EP0712922B1 - Procédé pour améliorer la qualité d'huile lubrifiante de base - Google Patents
Procédé pour améliorer la qualité d'huile lubrifiante de base Download PDFInfo
- Publication number
- EP0712922B1 EP0712922B1 EP95203127A EP95203127A EP0712922B1 EP 0712922 B1 EP0712922 B1 EP 0712922B1 EP 95203127 A EP95203127 A EP 95203127A EP 95203127 A EP95203127 A EP 95203127A EP 0712922 B1 EP0712922 B1 EP 0712922B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- activated carbon
- base oil
- lubricating base
- oil
- lubricating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002199 base oil Substances 0.000 title claims description 105
- 238000000034 method Methods 0.000 title claims description 68
- 230000001050 lubricating effect Effects 0.000 title claims description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 174
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- 238000004438 BET method Methods 0.000 claims description 2
- 239000003921 oil Substances 0.000 description 27
- 239000003463 adsorbent Substances 0.000 description 17
- 238000003860 storage Methods 0.000 description 17
- 238000001179 sorption measurement Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000005187 foaming Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 239000010687 lubricating oil Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000002459 porosimetry Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010021580 Inadequate lubrication Diseases 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002569 water oil cream 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
Definitions
- the present invention relates to a process for improving the quality of lubricating base oils.
- the "quality" of a lubricating base oil is determined by a combination of properties. Very important properties in this respect are storage stability and filterability of the base oil, and interfacial properties such as demulsibility, air release and foaming tendency.
- the present invention is particularly concerned with improving the storage stability, demulsibility and filterability of the base oil, whilst other relevant properties like air release and foaming tendency of the base oil are at least not negatively influenced. Under certain conditions air release and/or foaming may even be improved too in the process of the present invention. In any event, the overall quality of the lubricating base oil is improved.
- the storage stability indicates the number of days for an oil to produce a detectable change, other than a change in colour, when stored in the dark at a certain temperature under oxidative conditions, usually in air. This is a very important characteristic of a lubricating base oil, since it gives an indication of how long a lubricating base oil could be stored whilst maintaining free of any deposits, haze or flocculation.
- the demulsibility of a lubricating base oil is the ability of this oil to separate from water after the water and the oil have been intimately contacted and agitated so that an emulsion is formed.
- the demulsibility accordingly, gives an indication of the rate of coalescence of water drops in the water- oil emulsion.
- This rate of coalescence, in return, is a good indication of the content of surface-active compounds (i.e. contaminants, hetero-atoms and aromatics) in the base oil, which compounds may originate from their natural occurrence in the fresh oil, from contaminants and/or from degradation reactions taking place during the manufacturing process of the base oil.
- Demulsibility is determined according to ASTM D1401.
- the filterability of a lubricating base oil is a measure for the filter-blocking tendency of this oil. It is an important quality characteristic of a lubricating base oil, since many systems requiring lubrication contain filters whereby plugging of the filters needs to be avoided. Filterability is expressed in terms of the time needed to filter a certain volume of oil through a certain filter under certain conditions. This method for determining the filterability is known as the CETOP filterability method.
- the foaming tendency of a lubricating base oil indicates the volume of foam which is generated after bubbling air through the oil for five minutes at a constant rate and temperature and the volume of foam still left ten minutes after the bubbling of air through the oil has stopped. It will be understood that foaming of a lubricating oil during operation may give rise to inadequate lubrication.
- the standard test method for determining foaming tendency of lubricating oils is ASTM D892.
- the air release value of a lubricating base oil indicates the ability of this oil to separate entrained air and is defined as the number of minutes for air entrained in the oil to reduce in volume to 0.2% of its original volume at a certain temperature.
- a high air release value may indicate that the test oil contains a relatively high amount of air-retaining constituents, such as hetero-atoms (nitrogen, sulphur), polyaromatics and other polar compounds.
- the air release value is determined according to standard test method IP-313, which is technically identical to ASTM D3427.
- U.S. patent specification US 4,795,546A a process for improving the storage stability of hydrocracked, catalytically dewaxed lubricating base oils is disclosed comprising a hydrofinishing step followed by a nonhydrogenative stabilisation step.
- the hydrofinishing step involves contacting the dewaxed effluent with hydrogen in the presence of a suitable hydrogenation catalyst under mild hydrogenation conditions.
- the subsequent nonhydrogenative stabilisation step involves contacting the hydrofinished dewaxed oil with a minor amount of an olefinic stabilising agent in the presence of a heterogeneous acidic catalyst, such as acid resins, clays and aluminosilicates.
- a first drawback of the stabilisation method disclosed is the necessity of two distinct process step, both requiring the presence of a different catalyst. It will be understood that this is undesired from a cost perspective.
- a further drawback is that the use of a stabilising agent in the base oil may give rise to blending problems when adding additive packages lateron. The olefinic stabilising agent, namely, could easily interfere with the compounds constituting the additive package, which may give rise to problems with obtaining a stable and uniform blend.
- the possible interference between olefinic stabilising agent and additive package may even cause (partial) neutralisation of the effect of either the olefinic stabilising agent or the additive package, which, in return, may have a detrimental effect on the stability of the final lubricating oil.
- EP 0,535,910A a process for improving the demulsibility of lubricating base oils is disclosed, which process comprises contacting the base oil with an adsorption means, which is either an acidic ion exchange resin or a silica adsorbent.
- the lubricating base oil is defined as an oil which has been solvent extracted and/or dewaxed and/or hydrotreated. From the disclosure it is, however, clear that the base oil has preferably been solvent extracted prior to contacting with the adsorbent in order to remove aromatic hydrocarbons. It is, however, clear from this patent application that any adsorbent other than an acidic ion exchange resin or silica is not expected to positively affect the base oil's demulsibility performance.
- U.S. patent specification US 4,600,502A relates to a process for decreasing the foaming tendency of lubricating base oils.
- the process involves passing the base oil through an adsorption zone in order to remove the foam producing compounds, which usually constitute less than 1% by weight of the total weight of the base oil.
- the base oil Before being passed through the adsorption zone the base oil has already been solvent extracted an/or hydrotreated and/or dewaxed in order to remove aromatic compounds.
- the adsorbent is chosen such, that the adsorption step is solely intended to remove foam producing compounds from the base oil and not to remove any other undesired species, such as certain aromatic compounds.
- the adsorbents used suitably are neutral or basic, with basic adsorbents being preferred.
- charcoal treated with a solution of a strong base is listed too. However, there is no suggestion that untreated charcoal might be suitable as well.
- UK patent specification GB 1,109,731A describes to a process for producing lubricating base oil, which involves the step of contacting the oil with an absorbent material, preferably an active clay, in order to improve the quality of the lubricating base oil.
- an absorbent material preferably an active clay
- Activated carbon is mentioned as a possible absorbent material. Dry activated carbon is not disclosed.
- U.S. patent specification US 2,300,420A discloses a process for dewaxing white oils. The process comprises removing said wax from the oil by contacting it with activated carbon.
- the present invention aims to provide a process for improving the overall quality -and in particular the storage stability, demulsibility and filterability- of lubricating base oils. Furthermore, the present invention aims to provide a process for improving the quality of lubricating base oils by only one single process step. The present invention also aims to provide a quality-improving process which can be installed and operated at relatively low expenses within existing refinery installations.
- One aspect in this connection is that the adsorbent to be used should be commercially available at an attractive and competitive price.
- Yet another aim of the present invention is to provide a process wherein the storage stability of a lubricating base oil is improved without employing any stabilising agent in view of the addition of any additive packages to the base oil lateron, when manufacturing the final tailor-made lubricating oil products. All these aims have been achieved by the process according to the present invention, which involves improving the overall quality of lubricating base oils via one single adsorption step using dry activated carbon, wherein the water content of the dry activated carbon is less than 1% by weight, based on total weight of activated carbon, as the adsorbent.
- activated carbon is well known.
- activated carbon is known to be particularly suitable for adsorbing polynuclear aromatic compounds.
- U.S. patent specifications US 3,697,414A; US 4,447,315A; US 4,747,937A and US 4,954,242A all describe the use of activated carbon as an adsorbent for removing polynuclear aromatic compounds from different kinds of hydrocarbon streams.
- activated carbon is known for the dewaxing, decolorizing and improvement of lubricating oils.
- the present invention relates to a process for improving the quality of lubricating base oils, which process comprises contacting a lubricating base oil with dry activated carbon. More particularly, the present invention relates to a process for improving the quality of lubricating base oils in terms of storage stability, demulsibility and filterability, which process comprises the single step of contacting a lubricating base oil with dry activated carbon.
- activated carbon is a microcrystalline, nongraphitic form of carbon, which has been processed to develop internal porosity due to which it has a large surface area.
- the use of activated carbon as adsorbent for removing impurities from liquids and gases is well known and many commercial grades of activated carbon are available.
- any activated carbon grade suitable as a liquid-phase adsorbent may be used.
- Activated carbons which have been found particularly suitable, are those having a surface area (N2, BET method) in the range from 500 to 1500 m 2 /g, preferably from 900 to 1400 m 2 /g, and a Hg pore volume in the range from 0.1 to 1.0 ml/g, preferably from 0.2 to 0.8 ml/g.
- Hg pore volume is meant the pore volume as determined by mercury porosimetry.
- activated carbons which additionally have a micropore size distribution of 0.2 to 2 nm with an average of 0.5 to 1 nm, a pore size distribution (Hg porosimetry) in the range from 1 to 10,000 nm, preferably from 1 to 5,000 nm, and a total pore volume as determined by nitrogen porosimetry in the range from 0.4 to 1.5 ml/g, preferably from 0.5 to 1.3 ml/g.
- Other preferred physical characteristics include an apparent bulk density of from 0.25 to 0.55 g/ml, a particle size of from 0.4 to 3.5 nm, preferably 0.5 to 1.5 nm, and a bulk crushing strength of at least 0.8 MPa, preferably at least 1.0 MPa.
- suitable commercially available activated carbons include FILTRASORB 400, DARCO GCL 8*30 and DARCO GCL 12*40 (FILTRASORB and DARCO are trade marks).
- the activated carbon used in the process according to the present invention must be dry activated carbon.
- the water content of the activated carbon should be less than 1% by weight and more preferably less than 0.5% by weight, based on total weight of activated carbon.
- the lubricating base oil to be used in the process of the present invention may be any base oil prepared by methods known in the art. Accordingly, the base oil may, for instance, be obtained by the conventional process involving the successive steps of separating an atmospheric residue into one or more distillate fractions and a vacuum residue, deasphalting the vacuum residue, passing the distillate fraction(s) and the deasphalted vacuum residue through a solvent extraction unit and finally passing the solvent extracted oils through a solvent dewaxing unit.
- the base oil can be obtained via a process involving a catalytic dewaxing step instead of a solvent dewaxing step.
- Another process for producing suitable base oils is the process disclosed in British patent specification GB 1,546,504A, wherein waxy distillate fractions and/or a deasphalted waxy mineral oil fraction are catalytically hydrotreated in two successive stages, optionally followed by a dewaxing step.
- Another example of a process producing suitable base oils is the process described in European patent application EP 0,178,710A. In this process lubricating base oils are prepared by solvent extracting distillate fractions and/or deasphalted oils prior to subjecting them to a single-stage catalytic hydrotreatment, optionally followed by a dewaxing treatment.
- Hydroprocessed lubricating base oils prepared via the process described in European patent application EP 0,272,729A which process involves the catalytic hydrotreatment and subsequent dewaxing of flashed distillates produced via a residue conversion process, such as hydrocracking, are also useful to be stabilised via the process according to the present invention. Beside the processes described above there are many other ways known in the art involving at least one hydrotreatment step, which can also be used for producing suitable hydroprocessed lubricating base oils.
- hydroprocessed lubricating base oils produced according to any of the methods disclosed in British patent specification GB 1,546,504A and European patent application EP 0,178,710A have been found to be particularly suitable for use in the process according to the present invention, whereby base oils produced by the method disclosed in British patent specification GB 1,546,504A are most advantageously applied.
- the conditions (temperature, pressure, space velocity) under which the lubricating base oil is contacted with the dry activated carbon may vary within broad ranges in order to still attain an improved base oil quality.
- the temperature at which the contacting between base oil and activated carbon takes place is nevertheless an important parameter in view of its influence on the viscosity of the base oil. It will be understood that in order to allow optimum contact between the activated carbon and the base oil, the viscosity of the base oil should be such that the contact between the base oil and the activated carbon enables the undesired species to be adsorbed. Accordingly, the temperature should be such that the viscosity of the base oil at that temperature allows effective contact between the base oil and the activated carbon, so that the undesired species can be adsorbed.
- the operating pressure of the process according to the present invention is not particularly critical and may be in the range of from 1 to 200 bar, preferably 1 to 100 bar, most preferably 1 to 20 bar.
- a suitable weight hourly space velocity has been found to be in the range of from 0.2 to 25 kg/l/hr, preferably from 0.5 to 10 kg/l/hr and more preferably from 1 to 5 kg/l/hr.
- Contacting the lubricating base oil with the activated carbon may be realised in ways known in the art, such as by suspending the activated carbon particles throughout the base oil followed by filtration.
- Another way of contacting a base oil with activated carbon is passing the base oil through a filter of activated carbon. It has, however, been found very advantageous to pass the lubricating base oil through at least one fixed bed of activated carbon, after which the stabilised base oil can be recovered.
- the number of fixed beds of activated carbon is determined by parameters, such as base oil manufacture capacity, level of contaminants present in the base oils and correlated fouling rate of the activated carbon beds. In case more than one fixed bed of activated carbon is used, these beds may be arranged in series, in parallel or in a combination of both.
- the fixed beds of activated carbon in such mode that at least one spare bed of activated carbon is available and that each bed can be bypassed, so that replacement of fouled activated carbon beds is possible without having to interrupt the supply of base oil feed.
- the beds are arranged in series, this situation may for instance be attained by systems known from the field of residue hydroconversion fixed bed operations, such as those systems disclosed in British patent specification GB 2,014,058A and European patent application EP 0,026,508A.
- the beds are arranged in parallel, a two-bed configuration whereby both beds are alternately operated -as described in European patent application No. 0,450,997 for hydrodemetallisation guard bed reactors- may be applied.
- Another option is to arrange the fixed beds such, that there is always at least one spare bed which is not in operation. Accordingly, if the activated carbon in one fixed bed is fouled and needs to be replaced, then the flow of base oil can be passed over the spare bed and the fouled bed can be bypassed, thus allowing the contaminated activated carbon to be replaced by fresh or regenerated activated carbon. This bed can then be kept as the spare bed until the next bed is fouled. Such mode of operation, thus, allows a continuous flow of base oil to be contacted with activated carbon for improving its quality.
- a lubricating base oil having the properties listed in Table I (“Feed”) was passed over a bed of activated carbon, which had not been dried prior to contact with the base oil, at an operating temperature of 70 °C, a space velocity of 4 kg/l/hr (9.3 kg/kg/hr) and an operating pressure of 1 bar.
- the activated carbon used was DARCO GCL 8*30 ex NORIT (Hg pore volume 0.40 ml/g, N2 surface area 1050 m 2 /g) and 100 ml (48 g) of this activated carbon was loaded into a reactor (diameter 20 mm, volume 300 ml), so that a fixed bed of activated carbon was obtained.
- Relevant properties of the treated base oil are listed in Table I ("Comp.Ex. 1").
- Storage stability was measured by determining the number of days for the oil to produce a detectable change (deposits, haze, suspension), other than a change in colour, when stored in the dark at 70 °C under an air blanket in a sealed test cylinder of transparent glass. In these experiments, a storage stability of less than 60 days is considered unacceptable.
- Demulsibility was determined according to ASTM D1401 and is expressed as volume of oil phase in ml/volume of water phase in ml/volume of emulsion layer between oil and water phase in ml (time required to obtain the state indicated in minutes).
- Adsorption over dry activated carbon Feed Comp. Ex. 1 Ex. 1 Vk40 (cSt) 71.4 71.1 71.7 Vk100 (cSt) 9.0 9.0 9.0 VI 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 Storage Stability (days) 17 18 >60 Demulsibility 40/37/3 40/37/3 40/40/0 (ml/ml/ml (min)) (15) (50) (5)
- Vk40 stands for kinematic viscosity at 40 °C
- Vk100 for kinematic viscosity at 100 °C
- VI Viscosity Index
- a continuous flow of hydroprocessed lubricating base oil obtained by the process according to British patent specification No. 1,546,504 and having the properties as listed in Table II was passed over the bed of dry activated carbon for two months at an operating temperature of 130 °C, a space velocity of 2.6 kg/l/hr (6 kg/kg/hr) and an operating pressure of 10 bar.
- the properties of the untreated base oil (feed) and those of a sample of treated base oil obtained after two months of operation are listed in Table II.
- Filterability was determined according to the CETOP method and the time needed to filter 1000 ml of oil is indicated.
- Air release was determined according to the method IP 313 and is expressed in minutes.
- Foaming tendency was determined according to ASTM D892 and is expressed in ml/ml: volume in millilitres of foam directly after bubbling air through for five minutes/volume in millilitres of foam left ten minutes after bubbling of air has stopped. Improvement of hydroprocessed lubricating base oil quality by activated carbon adsorption Feed Product Vk40 (mm 2 /s) 71.9 71.8 Vk100 (mm 2 /s) 9.11 9.11 VI 101 101 Total sulphur (mg/kg) 148 142 Total nitrogen (mg/kg) 4 3 Monoaromatics (mmole/100 g) 43.2 43.4 Diaromatics (mmole/100 g) 1.8 1.8 Polyaromatics (mmole/100 g) 2.2 2.1 Storage stability (days) 6 >60 Demulsibility (ml/ml/ml (min)) 40/33/7 (60) 40/40/0 (9) Time to filter 1000 ml (min) >60 45 Foaming tendency (m
- activated carbon FILTRASORB 400 ex CHEMVIRON, Hg pore volume 0.40 ml/g, N 2 surface area 1100 m 2 /g
- the activated carbon was subsequently dried in situ for 24 hours at 180 °C with a nitrogen flow of 50 Nl/hr under 10 bar pressure, so that its water content was reduced to below 0.5% by weight.
- the conditions applied in this example for both feeds were an operating temperature of 70 °C, a space velocity of 4 kg/l/hr (9.3 kg/kg/hr) and an operating pressure of 1 bar.
- Table III again illustrates that activated carbon adsorption improves the quality of lubricating base oils.
- Table III also shows that for a solvent extracted base oil particularly the demulsibility is improved by activated carbon adsorption, whilst filterability and storage stability of the untreated base oil are already good in this case and remain good after the adsorption treatment.
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)
- Lubricants (AREA)
Claims (8)
- Procédé pour améliorer la qualité d'huiles de base lubrifiantes, lequel procédé comprend la mise en contact d'une huile de base lubrifiante avec du carbone activé sec, dans lequel la teneur en eau du carbone activé sec est inférieure à 1% en poids, par rapport au poids total de carbone activé.
- Procédé suivant la revendication 1, dans lequel l'huile de base lubrifiante et le carbone activé sec sont mis en contact à une température dans l'intervalle de 20 à 300°C.
- Procédé suivant la revendication 2, dans lequel l'huile de base lubrifiante et le carbone activé sec sont mis en contact à une température dans l'intervalle de 30 à 200°C.
- Procédé suivant l'une quelconque des revendications précédentes, dans lequel la mise en contact avec le carbone activé sec se fait en faisant passer l'huile de base lubrifiante à travers au moins un lit fixe de carbone activé sec.
- Procédé suivant la revendication 4, dans lequel on obtient du carbone activé sec par séchage après que le carbone activé a été tassé dans le lit.
- Procédé suivant la revendication 5, dans lequel le carbone activé est séché à une température dans l'intervalle de 100 à 500°C pendant 1 à 48 heures.
- Procédé suivant l'une quelconque des revendications précédentes, dans lequel l'huile de base lubrifiante est une huile de base lubrifiante hydrotraitée.
- Procédé suivant l'une quelconque des revendications précédentes, dans lequel le carbone activé sec a une aire superficielle (N2, méthode BET) dans la gamme de 500 à 1500 m2/g et un volume des pores au Hg dans la gamme de 0,1 à 1,0 ml/g.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95203127A EP0712922B1 (fr) | 1994-11-16 | 1995-11-15 | Procédé pour améliorer la qualité d'huile lubrifiante de base |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94402602 | 1994-11-16 | ||
EP94402602 | 1994-11-16 | ||
EP95203127A EP0712922B1 (fr) | 1994-11-16 | 1995-11-15 | Procédé pour améliorer la qualité d'huile lubrifiante de base |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0712922A2 EP0712922A2 (fr) | 1996-05-22 |
EP0712922A3 EP0712922A3 (fr) | 1996-10-23 |
EP0712922B1 true EP0712922B1 (fr) | 2000-02-23 |
Family
ID=26137551
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95203127A Expired - Lifetime EP0712922B1 (fr) | 1994-11-16 | 1995-11-15 | Procédé pour améliorer la qualité d'huile lubrifiante de base |
Country Status (1)
Country | Link |
---|---|
EP (1) | EP0712922B1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8236168B2 (en) | 2009-10-13 | 2012-08-07 | Exxonmobil Research And Engineering Company | Onset haze measurement apparatus and procedure |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6468417B1 (en) * | 1999-06-11 | 2002-10-22 | Chevron U.S.A. Inc. | Filtering lubricating oils to remove haze precursors |
CN1286953C (zh) | 2000-07-17 | 2006-11-29 | 国际壳牌研究有限公司 | 制备水白润滑油基础油的方法 |
GB2386608B (en) * | 2000-12-05 | 2004-06-09 | Chevron Usa Inc | Process for preparing lubes with high viscosity index values |
US6773578B1 (en) | 2000-12-05 | 2004-08-10 | Chevron U.S.A. Inc. | Process for preparing lubes with high viscosity index values |
ATE302255T1 (de) | 2000-12-19 | 2005-09-15 | Shell Int Research | Verfahren zur herstellung von spindelölen, leichten maschinenölen und mittleren maschinenölen |
US7691258B2 (en) | 2007-06-04 | 2010-04-06 | Emirates National Oil Company Limited (Enoc) Llc | Process for treating hydrocarbon liquid compositions |
EP2075314A1 (fr) | 2007-12-11 | 2009-07-01 | Shell Internationale Research Maatschappij B.V. | Formules de graisse |
WO2009080672A1 (fr) | 2007-12-20 | 2009-07-02 | Shell Internationale Research Maatschappij B.V. | Compositions de caburant |
JP2011508000A (ja) | 2007-12-20 | 2011-03-10 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | 燃料組成物 |
JP6266606B2 (ja) | 2012-06-21 | 2018-01-24 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイShell Internationale Research Maatschappij Besloten Vennootshap | 重質フィッシャー・トロプシュ由来及びアルキル化芳香族基油を含む潤滑油組成物 |
US20140042056A1 (en) * | 2012-08-10 | 2014-02-13 | Exxonmobil Research And Engineering Company | Co-production of heavy and light base oils |
CA2968897A1 (fr) * | 2014-12-30 | 2016-07-07 | Exxonmobil Research And Engineering Company | Traitement catalytique et traitement par voie humide pour la production d'huile de base |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE637589A (fr) * | ||||
US2038604A (en) * | 1931-12-21 | 1936-04-28 | Standard Oil Dev Co | Process for treating lubricating oils |
US2300420A (en) * | 1940-08-31 | 1942-11-03 | West Virginia Pulp & Paper Co | Dewaxing of white mineral oils |
US2905624A (en) * | 1955-11-07 | 1959-09-22 | Universal Oil Prod Co | Manufacture of lubricating oil |
GB1109731A (en) * | 1965-03-23 | 1968-04-10 | Mobil Oil Corp | Process for producing lubricating oils |
US3697414A (en) | 1971-04-05 | 1972-10-10 | Ashland Oil Inc | Method for producing naphthalene |
CA1003778A (en) | 1972-04-06 | 1977-01-18 | Peter Ladeur | Hydrocarbon conversion process |
FR2306254A1 (fr) | 1975-04-02 | 1976-10-29 | Shell France | Procede de preparation d'une huile lubrifiante |
NL191022C (nl) | 1978-01-20 | 1994-12-16 | Shell Int Research | Inrichting geschikt voor het katalytisch hydrogenerend behandelen van zware koolwaterstofoliën. |
NL191763C (nl) | 1979-09-26 | 1996-07-02 | Shell Int Research | Werkwijze voor ontmetalliseren van een koolwaterstofolie. |
US4447315A (en) | 1983-04-22 | 1984-05-08 | Uop Inc. | Hydrocracking process |
GB8425837D0 (en) | 1984-10-12 | 1984-11-21 | Shell Int Research | Manufacture of lubricating base oils |
US4600502A (en) | 1984-12-24 | 1986-07-15 | Exxon Research And Engineering Co. | Adsorbent processing to reduce basestock foaming |
US4795546A (en) | 1985-09-30 | 1989-01-03 | Chevron Research Company | Process for stabilizing lube base stocks derived from neutral oils |
US4747937A (en) | 1986-11-24 | 1988-05-31 | Uop Inc. | Process for the removal of hydrogenatable hydrocarbonaceous compounds from a hydrocarbonaceous stream and hydrogenating these compounds |
GB8629476D0 (en) | 1986-12-10 | 1987-01-21 | Shell Int Research | Manufacture of lubricating base oils |
US4954242A (en) | 1989-07-19 | 1990-09-04 | Uop | Process for refractory compound removal in a hydrocracker recycle liquid |
FR2660322B1 (fr) | 1990-03-29 | 1992-06-19 | Inst Francais Du Petrole | Procede d'hydrotraitement d'un residu petrolier ou d'une huile lourde en vue de les raffiner et de les convertir en fractions plus legeres. |
US5282960A (en) | 1991-10-02 | 1994-02-01 | Exxon Research And Engineering Company | Method for improving the demulsibility of base oils |
-
1995
- 1995-11-15 EP EP95203127A patent/EP0712922B1/fr not_active Expired - Lifetime
Non-Patent Citations (3)
Title |
---|
"Fluka guide", FLUKA CHEMIE AG, BUCHS (CH), 1997 * |
A. CAPELLE, F. DE VOOYS: "Activated Carbon...a fascinating material", NORIT N.V., AMERSFOORT (NL), 1983 * |
J.S. MATTSON, H.B. MARK,JR.: "Activated Carbon", MARCEL DECCKER INC., NEW-YORK, 1971 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8236168B2 (en) | 2009-10-13 | 2012-08-07 | Exxonmobil Research And Engineering Company | Onset haze measurement apparatus and procedure |
Also Published As
Publication number | Publication date |
---|---|
EP0712922A3 (fr) | 1996-10-23 |
EP0712922A2 (fr) | 1996-05-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0712922B1 (fr) | Procédé pour améliorer la qualité d'huile lubrifiante de base | |
AU731718B2 (en) | Sulfur resistant hydroconversion catalyst and hydroprocessing of sulfur-containing lube feedstock | |
CA2668842C (fr) | Procede de retrait de l'azote et des aromatiques polynucleaires d'un hydrocraqueur et de charges fcc | |
KR101320813B1 (ko) | 경질 유분의 흡착에 의한 탈황 및 중질 유분의수소화탈황을 포함하는 가솔린의 탈황 방법 | |
US6468417B1 (en) | Filtering lubricating oils to remove haze precursors | |
US5393408A (en) | Process for the stabilization of lubricating oil base stocks | |
US5997732A (en) | Clay treatment process for white mineral oil | |
JPH10251666A (ja) | 金属で汚染された炭化水素系原料の水素処理方法 | |
CA2162813C (fr) | Methode pour ameliorer la qualite d'huile de base lubrifiante | |
EP3240871A1 (fr) | Traitement catalytique et traitement par voie humide pour la production d'huile de base | |
JPWO2004078887A1 (ja) | 軽油留分の水素化処理方法 | |
KR100877004B1 (ko) | 연료유 수소화 분해공정의 미전환유 및 이의 감압증류분획 유분으로부터 질소화합물을 제거하는 방법 | |
JP2005505681A (ja) | 予備処理した使用済み油の品質向上 | |
KR100603225B1 (ko) | 의약용 오일 및 임의로 중간 증류물의 융통적인 제조 방법 | |
US4952303A (en) | Process for preparing a very high quality lube base stock oil | |
CN1662632A (zh) | 制备医用白油和工业白油的方法 | |
EP0535910B1 (fr) | Méthode pour améliorer la démulsibilité d'huiles de base | |
NZ561699A (en) | Process for removing color bodies from hydrocarbon-based fuels using activated carbon | |
US4006077A (en) | Demetallization of asphaltene-containing petroleum hydrocarbons | |
CA1323842C (fr) | Procede d'elimination par adsorption des substances aromatiques et de la cire contenues dans les huiles de lubrification | |
US4701254A (en) | Static bed wax decolorization process | |
RU1796662C (ru) | Способ переработки остаточного нефт ного сырь | |
JPH0633368B2 (ja) | 石油留分の前処理方法 | |
JPH07197040A (ja) | 石油蒸留物の高品質化方法 | |
MXPA99000643A (en) | Sulfur resistant hydroconversion catalyst and hydroprocessing of materials in storage of lubricants feeding contai azu |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): BE DE FR GB IT NL |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): BE DE FR GB IT NL |
|
17P | Request for examination filed |
Effective date: 19970212 |
|
17Q | First examination report despatched |
Effective date: 19981028 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE FR GB IT NL |
|
ITF | It: translation for a ep patent filed | ||
REF | Corresponds to: |
Ref document number: 69515158 Country of ref document: DE Date of ref document: 20000330 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20080919 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20081127 Year of fee payment: 14 Ref country code: DE Payment date: 20081127 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20081010 Year of fee payment: 14 Ref country code: BE Payment date: 20081027 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20081022 Year of fee payment: 14 |
|
BERE | Be: lapsed |
Owner name: *SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V. Effective date: 20091130 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: V1 Effective date: 20100601 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20091115 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20100730 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100601 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20091130 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20091130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100601 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20091115 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20091115 |