysts used to treat crude oils such as fixed bed hydrotreaters and hydrocracking units. Thus, crude oil processors are often faced with a dilemma, as corrosion itself, if not inhibited, can result in accumulation in the hydrocarbon fluid of an amount harmful to iron catalyst, as high as 10 to 20. ppm in some cases. Unfortunately, while there are numerous commercially available non-phosphorus-based inhibitors, they are known to be generally somewhat less effective than phosphorus-based compounds.
Um avanço significativo em inibidores de corrosão induzida por ácido naftênico com base em fósforo está reportado na Patente US 4.941.994. Nesta Patente, é descrito que a corrosão de metal em hidrocar- bonetos líquidos, ácidos, quentes é inibida pela presença de uma quantidade inibidora de corrosão de um fosfito de dialquila e/ou trialquila com uma tiazo- Iina opcional. Uma outra patente, a Patente 5.863.415 menciona que os compostos de tiofósforo de uma fórmula específica são particularmente úteis para inibição de corrosão em hidrocarbonetos líquidos quentes e podem ser usados em concentrações que adicionam ao fluido menos do fósforo que prejudica o catalisador que alguns dos inibidores de corrosão com base em fósforo, anteriores. Esses compostos de tiofósforo também oferecem a van- tagem de poderem ser preparados a partir de materiais de partida de custo relativamente baixo.A significant advance in phosphorus-based naphthenic acid-induced corrosion inhibitors is reported in US Patent 4,941,994. In this Patent, it is described that corrosion of metal in hot, acidic liquid hydrocarbons is inhibited by the presence of a corrosion inhibiting amount of a dialkyl and / or trialkyl phosphite with an optional thiazoline. Another patent, Patent 5,863,415 mentions that thiophosphorus compounds of a specific formula are particularly useful for corrosion inhibition in hot liquid hydrocarbons and may be used at concentrations that add less of the catalyst-damaging phosphorus to the fluid than some of the previous phosphorus-based corrosion inhibitors. Such thiophosphorus compounds also offer the advantage that they can be prepared from relatively low cost starting materials.
Em vista do acima, seria desejável na técnica encontrar um mé- todo e composições adicionais para inibir e controlar a corrosão induzida por ácido naftênico em óleos brutos que oferecem vantagens sobre a técnica anterior. Em um aspecto, a presente invenção é um método para inibir a corrosão de ácido naftênico em um fluido contendo uma quantidade corrosi- va de ácido naftênico, em que o método compreende adicionar, ao fluido ou a uma alimentação para ele, um composto de tiofósforo e um composto de remoção de sulfeto de hidrogênio, em que o composto de tiofósforo e o composto de remoção de hidrogênio estão em quantidades eficazes para inibir a corrosão.In view of the above, it would be desirable in the art to find additional method and compositions for inhibiting and controlling naphthenic acid-induced corrosion in crude oils which offer advantages over the prior art. In one aspect, the present invention is a method for inhibiting corrosion of naphthenic acid in a fluid containing a corrosive amount of naphthenic acid, wherein the method comprises adding to the fluid or a feed therefor a thiophosphorus compound. and a hydrogen sulfide removal compound, wherein the thiophosphorus compound and hydrogen removal compound are in effective amounts to inhibit corrosion.
Em um outro aspecto, a invenção é uma composição útil para inibir a corrosão por ácido naftênico em um fluido contendo uma quantidade corrosiva de ácido naftênico, que compreende uma mistura de um composto de tiofósforo e um composto de remoção de sulfeto de hidrogênio.In another aspect, the invention is a composition useful for inhibiting naphthenic acid corrosion in a fluid containing a corrosive amount of naphthenic acid comprising a mixture of a thiophosphorus compound and a hydrogen sulfide removal compound.
Em um aspecto, a presente invenção é um método para inibir corrosão por ácido naftênico em um fluido que contém uma quantidade cor- rosiva de ácido naftênico, em que o método compreende adicionar ao fluido ou a uma alimentação para este, em quantidades suficientes para efetuar a inibição de corrosão no fluido, um composto de tiofósforo e um composto de remoção de sulfeto de hidrogênio. O fluido pode ser, por exemplo, um hidro- carboneto tal como um óleo bruto ou uma fração mais leve deste. Os com- postos de tiofósforo úteis com a presente invenção incluem aqueles que es- tão descritos na Patente US 5.863.415 de Zetlmeisl, cujo conteúdo é aqui incorporado aqui a título de referência em sua totalidade. Por exemplo, os compostos de tiofósforo úteis na prática da presente invenção incluem os sais dos compostos de tiofósforo, ésteres alquílicos e arílicos dos compostos de tiofósforo, e isômeros dos compostos de tiofósforo. Quaisquer compostos de tiofósforo que efetuam a inibição de corrosão induzida por ácido naftênico em fluidos podem ser usados na presente invenção.In one aspect, the present invention is a method for inhibiting naphthenic acid corrosion in a fluid containing a corrosive amount of naphthenic acid, wherein the method comprises adding to the fluid or a feed therein in sufficient amounts to effect corrosion inhibition in the fluid, a thiophosphorus compound and a hydrogen sulfide removal compound. The fluid may be, for example, a hydrocarbon such as a crude oil or a lighter fraction thereof. Thiophosphorus compounds useful with the present invention include those described in Zetlmeisl U.S. Patent 5,863,415, the contents of which are incorporated herein by reference in their entirety. For example, thiophosphorus compounds useful in the practice of the present invention include the salts of thiophosphorus compounds, alkyl and aryl esters of thiophosphorus compounds, and isomers of thiophosphorus compounds. Any thiophosphorus compounds which effect naphthenic acid-induced corrosion inhibition in fluids may be used in the present invention.
Em uma modalidade não-limitativa, são úteis na presente inven- ção compostos de tiofósforo da fórmula geral: <formula>formula see original document page 6</formula>In a non-limiting embodiment, thiophosphorus compounds of the general formula are useful in the present invention: <formula> formula see original document page 6 </formula>
FÓRMULA 1FORMULA 1
em que R1 é R3(OCH2CH2)n-, ou R3(OCH2CH2)nO-, R2 é igual a R1 ou é -XH, cada X é independentemente enxofre ou oxigênio, com a condição, contudo, que pelo menos um de X seja enxofre, R3 é um grupo alquila de cerca de 6 a cerca de 18 átomos de carbono, e η é um número inteiro de O a cerca de 12.wherein R1 is R3 (OCH2CH2) n-, or R3 (OCH2CH2) nO-, R2 is equal to R1 or is -XH, each X is independently sulfur or oxygen, provided, however, that at least one of X is sulfur, R3 is an alkyl group of about 6 to about 18 carbon atoms, and η is an integer from O to about 12.
Os compostos de remoção de sulfeto de hidrogênio úteis na invenção incluem aqueles descritos nas Patentes US 5.169.411 de Weers e US 6.663.841 de Salma et al., cujo conteúdo é aqui incorporado a título de refe- rência em sua totalidade. Incluídos nos compostos estão o composto imina não ácido, que é o produto de condensação de uma amina ou poliamina e um aldeído, dialdeído ou cetona. Por exemplo, eles incluem, em modalida- des não-limitativas, aqueles compostos tendo a fórmula geral:Hydrogen sulfide removal compounds useful in the invention include those described in US Patents 5,169,411 to Weers and US 6,663,841 to Salma et al., The contents of which are incorporated herein by reference in their entirety. Included in the compounds are the non-acidic imine compound, which is the condensation product of an amine or polyamine and an aldehyde, dialdehyde or ketone. For example, they include, in non-limiting embodiments, those compounds having the general formula:
<formula>formula see original document page 6</formula><formula> formula see original document page 6 </formula>
em que χ é um número inteiro de cerca de 1 a cerca de 10; R1 é indepen- dentemente selecionado do grupo que consiste emwhere χ is an integer from about 1 to about 10; R1 is independently selected from the group consisting of
<formula>formula see original document page 6</formula> <formula>formula see original document page 7</formula><formula> formula see original document page 6 </formula> <formula> formula see original document page 7 </formula>
FÓRMULA 5FORMULA 5
cicloalquila tendo de cerca de 4 a cerca de 7 átomos de carbono, fenila, benzila, alquila tendo de 1 a cerca de 20 átomos de carbono, e alquenila tendo de 1 a cerca de 20 átomos de carbono; R3 é hidrogênio, alquila tendo de 1 a cerca de 20 átomos de carbono, alquenila tendo de 1 a cerca de 20 átomos de carbono, ou arila; η é um número inteiro de 1 a 6; R4, R5, e R6 são, cada um, independentemente, selecionados do grupo que consiste em alquila contendo de 1 a cerca de 20 átomos de carbono ecycloalkyl having from about 4 to about 7 carbon atoms, phenyl, benzyl, alkyl having from 1 to about 20 carbon atoms, and alkenyl having from 1 to about 20 carbon atoms; R3 is hydrogen, alkyl having from 1 to about 20 carbon atoms, alkenyl having from 1 to about 20 carbon atoms, or aryl; η is an integer from 1 to 6; R4, R5, and R6 are each independently selected from the group consisting of alkyl containing from 1 to about 20 carbon atoms and
<formula>formula see original document page 7</formula><formula> formula see original document page 7 </formula>
FÓRMULA 6FORMULA 6
R7 é hidrogênio ou alquila tendo de 1 a cerca de 20 átomos de carbono, e é igual a R2 com a condição que somente um de R4, R5 e R6 possa serR7 is hydrogen or alkyl having from 1 to about 20 carbon atoms, and is equal to R2 with the proviso that only one of R4, R5 and R6 can be
<formula>formula see original document page 7</formula><formula> formula see original document page 7 </formula>
FÓRMULA 6FORMULA 6
e R2 é independentemente selecionado do grupo que consiste em =CH2, cicloexila, <formula>formula see original document page 8</formula>and R2 is independently selected from the group consisting of = CH2, cyclohexyl, <formula> formula see original document page 8 </formula>
FORMULA 7FORMULA 7
alquila contendo de 1 a cerca de 20 átomos de carbono, e alquenila conten- do de 1 a cerca de 20 átomos de carbono. Nas FÓRMULAS 5 e 6, o "S" sig- nifica pelo menos um átomo de enxofre no anel, sem ser específico quanto às sua localização ou localizações.alkyl containing from 1 to about 20 carbon atoms; and alkenyl containing from 1 to about 20 carbon atoms. In FORMS 5 and 6, the "S" means at least one sulfur atom in the ring, without being specific for its location or locations.
Verificou-se que os inibidores da presente invenção são tanto eficazes quanto exibem níveis muito baixos de evolução de sulfeto de hidro- gênio durante armazenamento e uso. A quantidade do composto de tiofósfo- ro é, desejavelmente, em certas modalidades não limitativas, de cerca de 40 a cerca de 70% em peso de um aditivo total que compreende tanto o com- posto de tiofósforo como o composto de remoção de sulfeto de hidrogênio. Em outras modalidades, o composto de remoção de sulfeto de hidrogênio pode ser de 1% a 10% em peso, preferivelmente de cerca de 4% a cerca de 6% em peso. O restante do aditivo pode ser um material inerte que é compa- tível com o fluido, tal como, por exemplo, óleo mineral. Em outras modalida- des não limitativas, o composto de tiofósforo pode representar de cerca de 90% a cerca de 99% em peso do aditivo total, e em ainda outras modalida- des não limitativas, ele pode representar de cerca de 90 a cerca de 96% em peso.Inhibitors of the present invention have been found to be both effective and exhibit very low levels of hydrogen sulfide evolution during storage and use. The amount of the thiophosphate compound is desirably, in certain non-limiting embodiments, from about 40 to about 70% by weight of a total additive comprising both the thiophosphorus compound and the sulfide removal compound. hydrogen. In other embodiments, the hydrogen sulfide removal compound may be from 1% to 10% by weight, preferably from about 4% to about 6% by weight. The remainder of the additive may be an inert material that is compatible with the fluid, such as, for example, mineral oil. In other non-limiting modalities, the thiophosphorus compound may represent from about 90% to about 99% by weight of the total additive, and in still other non-limiting modalities, it may represent from about 90 to about 90%. 96 wt%.
A combinação de aditivo de o composto de tiofósforo e o com- posto de remoção de sulfeto de hidrogênio pode ser empregada no fluido, contendo o ácido naftênico corrosivo, em qualquer quantidade que seja efi- caz para inibir a corrosão efetuada pelo fluido/ácido naftênico. Tal pode ser relativamente baixa, de cerca de 100 ppm a cerca de 5.000 ppm, mas quan- tidades maiores ou menores podem ser empregadas se tais forem eficazes. Em muitas modalidades desejáveis, foi verificado que um nível de cerca de 500 ppm a cerca de 2.000 ppm é eficaz, e em outras modalidades desejá- veis tal pode estar na faixa de cerca de 750 ppm a cerca de 1.250 ppm. Os seguintes exemplos são proporcionados para ilustrar a pre- sente invenção. Os exemplos não são destinados a limitar o escopo da pre- sente invenção e não devem ser interpretados desse modo. As quantidades estão em partes por peso ou percentagens em peso a menos que de outro modo indicado.The additive combination of the thiophosphorus compound and the hydrogen sulfide removal compound may be employed in the fluid containing the corrosive naphthenic acid in any amount that is effective to inhibit corrosion by the fluid / naphthenic acid. . This may be relatively low, from about 100 ppm to about 5,000 ppm, but larger or smaller amounts may be employed if they are effective. In many desirable embodiments, it has been found that a level of from about 500 ppm to about 2,000 ppm is effective, and in other desirable embodiments it may be in the range of about 750 ppm to about 1,250 ppm. The following examples are provided to illustrate the present invention. The examples are not intended to limit the scope of the present invention and should not be construed accordingly. Quantities are in parts by weight or weight percent unless otherwise indicated.
Exemplo 1Example 1
Um teste da invenção é realizado por se determinar primeira- mente o nível de corrosão para uma peça bruta.A test of the invention is performed by first determining the corrosion level for a blank.
O procedimento inclui a etapa de adicionar 282 gramas de óleo mineral ao frasco de reação. Uma célula de teste é espargida com nitrogênio em uma vazão de 10 a 20 mL/min, por um período de 30 a 60 minutos com agitação contínua. Os aquecedores são estabelecidos em 288°C e a célula de teste é pulverizada com 1% em mol de H2S em nitrogênio pelo restante do teste. O procedimento de teste é realizado com um índice de acidez total de 10 mg de KOH1 temperatura de 288°C, um tempo de operação de 24 ho- ras, e 1% em mol de sulfeto de hidrogênio em nitrogênio, usando corpos de prova de aço carbono C1018. Uma "peça bruta" é inicialmente testada, sem inibidor de corrosão, para determinar a quantidade de corrosão que ocorre. Cerca de 20 g de ácidos naftênicos comerciais tendo um índice de acidez total de 151 são injetados 30 minutos depois do corpo de prova ser inserido na célula de teste. Então, um primeiro teste da invenção é efetuado usando um outro corpo de prova e o mesmo procedimento, exceto que o inibidor de corrosão da invenção foi incluído. O inibidor de corrosão é uma mistura de um composto de tiofósforo e um composto de remoção de sulfeto de hidro- gênio em um nível de 1.000 ppm por volume, onde o composto de tiofósforo está presente em 55% em peso e o composto de remoção está presente em 5% em peso, com o restante da mistura sendo um óleo mineral. Os corpos de prova são, em todos os casos, removidos depois de 24 horas na célula de teste para avaliação. O procedimento para testar a invenção é também completado com um outro corpo de prova em um segundo teste.The procedure includes the step of adding 282 grams of mineral oil to the reaction flask. A test cell is sparged with nitrogen at a flow rate of 10 to 20 mL / min for a period of 30 to 60 minutes with continuous agitation. The heaters are set at 288 ° C and the test cell is sprayed with 1 mol% H2S nitrogen for the remainder of the test. The test procedure is performed with a total acidity index of 10 mg KOH1 temperature of 288 ° C, an operating time of 24 hours, and 1% mol of hydrogen sulfide in nitrogen, using test specimens. C1018 carbon steel. A "blank" is initially tested without corrosion inhibitor to determine the amount of corrosion that occurs. About 20 g of commercial naphthenic acids having a total acidity index of 151 are injected 30 minutes after the specimen is inserted into the test cell. Then a first test of the invention is performed using another specimen and the same procedure except that the corrosion inhibitor of the invention was included. The corrosion inhibitor is a mixture of a thiophosphorus compound and a hydrogen sulfide removal compound at a level of 1,000 ppm by volume, where the thiophosphorus compound is present at 55 wt.% And the removal compound. present at 5% by weight, with the remainder of the mixture being a mineral oil. The specimens are in all cases removed after 24 hours in the test cell for evaluation. The procedure for testing the invention is also completed with another specimen in a second test.
No primeiro teste, e quando em comparação com a "peça bruta", o nível de proteção proporcionado pela invenção é determinado como sendo -94,2%. No segundo teste da invenção, o nível de proteção é determinado como sendo 99,7%. Exemplo Comparativo 2In the first test, and when compared to the "blank", the level of protection provided by the invention is determined to be -94.2%. In the second test of the invention, the level of protection is determined to be 99.7%. Comparative Example 2
O Exemplo 1 é repetido de forma substancialmente idêntica, ex- ceto pelo fato que não foi usado o composto de remoção de sulfeto de hi- drogênio, mas é usada a mesma quantidade de composto de tiofósforo. Em um primeiro teste, o nível de proteção é determinado como sendo 80,1%. Em um segundo teste, o nível de proteção é determinado como sendo -89,2%.Example 1 is repeated substantially identically except that the hydrogen sulfide removal compound was not used, but the same amount of thiophosphorus compound is used. In a first test, the protection level is determined to be 80.1%. In a second test, the protection level is determined to be -89.2%.
Claims (17)
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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 |
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 |
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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 |
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- 2006-11-20 EP EP06846353A patent/EP1963462A4/en not_active Withdrawn
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