Method for obtaining hydrocarbon solvents with boiling point above 300°C. and pour point lower than or equal to −25°C

• US 10,047,305 B2
• Filed: 12/09/2013
• Issued: 08/14/2018
• Est. Priority Date: 12/10/2012
• Status: Active Grant

• Current Assignee: Totalenergies Onetech
• Original Assignee: Total Marketing Services SA (Totalenergies Se)
• Inventors: Aubry, Christine, Grasso, Giacomo, Dath, Jean-Pierre
• Primary Examiner(s): Boyer, Randy
• Application Number:
  US14/651,015
• Publication Number:
  US 20160281009A1
• Time in Patent Office: 1,709 Days
• CPC Class Codes: B01J 21/04 Alumina
• CPC Class Codes: B01J 23/882 and cobalt
• CPC Class Codes: B01J 23/883 and nickel
• CPC Class Codes: B01J 23/888 Tungsten
• CPC Class Codes: B01J 37/20 Sulfiding
• CPC Class Codes: C09D 11/033 characterised by the solvent
• CPC Class Codes: C09K 3/00 Materials not provided for elsewhere
• CPC Class Codes: C10G 2300/1059 Gasoil having a boiling range of about 330 - 427 °C
• CPC Class Codes: C10G 2300/301 Boiling range
• CPC Class Codes: C10G 2300/302 Viscosity
• CPC Class Codes: C10G 2300/304 Pour point, cloud point, cold flow properties
• CPC Class Codes: C10G 2400/10 Lubricating oil
• CPC Class Codes: C10G 2400/18 Solvents
• CPC Class Codes: C10G 45/02 to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
• CPC Class Codes: C10G 45/44 Hydrogenation of the aromatic hydrocarbons
• CPC Class Codes: C10G 45/58 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 C10G32/00 takes precedence; improving or increasing the octane number or aromatic content of naphtha C10G35/00
• CPC Class Codes: C10G 45/64 containing crystalline alumino-silicates, e.g. molecular sieves
• CPC Class Codes: C10G 47/18 the catalyst containing platinum group metals or compounds thereof
• CPC Class Codes: C10G 47/20 the catalyst containing other metals or compounds thereof
• CPC Class Codes: C10G 65/043 at least one step being a change in the structural skeleton
• CPC Class Codes: C10G 65/08 : at least one step being a hydrogenation of the aromatic hydrocarbons
• CPC Class Codes: C10G 65/12 : including cracking steps and other hydrotreatment steps
• CPC Class Codes: C10G 69/02 : plural serial stages only
• CPC Class Codes: C10G 69/04 : including at least one step of catalytic cracking in the absence of hydrogen
• CPC Class Codes: C10G 73/02 : Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
• CPC Class Codes: C10M 101/02 : Petroleum fractions
• CPC Class Codes: C10M 2203/1006 : used as base material
• CPC Class Codes: C10M 2203/1065 : used as base material
• CPC Class Codes: C10N 2020/011 : Cloud point
• CPC Class Codes: C10N 2020/015 : Distillation range
• CPC Class Codes: C10N 2020/02 : Viscosity; Viscosity index
• CPC Class Codes: C10N 2030/40 : Low content or no content compositions
• CPC Class Codes: C10N 2030/43 : Sulfur free or low sulfur content compositions
• CPC Class Codes: C10N 2040/20 : Metal working

Abstract

A method for producing hydrocarbon solvents having a sulfur content of less than 10 ppm, aromatic hydrocarbon content of less than 500 ppm, an initial boiling point higher than or equal to 300° C. and final boiling point lower than or equal to 500° C., for a fraction interval of a maximum of 100° C., and pour point lower than −25° C. according to the standard ASTM D5950, comprising of the following steps of:

• • dewaxing of a hydrocarbon fraction having initial boiling point higher than 300° C. derived from the distillation of a gas oil fraction,
  • hydrodearomatization of all or part of the dewaxed effluent, in the presence of a catalyst comprising nickel on an alumina base, at a pressure ranging from 60 to 200 bar and a temperature ranging from 80° C. to 250° C.,
  • recovery of the dewaxed and dearomatized fraction,
  • distillation in fractions of the dewaxed and dearomatized fraction,
  • recovery of at least one 300° C.+ fraction having pour point lower than −25° C., this fraction having a distillation interval lower than 100° C.

Claims

1. A method for producing hydrocarbon solvents having a sulfur content of less than 10 ppm, aromatic hydrocarbon content of less than 500 ppm, an initial boiling point higher than or equal to 300°

C. and final boiling point lower than or equal to 500°

C., as determined according to the standard ASTM D86, for a fraction interval of a maximum of 100°

C., and pour point lower than −

25°

C. according to the standard ASTM D5950, comprising the following steps of;

dewaxing of a hydrocarbon fraction having initial boiling point higher than 300°

C. derived from the distillation of a gas oil fraction obtained by any crude oil refining process, and recovery of all or part of the dewaxed effluent, the step of dewaxing comprising at least one first section for mild cracking in the presence of a silicalite based catalyst, having silica/alumina ratio greater than 130, comprising 0% to 10% by weight of at least one metal from group VIII, and possibly 0% to 10% by weight of a metal from Group VI,

hydrodearomatisation of all or part of the dewaxed effluent, in the presence of a catalyst comprising nickel on an alumina base, at a pressure ranging from 60 to 200 bar and a temperature ranging from 80°

C. to 250°

C., and said dewaxed effluent being possibly previously desulphurised in advance if its sulfur content is greater than 15 ppm,

recovery of the dewaxed fraction, possibly desulphurised, and dearomatised,

distillation (DA1) in fractions of the said dewaxed and dearomatised fraction,

and finally recovery of at least one 300°

C.+ fraction having pour point lower than −

25°

C. that is usable as solvent, this fraction having a distillation interval lower than 100°

C.;

characterised in that the dewaxed effluent is sent to an additional separation step (DA2) before reaching the step of hydrodearomatisation, and is separated into at least two effluents, one hydrocarbon fraction of C1 to C4, and at least one dewaxed fraction of which at least one part distills above 300°

C. and has a pour point lower than or equal to −

25°

C.

2. A method according to claim 1, characterised in that the gas oil fraction obtained by any refining process, is selected from among the atmospheric distillation gas oils, vacuum distillation gas oils, hydrocracked gas oils, gas oils from catalytic cracking, gas oils from visbreaking, coking gas oils, deasphalted gas oils, gas oils with a sulfur content greater than 15 ppm being necessarily desulphurised by hydrotreating and/or hydrocracking.

3. A method according to claim 1, characterised in that the hydrocarbon fraction having a boiling point higher than or equal to 300°

C. is obtained by separation (DF) of the gas oil fraction into two fractions, one light fraction (Cl) having the final boiling point below 300°

C. and at least one heavy fraction (CL) having the initial boiling point higher than or equal to 300°

C.

4. A method according to claim 1, characterised in that the step of dewaxing comprises a second section for hydrogenation of olefins in the presence of a silica based catalyst, alumina and/or silica/alumina comprising from 0.1% to 10% by weight of a metal from Group VIII and from 0.1% to 20% of a metal from group VI.

5. A method according to claim 4, characterised in that the step of dewaxing comprises at least two sections for mild cracking (S1).

6. A method according to claim 4, characterised in that the dewaxing catalyst is selected from among silicalites having a silica/alumina ratio greater than 200, these silicalites being able to support nickel alone or a nickel/tungsten combination and in that the catalyst for hydrogenation of olefins is an alumina supporting a metal combination selected from among the cobalt/molybdenum, nickel/tungsten, cobalt/tungsten and nickel/molybdenum combinations.

7. A method according to claim 4, characterised in that the step of dewaxing is carried out under hydrogen pressure, at a temperature ranging from 150°

C. to 450°

C. under a total pressure ranging from 10 to 400 bar.

11. A method according to claim 1, characterised in that the dewaxed fraction of highest initial distillation boiling point derived from the dewaxed effluent is sent to the step of hydrodearomatisation, the latter comprising of one or more hydrodearomatisation sections.

13. A method according to claim 1, characterised in that the 300°

C.+ fraction with pour point lower than −

25°

C. after a last step of atmospheric distillation is recycled in its entirety or partially in the dewaxed fraction sent to the step of hydrodearomatisation.

14. A method according to claim 1, characterised in that the steps of dewaxing and hydrodearomatisation are carried out at the same pressure ranging from 60 to 200 bar in a hydrogen atmosphere, at a temperature ranging from 150°

C. to 450°

C., the temperature of the dewaxed effluent being adjusted before the step of hydrodearomatisation by injection of at least one liquid or gaseous compound with a temperature lower by at least 50°

C. than that of the dewaxed effluent.

15. A method according to claim 14, characterised in that the liquid or gaseous compound is selected from among hydrogen, the light fraction (Cl) resulting from a boiling point below 300°

C. and the 300°

C.+ fraction with pour point lower than −

25°

C. recovered after distillation of the dewaxed effluents, possibly desulphurised and dearomatised.

16. A method according to claim 1, characterised in that the steps of hydrodearomatisation and dewaxing are conducted in the same reactor comprising catalyst beds, the catalyst beds being separated by a cavity allowing for the mixing of the dewaxed effluent with the liquid or gaseous compounds, hydrogen or the recycle of the Cl and/or 300°

C.+ fractions with pour point lower than −

25°

C. recovered after the atmospheric distillation tower (DA1).

17. A method according to claim 5, characterised in that the step of dewaxing comprises at least two sections for mild cracking (S1) alternating with two sections for hydrogenation (S2) of the olefins.

18. A method according to claim 7, characterised in that the step of dewaxing is carried out under hydrogen pressure, at a temperature ranging from 280°

C. to 380°

C. under a total pressure ranging from 20 to 200 bar.

19. A method according to claim 14, characterised in that the steps of dewaxing and hydrodearomatisation are carried out at the same pressure ranging from 60 to 200 bar in a hydrogen atmosphere, at a temperature ranging from 280°

C. to 380°

C. for the dewaxing step and at a temperature ranging from 80°

C. to 250°

C. for the hydrodearomatisation step, the temperature of the dewaxed effluent being adjusted before the step of hydrodearomatisation by injection of at least one liquid or gaseous compound with a temperature lower by at least 50°

C. than that of the dewaxed effluent.

8. A method for producing hydrocarbon solvents having a sulfur content of less than 10 ppm, aromatic hydrocarbon content of less than 500 ppm, an initial boiling point higher than or equal to 300°

C. and final boiling point lower than or equal to 500°

C., as determined according to the standard ASTM D86, for a fraction interval of a maximum of 100°

C., and pour point lower than −

25°

C. according to the standard ASTM D5950, comprising the following steps of;

dewaxing of a hydrocarbon fraction having initial boiling point higher than 300°

C. derived from the distillation of a gas oil fraction obtained by any crude oil refining process, and recovery of all or part of the dewaxed effluent, the step of dewaxing comprising at least one first section for mild cracking in the presence of a silicalite based catalyst, having silica/alumina ratio greater than 130, comprising 0% to 10% by weight of at least one metal from group VIII, and possibly 0% to 10% by weight of a metal from Group VI,

hydrodearomatisation of all or part of the dewaxed effluent, in the presence of a catalyst comprising nickel on an alumina base, at a pressure ranging from 60 to 200 bar and a temperature ranging from 80°

C. to 250°

C., and said dewaxed effluent being possibly previously desulphurised in advance if its sulfur content is greater than 15 ppm,

recovery of the dewaxed fraction, possibly desulphurised, and dearomatised,

distillation (DA1) in fractions of the said dewaxed and dearomatised fraction,

and finally recovery of at least one 300°

C.+ fraction having pour point lower than −

25°

C. that is usable as solvent, this fraction having a distillation interval lower than 100°

C.;

characterised in that the hydrocarbon fraction having a boiling point higher than or equal to 300°

C. is obtained by separation (DF) of the gas oil fraction into two fractions, one light fraction (Cl) having the final boiling point below 300°

C. and at least one heavy fraction (CL) having the initial boiling point higher than or equal to 300°

C.; and

characterised in that the light fraction (Cl) resulting from the separation of the gas oil fraction into two fractions is mixed in whole or part with the dewaxed fraction (CDP) sent to the step of hydrodearomatisation.

9. A method according to claim 8, characterised in that the dewaxed effluent is sent to an additional separation step (DA2) before reaching the step of hydrodearomatisation, and is separated into at least two effluents, one hydrocarbon fraction of C1 to C4, and at least one dewaxed fraction of which at least one part distills above 300°

C. and has a pour point lower than or equal to −

25°

C.

10. A method for producing hydrocarbon solvents having a sulfur content of less than 10 ppm, aromatic hydrocarbon content of less than 500 ppm, an initial boiling point higher than or equal to 300°

C. and final boiling point lower than or equal to 500°

C., as determined according to the standard ASTM D86, for a fraction interval of a maximum of 100°

C., and pour point lower than −

25°

C. according to the standard ASTM D5950, comprising the following steps of;

dewaxing of a hydrocarbon fraction having initial boiling point higher than 300°

C. derived from the distillation of a gas oil fraction obtained by any crude oil refining process, and recovery of all or part of the dewaxed effluent, the step of dewaxing comprising at least one first section for mild cracking in the presence of a silicalite based catalyst, having silica/alumina ratio greater than 130, comprising 0% to 10% by weight of at least one metal from group VIII, and possibly 0% to 10% by weight of a metal from Group VI,

hydrodearomatisation of all or part of the dewaxed effluent, in the presence of a catalyst comprising nickel on an alumina base, at a pressure ranging from 60 to 200 bar and a temperature ranging from 80°

C. to 250°

C., and said dewaxed effluent being possibly previously desulphurised in advance if its sulfur content is greater than 15 ppm,

recovery of the dewaxed fraction, possibly desulphurised, and dearomatised,

distillation (DA1) in fractions of the said dewaxed and dearomatised fraction,

and finally recovery of at least one 300°

C.+ fraction having pour point lower than −

25°

C. that is usable as solvent, this fraction having a distillation interval lower than 100°

C.;

characterised in that the dewaxed effluent may be separated into two dewaxed fractions, three dewaxed fractions or four dewaxed fractions;

one hydrocarbon fraction of C1 to C4 and one hydrocarbon fraction of more than 5 carbon atoms (or C5+);

or one hydrocarbon fraction of C1 to C4 and two hydrocarbon fractions, one of C5 distilling at 150°

C. (or C5-150) and the other distilling above 150°

C. (or 150°

C.+);

or one hydrocarbon fraction of C1 to C4 and three hydrocarbon fractions, the first one of C5 distilling at 150°

C. (or C5-150), the second distilling from 150°

C. to 300°

C. (or 150-300) and the third distilling above 300°

C. (or 300°

C.+).

12. A method for producing hydrocarbon solvents having a sulfur content of less than 10 ppm, aromatic hydrocarbon content of less than 500 ppm, an initial boiling point higher than or equal to 300°

C. and final boiling point lower than or equal to 500°

C., as determined according to the standard ASTM D86, for a fraction interval of a maximum of 100°

C., and pour point lower than −

25°

C. according to the standard ASTM D5950, comprising the following steps of;

dewaxing of a hydrocarbon fraction having initial boiling point higher than 300°

C. derived from the distillation of a gas oil fraction obtained by any crude oil refining process, and recovery of all or part of the dewaxed effluent, the step of dewaxing comprising at least one first section for mild cracking in the presence of a silicalite based catalyst, having silica/alumina ratio greater than 130, comprising 0% to 10% by weight of at least one metal from group VIII, and possibly 0% to 10% by weight of a metal from Group VI,

hydrodearomatisation of all or part of the dewaxed effluent, in the presence of a catalyst comprising nickel on an alumina base, at a pressure ranging from 60 to 200 bar and a temperature ranging from 80°

C. to 250°

C., and said dewaxed effluent being possibly previously desulphurised in advance if its sulfur content is greater than 15 ppm,

recovery of the dewaxed fraction, possibly desulphurised, and dearomatised,

distillation (DA1) in fractions of the said dewaxed and dearomatised fraction,

and finally recovery of at least one 300°

C.+ fraction having pour point lower than −

25°

C. that is usable as solvent, this fraction having a distillation interval lower than 100°

C.;

characterised in that the hydrocarbon fraction having a boiling point higher than or equal to 300°

C. is obtained by separation (DF) of the gas oil fraction into two fractions, one light fraction (Cl) having the final boiling point below 300°

C. and at least one heavy fraction (CL) having the initial boiling point higher than or equal to 300°

C.; and

characterised in that at least a part of the heavy fraction (CL) resulting from the separation of the gas oil fraction into at least two fractions is sent to the step of dewaxing, the other part is mixed with the dewaxed fraction recovered upon being output from the step of separating the dewaxed effluent and sent to the step of hydrodearomatisation.