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
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G11/10—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with stationary catalyst bed
• • 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
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
  • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
  • C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
• • 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
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
  • C10G11/08—Halides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions

Definitions

• the present invention relates to an isomerization process in the presence of hydrogen (also sometimes called hydro-isomerization process), of a filler comprising in major part of normal paraffins (also called n-paraffins or normal paraffins) containing 5 to 8 carbon atoms molecule.
• hydrogen also sometimes called hydro-isomerization process
• a filler comprising in major part of normal paraffins (also called n-paraffins or normal paraffins) containing 5 to 8 carbon atoms molecule.
• n-butane normal butane
• isobutane which can be used in different applications.
• Isobutane can also, after dehydrogenation, be used in the reaction etherification with methanol or ethanol.
• ethers thus obtained - methyl tertio butyl ether (MTBE) or ethyl tertio butyl ether (ETBE) - have high octane numbers and can be directly incorporated into petrol.
• MTBE methyl tertio butyl ether
• ETBE ethyl tertio butyl ether
• the reaction temperature is generally higher than 200 ° C and often 300 ° C and the ratio of the number of moles of hydrogen to the number of moles of hydrocarbons is greater than 1.
• Patent FR 2735993 describes a catalyst and its use in processes isomerization of normal paraffins containing from 4 to 6 carbon atoms.
• This catalyst contains at least one halogen, preferably this halogen is chlorine, less a group VIII metal and a shaped support comprising alumina gamma and / or optionally eta alumina, the catalyst being characterized in that the smallest average dimension of said support is about 0.8 to 2 mm, preferably approximately 1 to 1.8 mm, and in that its chlorine content is approximately 4.5 to 15% by weight, preferably about 5 to 12% by weight.
• This catalyst is prepared by halogenation of a catalyst containing at least one group VIII metal on an alumina support. Once once the metal has been deposited, the support can undergo an activation treatment in air and / or under nitrogen.
• a halogenated catalyst can also be prepared from a support, shaped and treated with steam.
• a catalyst is the subject of a patent application on the part of the plaintiff, filed on the same day as this application, and in which is describes a catalyst containing at least one halogen, at least one metal from group VIII and a support comprising gamma alumina and / or eta alumina, shaped, and treated under a gas stream containing water vapor.
• the present invention relates to a process for isomerization in the presence of hydrogen of a filler mainly comprising normal paraffins containing from 5 to 8 atoms of carbon per molecule, characterized in that the sum of the normal paraffin contents at 7 and 8 carbon atoms per molecule contained in the charge is between 2 and 90% weight relative to the load, and in that said load is treated in at least one reaction zone, containing at least one fixed bed catalyst, said catalyst comprising a support, at least one halogen and at least one group VIII metal, the reaction being carried out at a temperature between 30 and 150 ° C.
• the present invention also relates to a method for increasing the index octane from a petroleum cut comprising normal paraffins containing from 5 to 8 carbon atoms per molecule.
• the present invention makes it possible in particular to overcome the aforementioned drawbacks.
• the method according to the invention makes it possible to convert charges for which the sum of the normal paraffin contents at 7 and at 8 carbon atoms per molecule contained in said charge is between 2 and 90 % by weight, preferably between 5 and 90% by weight, more preferably between 20 and 90% weight and very preferably between 40 and 90% by weight.
• the process according to the present invention allows, from a load to be treated comprising normal paraffins containing 5 to 8 carbon atoms per molecule, to obtain a paraffin yield branched containing at least 5 carbon atoms per molecule greater than 85% by weight.
• the process according to the present invention uses at least one reaction zone which comprises at least one reactor preferably containing at least one solid catalyst acid in a fixed bed, the reaction temperature is between 30 and 150 ° C, preferably between 70 and 130 ° C, and more preferably between 70 and 95 ° C.
• the catalyst used comprises a support, preferably based on alumina, containing at least one halogen, the halogen content being between 0.1 and 15% by weight, and at least one Group VIII metal.
• a catalyst based on chlorinated alumina preferably containing at least one solid catalyst acid in a fixed bed, the reaction temperature is between 30 and 150 ° C, preferably between 70 and 130 ° C, and more preferably between 70 and 95 ° C.
• the catalyst used comprises a support, preferably based on alumina, containing at least one halogen, the halogen content being between 0.1 and 15% by weight, and at least one Group VIII metal.
• a catalyst based on chlorinated alumina preferably containing at least one
• the catalyst used in the process according to the invention contains at least one metal of the group VIII on a support preferably based on alumina, on this support is deposited at least one halogen, preferably chosen from the group formed by fluorine, chlorine, bromine and iodine, more preferably the halogen is chlorine. Content halogen is between 0.1 and 15% by weight, preferably between 4 and 12%. in weight
• the catalyst support preferentially essentially comprises alumina.
• the alumina preferably used in the process according to the invention can be of gamma alumina and / or optionally eta alumina (i.e. be either gamma alumina, or eta alumina, or a mixture of these two aluminas).
• the alumina of the support comprises between 50 and 100% by weight, preferably between 80 and 100% by weight of alumina eta, more preferred 80 to 95% by weight of eta alumina, the balance being gamma alumina.
• the smallest average size of the catalyst support is about 0.8 to 2 mm, of preferably about 1 to 1.8 mm.
• said support is essentially formed of beads with an average diameter of about 0.8 to 2 mm, preferably about 1 to 1.8 mm, or well said support is formed essentially of extrudates whose smallest dimension is about 0.8 to 2 mm, preferably about 1 to 1.8 mm, i.e. the extrudates have has been shaped using any extrusion technique known to a person skilled in the art, such as for example a die with a diameter of about 0.8 to 2 mm, preferably about 1 to 1.8 mm.
• the gamma alumina optionally present in the catalyst support has a specific surface of approximately 150 to 300 m 2 / g and preferably approximately 180 to 250 m 2 / g, and a total pore volume generally of approximately 0, 4 to 0.8 cm 3 / g and preferably about 0.45 to 0.7 cm 3 / g.
• the alumina was optionally present in the catalyst support has a specific surface of approximately 400 to 600 m 2 / g and preferably of approximately 420 to 550 m 2 / g, and a total pore volume of approximately 0.3 at 0.5 cm 3 / g and preferably about 0.35 to 0.45 cm 3 / g.
• the metal of group VIII is chosen from the group formed by iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, preferably chosen in the group formed by platinum, palladium and nickel.
• the content is about 0.05 to 2% by weight and so preferred about 0.1 to 1.5% by weight.
• the weight content is from about 0.1 to 10% by weight and preferably from about 0.2 to 6% weight.
• the preparation of the catalyst is generally carried out by shaping the support. Said support shaped suddenly can optionally undergo a treatment under water vapor high temperature before or after the deposition of at least one Group VIII metal. A halogenation, preferably chlorination, is then carried out. It is also possible and preferred to carry out an activation step under hydrogen, before said step halogenation.
• these two types of aluminas are preferably mixed and shaped together, according to any technique known to those skilled in the art, for example by extrusion through a die, by pelleting or by coating.
• the smallest dimension of the geometric shape described by the support after shaping is approximately 0.8 to 2 mm, preferably approximately 1 to 1.8 mm, which makes it possible to obtain , during the halogenation stage of the support, a sufficient halogen content for a reduced halogenation period.
• the support preferably undergoes a treatment at high temperature under water vapor.
• the hydrothermal treatment is generally carried out for 0.5 to 6 hours, for example at a temperature of around 200 to 700 ° C. under a gas flow, for example air and / or nitrogen.
• the gas must contain water, for example at contents of about 0.2% to 100% by volume and preferably about 0.3% to 20% by volume.
• the activation of alumina by water vapor makes it possible to obtain much more acidic catalysts and therefore much more active in isomerization.
• At least one hydrogenating metal from group VIII chosen from the group formed by iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, preferably chosen from the group formed by platinum, palladium, and nickel, is then deposited on the support by any technique known to those skilled in the art, by example by anion exchange in the form of hexachloroplatinic acid in the case of platinum or in the form of chloride in the case of palladium. Hydrothermal treatment can be made after depositing the metal on the support.
• the support comprising the deposited metal can then optionally undergo treatment under hydrogen which makes it possible to obtain an active metallic phase.
• the procedure of this hydrogen treatment for example includes a slow rise in temperature under hydrogen flow up to the maximum reduction temperature which is around 300 to 700 ° C, and preferably between 340 to 680 ° C, followed by maintaining this temperature, generally for 1 to 6 hours, preferably for 1.5 to 4.5 hours.
• the halogenation step can be carried out according to any known technique of the skilled person.
• the halogen preferably chlorine
• Halogenation, preferably chlorination, alumina is carried out directly in the isomerization unit before injection of the load to be treated, or off site: in a separate unit, intended for halogenation.
• the halogenation can be carried out by any halogenating carbon agent, of preferably chlorinating agent, known to those skilled in the art.
• halogen preferably chlorine
• the reduction treatment under hydrogen can take place outside the unit (e.g. situ "), which implies taking special precautions for the transport of said catalyst to said unit, or else said treatment can take place within the unit ("in-situ") just before the use of said catalyst.
• the present invention relates to a process for the isomerization of a charge comprising for the most part normal paraffins containing from 5 to 8 carbon atoms per molecule, characterized in that the sum of the contents of normal paraffins at 7 and to 8 carbon atoms per molecule contained in the charge is between 2 and 90% by weight, preferably between 5 and 90% by weight, more preferably between 20 and 90% by weight, and very preferably between 40 and 90% by weight relative to the feed, and in that said feed is treated in at least one reaction zone, preferably containing at least one fixed-bed catalyst, said catalyst comprising a support, at least one halogen and at least one group VIII metal, the reaction being carried out at a temperature between 30 and 150 ° C, preferably 70 and 130 ° C, more preferably between 70 and 95 ° C, the feed to be treated, preferably containing at least one compound halogenated, more preferably a chlorinated compound, the content of which by weight in said charge is between 50 and 2000 ppm, and most often between 50 and 300
• Two embodiments of the invention can be considered, they will be chosen in function of the amount of excess hydrogen relative to the amount of hydrogen consumed by hydrogenation reactions, the opening of naphthenic cycles and cracking of paraffins. This can also be expressed by the ratio R of the number of moles of hydrogen on the number of moles of hydrocarbons in the effluent leaving the reactor.
• a small excess of hydrogen is used, so that the ratio R of the number of moles of hydrogen to the number of moles of hydrocarbons calculated on the basis of the composition of the effluent leaving the reactor either between 0.06 and 0.3, preferably 0.06 and 0.2. In this case it is not necessary to recycle the hydrogen not consumed towards the inlet of the reactor. We then operate at "Lost hydrogen".
• the ratio R of the number of moles of hydrogen to the number of moles of hydrocarbons calculated on the basis of the composition of the effluent leaving the reactor is then understood between 0.3 and 10, preferably between 0.3 and 5, and even more preferably between 0.5 and 3.
• the excess hydrogen is recycled to the inlet of the reactor for example by means of a gas-liquid separation tank and a recycling compressor. According to this mode of the invention it is possible to adjust the partial pressure of hydrogen in a wider range than in the first embodiment.
• the hourly space velocity (PPH) defined as the mass flow rate of feed to be treated per mass of catalyst and per hour is approximately 0.2 to 10 kg of feed per kg of catalyst and per hour (0.2 to 10 h -1 ), preferably around 0.3 to 5 kg of feed per kg of catalyst per hour (0.3 to 5 h -1 ) and even more preferably between 0.5 and 2 kg of load per kg of catalyst and per hour (0.5 to 2 h -1 ).
• the reactor pressure is about 0.1 to 10 MPa relative, preferably about 0.5 to 8 MPa relative, more preferably between 2 and 5 MPa.
• the reactor temperature is between 30 to 150 ° C, preferably between 70 to 130 ° C, more preferably between 70 and 95 ° C.
• a catalyst comprising a support, at least one halogen and at least one metal of group VIII, under the operating conditions indicated above leads to a surprisingly for obtaining high levels of conversion of C5-C8 n-paraffins, and more particularly n-heptane while retaining high yields of isomers, that is to say in light gasoline essentially consisting of hydrocarbons containing 5 to 8 carbon atoms.
• This catalyst therefore makes it possible to obtain a low cracking rate.
• the method according to the invention can treat all types of charges comprising in major part of normal paraffins containing from 5 to 8 carbon atoms, naphthenes, aromatic (in amounts usually less than 10% by weight). More specifically, the process according to the invention makes it possible to treat paraffinic cuts including the chain contains from 5 to 8 carbon atoms, and in which the sum of the paraffin contents normal to 7 and 8 carbon atoms per molecule included in the section is included between 2 to 90% by weight, preferably between 5 and 90% by weight, more preferably between 20 and 90% by weight and very preferably 40 to 90% by weight.
• the charges of the process according to the invention are free from water, oxygen, sulfur and more generally all compounds known to be poisons or inhibitors of alumina catalysts halogenated.
• a reactor with a volume of 200 ml is used, fed in upflow mode fluids by the mixture constituted by the charge to be treated and by the hydrogen.
• the effluent leaving the reactor is cooled and then analyzed by vapor phase chromatography.
• an industrial catalyst based on chlorinated alumina sold is used. by the company Procatalyse under the reference IS 612A.
• a reactor with a volume of 200 ml is also used, fed in flow mode ascending of fluids by the mixture constituted by the load to be treated and by hydrogen.
• the effluent leaving the reactor is cooled and then analyzed by phase chromatography steam.
• the operating conditions are as follows:
• the reactor is supplied with a feed comprising hydrocarbons containing from 5 to 7 carbon atoms and 800 ppm by weight of perchlorethylene (C 2 Cl 4 ) at the flow rate 87 g / h, the mass of the catalyst being 86 g, the PPH is 1.01 h -1 .
• the hydrogen flow rate is 4.5 10 -9 l / h.
• the total pressure is 3 MPa relative.
• isomerization 1 is carried out at a temperature of 105 ° C.
• the ratio R1 of the number of moles of hydrogen to the number of moles of hydrocarbons calculated at the outlet of the reactor is equal to 0.14
• isomerization 2 is carried out at 115 ° C. and the ratio R2 of the number of moles of hydrogen to the number of moles of hydrocarbons calculated at the outlet of the reactor is equal to 0.11.
• Example 1 the same catalyst and the same reactor are used as in Example 1.
• the reactor is supplied with a feed comprising hydrocarbons containing from 5 to 7 carbon atoms and 800 ppm by weight of perchlorethylene (C 2 Cl 4 ) at a flow rate of 84 g / h, the mass of the catalyst being 84 g, the PPH is 1 hr -1.
• the hydrogen flow rate is 60 10 - 9 l / h.
• the total pressure is 3 MPa relative.
• isomerization 3 is carried out at a temperature of 115 ° C.
• the ratio R3 of the number of moles of hydrogen to the number of moles of hydrocarbons calculated at the outlet of the reactor is equal to 2.67
• isomerization 4 is carried out at 130 ° C.
• the ratio R4 of the number of moles of hydrogen to the number of moles of hydrocarbons calculated at the outlet of the reactor is equal to 2.56.
• Example 2 corresponds to an isomerization process in which a large excess of hydrogen is used with respect to the feed to be converted.
• the composition of the charge and the results obtained are illustrated by means of Table 2.
• Compounds Load (% by weight) After isomerization 3 (% by weight) After isomerization4 (% by weight) C2-C4 0.87 5.99 9.51 iC5 9.95 11.73 12.5 nC5 7.79 6.33 6.18 cyclopentane 0.62 0.62 0.62 iC6 9.50 10.40 11.01 nC6 2.97 2.07 2.02 cyclohexane 5.10 3.79 3.19 methylcyclopentane 2.32 2.47 2.67 benzene 0.17 0 0 nC7 55.41 13.63 9.15 iC7 5.30 42.97 43.15 Isomerization 1 Isomerization 2 nC5 conversion 18.8% 20.7% nC6 conversion 30.3% 32% nC7 conversion 75.4% 83.5% C5
• Table 2 also illustrates the fact that 130 ° C is an appreciably low temperature. far from the maximum temperature compatible with obtaining high yields in isomers, in particular if it is estimated that a cracking rate in light products of 10% is the upper acceptable limit. In fact, at 130 ° C, 8.7% of products are already obtained light formed by cracking, therefore a yield of branched paraffins containing from 5 to 7 91.3% carbon atoms.
• the catalyst used in Example 3 is manufactured as follows: gamma alumina is formed by extrusion through a die with a diameter of 1.2 mm. The solid thus formed is treated at 500 ° C with air containing 3% by volume of water vapor. 0.2% of platinum-shaped alumina is deposited on said alumina by ion exchange with hexachloroplatinic acid in the presence of HCl as a competing agent. The solid obtained is reduced under hydrogen at 400 ° C. The solid obtained is then chlorinated, at a temperature of 280 ° C., by injection of carbon tetrachloride under a stream of nitrogen.
• the load to be treated consists of approximately 10% by weight of normal paraffins with 5 carbon atoms, 10% by weight of normal paraffins with 6 carbon atoms, 65% by weight of normal paraffins with 7 carbon atoms and 8% by weight of naphthenes with 6 carbon atoms.
• Said feed containing 100 ppm of carbon tetrachloride (CCl 4 ) expressed by weight of chlorine to maintain the chlorine content of the catalyst used.
• the isomerization operating conditions are as follows: the reactor temperature is 110 ° C., the total pressure of 3 relative MPa, the PPH of 1 h -1 and the ratio R5 of the number of moles of hydrogen to the number of moles of hydrocarbons calculated at the reactor outlet is equal to 0.47.

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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)
• Crystallography & Structural Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Catalysts (AREA)

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Citations (6)

• 1997
  • 1997-11-25 FR FR9714892A patent/FR2771417B1/fr not_active Expired - Lifetime
• 1998
  • 1998-11-19 DE DE69819286T patent/DE69819286T2/de not_active Expired - Lifetime
  • 1998-11-19 EP EP98402869A patent/EP0922747B1/de not_active Expired - Lifetime
  • 1998-11-24 CA CA002252065A patent/CA2252065A1/fr not_active Abandoned
  • 1998-11-25 KR KR1019980050665A patent/KR100567996B1/ko not_active IP Right Cessation
  • 1998-11-25 US US09/199,350 patent/US20020002319A1/en not_active Abandoned
  • 1998-11-25 JP JP10334558A patent/JPH11236577A/ja active Pending
• 2002
  • 2002-11-04 US US10/286,819 patent/US20030060673A1/en not_active Abandoned

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