AU2005235761A1 - Use of organic polysulfides against corrosion by acid crudes - Google Patents
Use of organic polysulfides against corrosion by acid crudes Download PDFInfo
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- AU2005235761A1 AU2005235761A1 AU2005235761A AU2005235761A AU2005235761A1 AU 2005235761 A1 AU2005235761 A1 AU 2005235761A1 AU 2005235761 A AU2005235761 A AU 2005235761A AU 2005235761 A AU2005235761 A AU 2005235761A AU 2005235761 A1 AU2005235761 A1 AU 2005235761A1
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- 230000007797 corrosion Effects 0.000 title claims description 26
- 238000005260 corrosion Methods 0.000 title claims description 26
- 239000002253 acid Substances 0.000 title description 3
- 150000008116 organic polysulfides Chemical class 0.000 title description 2
- 238000000034 method Methods 0.000 claims description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 125000005608 naphthenic acid group Chemical group 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- 239000005864 Sulphur Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- -1 poly(di-tert-butyl sulphide) Polymers 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 230000002378 acidificating effect Effects 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 229920001021 polysulfide Polymers 0.000 description 7
- 239000002480 mineral oil Substances 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 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 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 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
- 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
- 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
- C10G7/02—Stabilising gasoline by removing gases by fractioning
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
IN THE MATTER OF an Australian Application corresponding to PCT Application PCT/FR2005/000861 I, Andrew Harvey David SUMPTER BSc, translator to RWS Group Ltd, of Europa House, Marsham Way, Gerrards Cross, Buckinghamshire, England, do solemnly and sincerely declare that I am conversant with the English and French languages and am a competent translator thereof, and that to the best of my knowledge and belief the following is a true and correct translation of the PCT Application filed under No. PCT/FR2005/000861. Date: 1 November 2006 A. TER For and on behalf of RWS Group Ltd WO 2005/103208 PCT/FR2005/000861 USE OF ORGANIC POLYSULFIDES AGAINST CORROSION BY ACID CRUDES The present invention pertains to the field of the 5 treatment of acidic crude petroleums in refineries. It relates more especially to a method of combating corrosion in refining units which process acidic crudes, comprising the use of specific polysulphide compounds. 10 Petroleum refineries may be confronted with a serious corrosion problem when they are required to process certain crudes known as acidic crudes. These acidic crudes consist essentially of naphthenic acids, which 15 are the origin of this corrosion phenomenon, which is a very particular phenomenon since it takes place in a liquid medium which is a non-conductor of electrical current. These naphthenic acids correspond to saturated cyclic hydrocarbons which carry one or more carboxylic 20 groups. The acidity of a petroleum crude is described by a measurement standardized in accordance with ASTM standard D 664-01. It is expressed in mg of potassium hydroxide required to neutralize 1 g of petroleum and is referred to as TAN (total acid number) . It is known 25 in this technical field that a crude petroleum having a TAN of more than 0.2 is qualified as acidic, and may lead to damage within the units of a refinery. This corrosion reaction depends heavily on local 30 conditions such as, for example, the temperature and the metallic nature of the walls in the unit concerned, the space velocity of the hydrocarbon, and the presence of a gas/liquid interface. Accordingly, even after major studies on the topic, refiners encounter great 35 difficulty in predicting the extent of the corrosion reactions and their location. One of the industrial solutions to this corrosion - 2 problem involves using apparatus made of stainless steels - that is, alloys of iron with, in particular, chromium and molybdenum. However, this solution remains little used, owing to the high capital investment cost. 5 That choice, moreover, must preferably be considered during the design of the refinery, since stainless steels have mechanical properties inferior to those of the carbon steels normally used, and require an appropriate infrastructure. 10 The existence of these technical difficulties in processing acidic crudes therefore means that, in general, these crudes are sold to refiners at a price level lower than that of the standard crudes. 15 Another solution to the problem of processing an acidic crude petroleum, which is used in practice by refiners, involves diluting it with another, non-acidic petroleum crude, so as to give a low average acidity, lower for 20 example than the 0.2 TAN threshold. In this case the concentration of naphthenic acid becomes low enough to give rise to acceptable corrosion rates. This solution remains limited in scope, however. The reason for this is that certain acidic crudes have TANs of more than 2, 25 which curtails their use to not more than 10% of the total volume of crudes entering the refinery. Moreover, certain blends of crudes sometimes lead to the converse of the desired effect, even after dilution, in other words to an acceleration of the corrosion reactions by 30 naphthenic acids. An alternative approach for combating this corrosion problem is to introduce, into the acidic crude petroleum to be processed, chemical additives which 35 inhibit or prevent the attack of the metal walls of the unit in question. This route is often very economic in comparison to that indicated above, involving the use of special steels or alloys.
- 3 Laboratory studies, such as that of Turnbull (Corrosion - November 1998 in Corrosion, volume 54, No. 11, page 922), have envisaged the addition of small amounts (of the order of 0.1%) of hydrogen sulphide to 5 the crude petroleum, for the purpose of reducing the corrosion by naphthenic acids. This solution, however, is not applicable in the refinery, since the hydrogen sulphide, which is gaseous at ambient temperature, is highly toxic, thereby making the consequences of any 10 leak extremely serious, and limiting its use. Moreover, at even higher temperature, the hydrogen sulphide itself becomes highly corrosive and, in other parts of the refinery, will lead to aggravation of the generalized corrosion. 15 US Patent 5182013 describes the use, for solving this corrosion problem, of other sulphur compounds, namely polysulphides having alkyl radicals containing from 6 to 30 carbon atoms. 20 EP Patent 742277 describes the inhibitory activity of a combination of a trialkyl phosphate and an organic polysulphide. US Patent 5552085 recommends the use of thiophosphorus compounds such as organic thiophosphates 25 or thiophosphites. AU Patent 693975 discloses as inhibitor a mixture of trialkyl phosphate and phosphoric esters of sulphurized phenol neutralized with lime. 30 However, the handling of organophosphorus compounds is very delicate, owing to their high toxicity. In addition, they are poisons for the hydrotreating catalysts which are installed to purify the hydrocarbon cuts obtained from atmospheric and vacuum 35 distillations. For these two reasons at least, their use in the field of refining is undesirable. Surprisingly it has been found that the use of a specific class of organic polysulphides, namely poly- - 4 alkyl sulphides in which the number of carbons in each alkyl radical is between 2 and 5, allows the corrosion caused by naphthenic acids to be inhibited more effectively than using the organic polysulphides known 5 to date, and without the need to introduce phosphorus inhibitors as well. The invention accordingly provides a method of combating the corrosion caused by naphthenic acids to 10 the metal walls of a refining unit, characterized in that it comprises the addition to the hydrocarbon stream for processing by the unit of an effective amount of one or more hydrocarbon compounds of formula 15 R 2 in which - n is an integer between 2 and 15 and - the symbols R1 and R 2 , which are identical or different, each represent a linear or branched 20 alkyl radical containing between 2 and 5 carbon atoms, it being possible for these radicals to contain, optionally, one or more heteroatoms such as oxygen or sulphur; or - R and R 2 , which are identical or different, each 25 represent a cycloalkyl radical containing between 3 and 5 carbon atoms, it being possible for these radicals to contain, optionally, one or more heteroatoms such as oxygen or sulphur. 30 The polysulphides of formula (I) are prepared according to processes which are known per se, such as those described in patents US 2708199, US 3022351 and US 3038013. Some of them are commercial products. 35 Preferably R1 and R 2 are linear or branched alkyl radicals and n is between 2 and 6. According to another preferred version the radicals R 1 -5 and R 2 are identical, owing to the improved stability of the corresponding compound of formula (I). According to a version which is even more preferred, 5 poly(di-tert-butyl sulphide)s are used as a mixture of compounds of formula (I). These products, industrial in origin, are obtained for example from the reaction of sulphur with tert-butyl mercaptan. The reaction conditions allow industrial products to be prepared 10 that are composed of a mixture of polysulphides with a number of sulphur atoms varying between 3 and 10, with a number-average value of between 2 and 6. The amount of compound(s) of formula (I) to be added to 15 the hydrocarbon stream for processing by the refining unit corresponds generally to a concentration, expressed by equivalent weight of sulphur of the said compound relative to the weight of the hydrocarbon stream, of between 1 and 5000 ppm, preferably between 5 20 and 500 ppm. While remaining within this concentration range, it will be possible to set a high content at the start-up of the method according to the invention, then to reduce this content subsequently to a maintenance level. 25 The method according to the invention makes it possible advantageously to process hydrocarbon streams, and more particularly crude petroleums, whose TAN is greater than 0.2 and preferably greater than 1. 30 The temperature at which the method is employed corresponds to that at which the corrosion reactions by naphthenic acids take place, and is generally between 200 and 450 0 C and more particularly between 250 and 35 350 0 C. The addition of the compound of formula (I) to the hydrocarbon stream may be carried out in close proximity to where the corrosion reaction occurs or - 6 else, at a lower temperature, upstream of the process of the said unit. This addition may be carried out by any means known to the skilled person which ensures control of the injection rate and effective dispersion 5 of the additive in the hydrocarbon: for example, by means of a nozzle or of a mixer. The metal walls of the refining unit in which the corrosion can be prevented by the method according to 10 the invention are any walls liable to come into contact with the stream of acidic hydrocarbon to be processed. The walls involved may therefore equally be the inner walls proper of units such as the atmospheric and vacuum distillation towers, or the surface of internal 15 elements thereof, such as their plates or packings, or else peripheral elements thereof, such as their offtake and entry lines, pumps, preheating ovens or heat exchangers, in so far as these elements are taken to a local temperature of between 200 and 4500C. 20 Non-limiting examples of hydrocarbon streams to be processed in accordance with the method according to the invention include the petroleum crude, the residue from atmospheric distillation, the gas-oil cuts 25 obtained from atmospheric and vacuum distillations, and the vacuum residue and distillate obtained from vacuum distillation. The examples which follow are given purely to 30 illustrate the invention and should not be interpreted as limiting its scope. In these examples a corrosion test is implemented whose conditions are given below. 35 Description of the corrosion test: This test employs an iron powder, which simulates a metal surface, and a mineral oil in which is dissolved a mixture of naphthenic acids, simulating an acidic crude stream. The characteristics of these reactants are as follows: - white mineral oil having a density of 0.838 5 - powder of spherical iron particles having a size of -40+70 mesh (i.e. from approximately 212 to 425 pm) - mixture of naphthenic acids having from 10 to 18 carbon atoms, a boiling point of between 270 and 10 324 0 C and an average molar mass of 244 g/mol. The following components are introduced into a 150 ml glass reactor equipped with a dropping funnel and a water condenser and fitted with a stirring system and a 15 temperature-measurement system: - 70 ml (or 58.8 g) of the mineral oil, - 2 g of the iron powder, - 2.8 g of the naphthenic acid mixture. 20 The initial TAN of the reaction mixture is 10. These reactants are kept in contact at a temperature of 250 0 C for 2 hours under an atmosphere of dry nitrogen, in order to avoid oxidation reactions. 25 At the end of the test the concentration of iron dissolved in the medium is determined by a conventional method employing mineralization of a sample, the taking-up of the residue in acidified water, and an 30 assay using an electron torch. This concentration of dissolved iron (expressed in ppm) is directly proportional to the corrosion rate of the iron powder that is generated by the mixture of 35 naphthenic acids present in the mineral oil. EXAMPLE 1: Reference test in the absence of inhibitor The above test is employed without any compound of - 8 formula (I) being added, with 2 repetitions. The results are indicated in Table I below. Table I Iron concentration (ppm) Test 1 180 Test 2 227 Average 203.5 5 EXAMPLE 2: Tests in the presence of polyalkyl sulphides Example 1 is repeated with the addition of different types of polyalkyl sulphides in mineral oil during the 10 charging of the reactor. The amount of these derivatives added is calculated so as to give a concentration of 500 ppm, expressed in equivalent weight of sulphur, in the mineral oil present in the reactor. 15 The results collated in Table II below are obtained. Likewise indicated in this table is the degree of inhibition of the corrosion brought about by the 20 naphthenic acid mixture. This degree is expressed in % and is defined by the following formula: (1 [iron] with inhibitor inhibition (%) = 1I- 100 i [iron] without inhibitor) 25 in which [iron] is the concentration of dissolved iron measured with or without inhibitor, the concentration of iron without inhibitor being equal to 203.5 ppm in accordance with Example 1.
-9 Table II Compound of Commercial Iron Degree of formula (I) name* concentration inhibition (ppm) (%) Di-tert-butyl TPS 44 4 98% trisulphide Di-tert-butyl TPS 54 7 97% tetrasulphide * supplier: ARKEMA
Claims (8)
1. Method of combating the corrosion caused by naphthenic acids to the metal walls of a refining unit, 5 characterized in that it comprises the addition to the hydrocarbon stream for processing by the unit of an effective amount of one or more hydrocarbon compounds of formula 10 R1 n R2 in which - n is an integer between 2 and 15 and - the symbols R and R 2 , which are identical or different, each represent a linear or branched 15 alkyl radical containing between 2 and 5 carbon atoms, it being possible for these radicals to contain, optionally, one or more heteroatoms such as oxygen or sulphur; or - R 1 and R 2 , which are identical or different, each 20 represent a cycloalkyl radical containing between 3 and 5 carbon atoms, it being possible for these radicals to contain, optionally, one or more heteroatoms such as oxygen or sulphur. 25
2. Method according to Claim 1, characterized in that a compound of formula (I) is used in which R' and R 2 are linear or branched alkyl radicals and n is between 2 and 6. 30
3. Method according to either of Claims 1 and 2, characterized in that a compound of formula (I) is used in which the radicals R 1 and R 2 are identical.
4. Method according to one of Claims 1 to 3, 35 characterized in that a mixture of poly(di-tert-butyl sulphide)s is used in which the average value of the number of sulphur atoms is between 2 and 6. - 11
5. Method according to one of Claims 1 to 4, characterized in that the amount of compound(s) of formula (I) corresponds to a concentration, expressed 5 by equivalent weight of sulphur relative to the weight of the hydrocarbon stream, of between 1 and 5000 ppm, preferably between 5 and 500 ppm.
6. Method according to one of Claims 1 to 5, 10 characterized in that the stream of hydrocarbons to be processed has a TAN of more than 0.2 and preferably more than 1.
7. Method according to one of Claims 1 to 6, 15 characterized in that it is carried out at a temperature of between 200 and 450 0 C and more particularly between 250 and 350 0 C.
8. Method according to one of Claims 1 to 7, 20 characterized in that the hydrocarbon stream to be processed is selected from petroleum crude, the residue from atmospheric distillation, the gas-oil cuts obtained from atmospheric and vacuum distillations, and the vacuum residue and distillate obtained from vacuum 25 distillation.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0403838A FR2868787B1 (en) | 2004-04-13 | 2004-04-13 | USE OF ORGANIC POLYSULFIDES AGAINST CORROSION BY ACID BRUTS |
FR0403838 | 2004-04-13 | ||
PCT/FR2005/000861 WO2005103208A1 (en) | 2004-04-13 | 2005-04-08 | Use of organic polysulfides against corrosion by acid crudes |
Publications (2)
Publication Number | Publication Date |
---|---|
AU2005235761A1 true AU2005235761A1 (en) | 2005-11-03 |
AU2005235761B2 AU2005235761B2 (en) | 2009-12-17 |
Family
ID=34944754
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU2005235761A Expired - Fee Related AU2005235761B2 (en) | 2004-04-13 | 2005-04-08 | Use of organic polysulfides against corrosion by acid crudes |
Country Status (16)
Country | Link |
---|---|
US (1) | US20070163922A1 (en) |
EP (1) | EP1756251A1 (en) |
JP (1) | JP2007532745A (en) |
KR (1) | KR20070005676A (en) |
CN (1) | CN1973021A (en) |
AR (1) | AR050242A1 (en) |
AU (1) | AU2005235761B2 (en) |
BR (1) | BRPI0509789A (en) |
CA (1) | CA2562102A1 (en) |
EA (1) | EA010668B1 (en) |
FR (1) | FR2868787B1 (en) |
MX (1) | MXPA06011863A (en) |
NO (1) | NO20065183L (en) |
TW (1) | TWI314952B (en) |
UA (1) | UA84741C2 (en) |
WO (1) | WO2005103208A1 (en) |
Families Citing this family (3)
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CN104152192B (en) * | 2013-05-13 | 2016-05-25 | 刘爱国 | A kind of petrol and diesel oil anticorrisive agent |
KR101990826B1 (en) | 2019-03-18 | 2019-06-19 | 영화진흥위원회 | Viewing Providing system for Deafness |
US20210255609A1 (en) * | 2020-02-14 | 2021-08-19 | Exxonmobil Research And Engineering Company | Systems and methods for monitoring and predicting a risk state of an industrial process |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2708199A (en) * | 1951-10-24 | 1955-05-10 | Continental Oil Co | Preparation of organic polysulfides |
US3022351A (en) * | 1957-03-07 | 1962-02-20 | Phillips Petroleum Co | Production of organic polysulfides |
US3062612A (en) * | 1959-04-25 | 1962-11-06 | Inst Francais Du Petrole | Method of protecting metals against electrochemical corrosion of the acidic type |
US3038013A (en) * | 1959-08-25 | 1962-06-05 | Phillips Petroleum Co | Color improvement in synthesis of polysulfides |
DE3437936A1 (en) * | 1984-10-17 | 1986-04-17 | Peter, Siegfried, Prof.Dr., 8525 Uttenreuth | Process and agent for combating corrosion under reducing conditions |
US5182013A (en) * | 1990-12-21 | 1993-01-26 | Exxon Chemical Patents Inc. | Naphthenic acid corrosion inhibitors |
US5500107A (en) * | 1994-03-15 | 1996-03-19 | Betz Laboratories, Inc. | High temperature corrosion inhibitor |
US5457234A (en) * | 1994-06-20 | 1995-10-10 | Phillips Petroleum Company | Process for treating organic polysulfide compounds |
US5552085A (en) * | 1994-08-31 | 1996-09-03 | Nalco Chemical Company | Phosphorus thioacid ester inhibitor for naphthenic acid corrosion |
US5464525A (en) * | 1994-12-13 | 1995-11-07 | Betz Laboratories, Inc. | High temperature corrosion inhibitor |
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 |
ATE232894T1 (en) * | 1996-05-30 | 2003-03-15 | Baker Hughes Inc | NAPHTENIC ACID CORROSION CONTROL WITH THIOPHOSPHORUS COMPOUNDS |
-
2004
- 2004-04-13 FR FR0403838A patent/FR2868787B1/en not_active Expired - Fee Related
-
2005
- 2005-04-08 MX MXPA06011863A patent/MXPA06011863A/en active IP Right Grant
- 2005-04-08 CA CA002562102A patent/CA2562102A1/en not_active Abandoned
- 2005-04-08 KR KR1020067021376A patent/KR20070005676A/en not_active Application Discontinuation
- 2005-04-08 AU AU2005235761A patent/AU2005235761B2/en not_active Expired - Fee Related
- 2005-04-08 JP JP2007507813A patent/JP2007532745A/en not_active Withdrawn
- 2005-04-08 US US11/547,920 patent/US20070163922A1/en not_active Abandoned
- 2005-04-08 WO PCT/FR2005/000861 patent/WO2005103208A1/en active Application Filing
- 2005-04-08 CN CNA2005800194186A patent/CN1973021A/en active Pending
- 2005-04-08 EP EP05753703A patent/EP1756251A1/en not_active Withdrawn
- 2005-04-08 UA UAA200610725A patent/UA84741C2/en unknown
- 2005-04-08 EA EA200601679A patent/EA010668B1/en not_active IP Right Cessation
- 2005-04-08 BR BRPI0509789-4A patent/BRPI0509789A/en not_active IP Right Cessation
- 2005-04-11 TW TW094111355A patent/TWI314952B/en not_active IP Right Cessation
- 2005-04-12 AR ARP050101429A patent/AR050242A1/en active IP Right Grant
-
2006
- 2006-11-10 NO NO20065183A patent/NO20065183L/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
AU2005235761B2 (en) | 2009-12-17 |
US20070163922A1 (en) | 2007-07-19 |
TWI314952B (en) | 2009-09-21 |
JP2007532745A (en) | 2007-11-15 |
TW200606246A (en) | 2006-02-16 |
KR20070005676A (en) | 2007-01-10 |
FR2868787A1 (en) | 2005-10-14 |
WO2005103208A1 (en) | 2005-11-03 |
NO20065183L (en) | 2006-11-10 |
CN1973021A (en) | 2007-05-30 |
BRPI0509789A (en) | 2007-10-23 |
UA84741C2 (en) | 2008-11-25 |
MXPA06011863A (en) | 2007-04-16 |
EP1756251A1 (en) | 2007-02-28 |
EA010668B1 (en) | 2008-10-30 |
CA2562102A1 (en) | 2005-11-03 |
FR2868787B1 (en) | 2006-06-23 |
AR050242A1 (en) | 2006-10-11 |
EA200601679A1 (en) | 2007-04-27 |
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