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
  • C10G67/04—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 solvent extraction 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
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
  • C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
• • 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
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
• • 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/10—Lubricating oil

Definitions

• Lube oils which may be used as direct multigrade lube oils are obtained from paraffins, particularly from hydrocracking paraffins, by hydrogenation in the presence of both a group VIII noble metal carried on halogenated alumina and ammonia, followed with dewaxing.
• Viscosity cst Viscosity cst at 378 C at 989 C W 20 100 to 145 30 to 50 5.8 to 9.6 10W 30 130 to 150 50 to 77 9.6 to 13 10W40 140 70 13 to 17 20 W 20 20 to 130 42 to 85 5.8 to 9.6 20 W 30 90 to 138 70 to 120 9.6 to 13 20W40 110 to 143 to 17
• a multigrade oil is conventionally prepared by admixing a very fluid base oil with variable amounts of a polymer, for example of the polymethacrylate type, which both improves the viscosity characteristics versus temperature and thickens the oil.
• the conventional viscosity additives are usually less stable than the oil when subjected to mechanical actions (shearing effect) and to the temperature effect.
• the direct multigrade oils obtained according to the process of the invention may obviously be used with conventional viscosity additives so as to provide other types of multigrade oils.
• paraffins treated according to the process of the invention are preferably hydrocracking paraffins obtained by dewaxing a lubricating oil base resulting from the hydrocracking or hydrorefining of vacuum distillates or deasphalted vacuum residues, such as described, for example, in French Patent No. 1,582,758 (U.S. Pat. No. 3,365,390). These paraffins are nor mally solid at room temperature (20C). Reference is also made to U.S. Pat. No. 3,560,370 and to the French patent application 7,1 12,416 and U.S. Pat. application 241,690 filed Apr. 6, 1972, now U.S. Pat. No. 3,793,191.
• the invention is thus concerned with a process for manufacturing multigrade oils, according to which a mixture of hydrogen and paraffin is contacted with a catalyst comprising an alumina carrier, at least one noble metal of group VIII of the periodic classification and from 0.1 to 5% by weight of halogen, at a temperature of from 300 to 450C, the global product is fractionated and the oil obtained after said fractionation is dewaxed for removing at least a fraction of the unconverted paraffins, the process being remarkable in that said contacting step is carried out under an ammonia partial pressure of from 1 to 500 g/cm
• Normally solid hydrocracking paraffins may be obtained, for example, by contacting hydrogen and oil vacuum or deasphalted vacuum residues, normally boiling, at least partly, above 450C, with a hydrocracking catalyst, under hydrocracking conditions, fractionating the resulting product so as to isolate therefrom a fraction normally boiling above 380C and preferably above 430C and dewaxing said fraction according to a known technique, for example as described here
• Hydrocracking catalysts are known to contain, as rule, one or more metals or compounds of metals from groups VI and/or VIII, for example molybdenum, tungsten, nickel, cobalt and/ or platinum incorporated toor carried onan acidic carrier, for example alumina-silica or halogen-containing alumina.
• an acidic carrier for example alumina-silica or halogen-containing alumina.
• the so-obtained hydrocracking paraffins have a molecular weight higher than 500, the average. molecular weight of the paraffin feedstock being higher than about 400.
• Their viscosity is conventionally 8 to 20 centistokes at 989 C, their viscosity index about 130, their sulfur content lower than 30 ppm (parts per million of parts) by weight and their nitrogen content lower than 5 ppm by weight.
• the hydroisomerization reaction is carried out at a temperature of from 250 to 450C, preferably from 300 to 390C.
• the pressure may range, for example, from 10 to 150 kg/cm and preferably from 30 to 100 kg/cm
• the hourly feed rate by volume (VVH) is usefully of from 02m 5 liters, preferably from 0.5 to 2 liters of liquid hydrocarbons per liter of catalyst.
• the gaseous hydrogen feed rate is, for example, 300 to 3000, preferably 500 to 1500 liters per liter of liquid hydrocarbons under the normal temperature and pressure conditions. In these conditions, the hydrocarbon feed charge is practically 100% liquid.
• the feed charge may be supplied to the top of the reactor, which results in a trickling phase operation in hydrogen atmosphere,
• the specific catalysts employed and the purity of the charge permit the reaction to take place under moderate conditions (a pressure of from 50 to 80 kg/cm and a temperature of from 300 to 390C), so that the resulting oil has a negligible content of aromatics.
• a pressure of from 50 to 80 kg/cm and a temperature of from 300 to 390C so that the resulting oil has a negligible content of aromatics.
• platinum on fluorinated alumina we obtain at 350C, 45% by weight of oil of a 135 VI, whose aromatic content is substantially negligible, whereas at 420C the obtained oil contains 15% of aromatic hydrocarbons.
• the hydroisomerization treatment according to the invention is carried out in the presence of catalysts consisting of one or more noble metals of group VIII and- /or their alloys incorporated toor carried onan acid support of the halogen-containing alumina type.
• catalysts consisting of one or more noble metals of group VIII and- /or their alloys incorporated toor carried onan acid support of the halogen-containing alumina type.
• noble metals are possible owing to the great purity of the feed charge, in particular its very low sulfur content.
• Mixtures of metals may be used, for example platinum iridium, platinum cobalt, platinum rhenium, platinum germanium or platinum gold.
• the best catalysts for the process of the invention are those of the platinum-aluminahalogen type, the preferred halogen being fluorine.
• the halogen content of the catalyst may be advantageously selected within the range of from 0.1 to 5% by weight and preferably 0.3 to 0.8% for fluorine and 0.3 to 3% for chlorine.
• the halogen and noble metal of the catalyst may be supplied according to well-known methods, for example those used when manufacturing reforming catalysts.
• the hydroisomerization product may be fractionated, for example, as follows:
• a cut boiling above 380C which is dewaxed to yield a base oil whose viscosity index is from 130 to 150 with a viscosity higher than 7 centistokes at 989 C and a melting point of, for example, -20C; this base oil conforms to the 10 W multigrade oil standard;
• gas oil cut 250-3 80C whose diesel number is at least 90; its cetane number is higher than 70 (the motor gas oil specification requires a cetane number of at least 50);
• the jet cut is of particular interest since it constitutes about 50% of the 80380C cut, i.e. it represents a yield of from 10 to 20% with respect to the initial paraffin.
• the dewaxing treatment applied to the oil obtained by hydroisomerization may be carried out according to any known method, for example by treatment with a solvent such as methyl-isobutyl-ketone or a pair of solvents such as a mixture of methyl-ethyl-ketone with toluene, at a temperature from 0C to C.
• a solvent such as methyl-isobutyl-ketone or a pair of solvents such as a mixture of methyl-ethyl-ketone with toluene
• the invention is not limited to a particular mode of dewaxing.
• the paraffin obtained may also be deoiled according to known methods.
• paraffins obtained after dewaxing of the fraction boiling above 380C may be recycled, if so desired, before or after a second deoiling step depending on the fact that the oil is recycled or not; in many cases, a second deoiling step increases the oil yield.
• the oils according to the invention have the further advantage of remarkably homogeneous distributions of both the viscosity and the viscosity index. These distributions may be determined from the rheological characteristics of the various fractions obtained by thermal diffusion of the base oil.
• hydroisomerization charge has been prepared as follows:
• composition A1 0 56 by weight SiO 20 70 by weight M00; 16 by weight NiO 8 by weight Specific surface 250 m /g
• the catalyst was previously sulfurized with H S diluted with H in the following conditions:
• the resulting oil was distilled and the distillation residue, boiling above 380C was collected and dewaxed at 22C by means of methyl-isobutyl-ketone.
• EXAMPLE 1 (comparison) Manufacture of a direct 10 W 20 multigrade oil by hydroisomerization of hydrotreated paraffins with a halogen-free catalyst, without ammonia.
• the lubricating oil fraction was dewaxed at 20C by means of a mixture of methyl-ethyl-ketone and toluene in a ratio of III by volume.
• the oil yield was 40 by weight and the uncoverted paraffin yield 25 by weight.
• EXAMPLE 2 (comparision) The feed charge of example No. l is treated in the presence of the same catalyst to which 0.5 by weight of fluorine has been added by impregnation with H BF The operating conditions are as follows:
• the operating conditions are:
• the oil has the following properties:
• the desired isomerizing effect is illustrated by the change of the ratio from 0.065 to 0.16.
• the oil has the following hydrocarbon composition:
• This oil does not satisfy the requirements of 10 W/20 multigrade oil standard.
• Example 3 is repeated, except that the first dewaxing step is followed with a seconddeoiling step.
• Paraffins 25 by weight oil 48 by weight In that case, a second deoiling step resulted in a 3 points increase of the yield of W/ oil; the rheological properties of this oil are the following:
• the deoiling step following the first dewaxing step of the hydroisomerization product has resulted in the recovery of highly paraffinic heavy compounds.
• Example 3 is repeated with the catalyst of example 1 to which 0.5 by weight of fluorine have been added by impregnation, with hydrofluoric acid.
• the resulting 10 W 20 oil has practically the same characteristics as the oil obtained in example 3.
• the oil yield is 44 29 by weight of unconverted paraffins have been recovered.
• a process for manufacturing a multigrade oil in which a mixture of hydrogen with a paraffin wax containing less than 5 ppm. by weight of nitrogen is contacted with a catalyst comprising an alumina carrier, at least one noble metal of group VIII and 0.1 to 5% by weight of halogen at a temperature of from 250 to 450C, the oil obtained is dewaxed so as to remove therefrom at least one fraction of unconverted paraffin wax, said process comprising carrying said contact under an ammonia partial pressure of from 1 to 500 g/cm 2.
• said paraffin wax is wax recovered from hydrocrackate 3.
• the ammonia partial pressure is from 10 to glcm 4.
• the catalyst contains from 0.3 to 0.8 by weight of fluorine.
• a process according to claim 1, wherein the contacting pressure is from 10 to kglcm 7.

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• 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)
• Catalysts (AREA)

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Cited By (24)

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Citations (8)

• 1972
  • 1972-12-08 FR FR7243935A patent/FR2209827B1/fr not_active Expired
• 1973
  • 1973-12-03 BE BE1005550A patent/BE808116A/xx unknown
  • 1973-12-03 DE DE2360092A patent/DE2360092A1/de not_active Withdrawn
  • 1973-12-07 GB GB5691973A patent/GB1419286A/en not_active Expired
  • 1973-12-07 US US422902A patent/US3915843A/en not_active Expired - Lifetime
  • 1973-12-07 NL NL7316796A patent/NL7316796A/xx not_active Application Discontinuation
  • 1973-12-07 ES ES421295A patent/ES421295A1/es not_active Expired
  • 1973-12-08 JP JP48140243A patent/JPS5743118B2/ja not_active Expired
  • 1973-12-10 IT IT32033/73A patent/IT1002195B/it active

Patent Citations (8)

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