Method for obtaining hydrocarbon solvents with boiling point above 300?C. and pour point lower than or equal to ?25?C
10047305 · 2018-08-14
Assignee
Inventors
Cpc classification
C10G45/02
CHEMISTRY; METALLURGY
C10G65/08
CHEMISTRY; METALLURGY
C10G47/18
CHEMISTRY; METALLURGY
C10G45/64
CHEMISTRY; METALLURGY
C10G45/58
CHEMISTRY; METALLURGY
C10G69/04
CHEMISTRY; METALLURGY
C10G47/20
CHEMISTRY; METALLURGY
C10G2300/304
CHEMISTRY; METALLURGY
C10G65/043
CHEMISTRY; METALLURGY
C10G65/12
CHEMISTRY; METALLURGY
C10G2300/1059
CHEMISTRY; METALLURGY
C10N2030/43
CHEMISTRY; METALLURGY
C10G73/02
CHEMISTRY; METALLURGY
International classification
C10G69/04
CHEMISTRY; METALLURGY
C10G65/08
CHEMISTRY; METALLURGY
C10G45/02
CHEMISTRY; METALLURGY
C10G47/20
CHEMISTRY; METALLURGY
C10G65/12
CHEMISTRY; METALLURGY
C10G73/02
CHEMISTRY; METALLURGY
C10G47/18
CHEMISTRY; METALLURGY
C10G45/64
CHEMISTRY; METALLURGY
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.
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.+).
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.
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.
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.
Description
(1)
(2)
(3)
(4) In
(5) This heavy fraction CL is sent to the dewaxing reactor R1 referenced (2) fed in parallel by the hydrogen arriving via the pipe lines (31), and then (32). All of the dewaxed effluent is directed through the pipe line (14) into an atmospheric distillation unit DA2 referenced (5). Two, three or four effluents are distilled according to the choice of recovery process contemplated, only the dewaxed fraction CDP discharged via the pipe line (15) is sent to the step of dearomatisation.
(6) For example, the dewaxed effluent may be distilled in the distillation unit DA2 in two dewaxed fractions, three dewaxed fractions or four dewaxed fractions; one hydrocarbon fraction of C1 to C4 also called fuel gas is discharged through the pipe line (21) and a hydrocarbon fraction of more than 5 carbon atoms (or C5+) is discharged through the pipe line (15) to the dearomatisation reactor R2 referenced as (3), or one hydrocarbon fraction of C1 to C4 discharged through the pipe line (21) and two hydrocarbon fractions, one of C5 distilling at 150? C. (or C5-150) discharged through the pipe line (22) and the other distilling above 150? C. (or 150? C.+) is discharged through the pipe line (15) to the dearomatisation reactor R2 referenced as (3), or one hydrocarbon fraction of C1 to C4 discharged through the pipe line (21) and three hydrocarbon fractions, the first one of C5 distilling at 150? C. (or C5-150) discharged through the pipe line (22), the second distilling from 150? C. to 300? C. (or 150-300) is discharged through the pipe line (23) and the third distilling above 300? C. (or 300? C.+) discharged through the pipe line (15) to the dearomatisation reactor R2 referenced as (3).
(7) The dewaxed fraction CDP discharged through the pipe line (15) is sent through the pipe line (16) into the reactor R2 referenced as (3) fed in parallel by the hydrogen coming from the pipe line (31) through the pipe line (33).
(8) The dewaxed and dearomatised effluent is recovered upon being output from the reactor R2 (3) through the pipe line (17) and directed to a distillation unit DA1 referenced as (4) in order to be distilled therein into at least four fractions: the 300? C.+ fraction or fractions recovered through the pipe line (18), the (150-300) fraction discharged through the pipe line (27), the (C5-150) fraction discharged through the pipe line (26), and the C1-C4 fraction or fuel gas discharged through the pipe line (25).
(9) In a certain mode of implementation, the light fraction recovered through the pipe line (12) upon being output from the DF separator (1) may be introduced in whole or part through the pipe line (24) into the CDP effluent before its entry into the reactor R2 (3).
(10) In addition, the (C5-150) fractions upon being output from the distillation units DA1 and DA2 may advantageously be mixed together with the (150-300) fractions with all or part of the light fraction Cl in the pipe line (12) and upon being output from the distillation unit DA1 (4).
(11) In some preferred embodiments, the heavy fraction CL upon being output from the DF separator (11) is only partially sent to the reactor R1 (2), a part of the said fraction sent through the pipe line (20) being mixed with the CDP dewaxed effluent.
(12) Similarly, if the content of aromatic hydrocarbons is too high in the 300? C.+ fraction or if the viscosity of the CDP effluent is insufficient, a part of the 300? C.+ fraction upon being output from the distillation unit DA1 (4) is recycled via the pipe line (28) into the pipe line (16) directing the CDP effluent into the reactor R2 (3).
(13)
(14) The heavy fraction CL is sent to the section SR1 (2) of the reactor (5) fed in parallel by the hydrogen coming in through the pipe lines (31), and then (32) in order to be dewaxed therein. All of the dewaxed fraction is sent to the section SR2 (3), possibly after being mixed in the cavity (30) separating the two sections with the additional hydrogen arriving from the pipe line (33). This injection of hydrogen is useful to the dearomatisation reaction but also serves the function of adjusting the inlet temperature of the feed stock or dewaxed fraction in the section SR2 (3) by quenching (or quench) thereby enabling the lowering of the inlet temperature of the section SR2 (3).
(15) In a particular embodiment of the invention, it is also possible to inject all or part of the light fraction (Cl) through the pipe line (24) into the cavity (30) in order for it to be dearomatised like the dewaxed heavy fraction (CL). The quantity of hydrogen will be adjusted accordingly as well as the inlet temperature in the section SR2 (3).
(16) As in
(17) Similarly, if the content of aromatic hydrocarbons is too high in the 300? C.+ fraction or fractions, a part of the 300? C.+ fraction upon being output from the distillation unit DA1 (4) is recycled via the pipe line (28) into the cavity (30) of the reactor (5) in order to be dearomatised therein once again, in section SR2 of the said reactor (5).
(18)
(19) The performance of the present invention will now be illustrated in the following section of the present description, however these examples are not intended to limit the scope thereof.
EXAMPLE 1
(20) This present example describes the preparation of a dewaxed and dearomatised fraction according to the invention, having an initial boiling point higher than 300? C. and whose pour point is below ?30? C.
(21) The process is operated as described in
(22) The reaction temperature in the dewaxing reactor is 305? C. under a pressure of 30 barg, with a defined Hourly Space Velocity (HSV) corresponding to the ratio of flow rate of the feed stock volume (m3/h) over the catalyst volume (m3/h) of 1 h.sup.?1 and a hydrogen/feed stock ratio of 250 Nl (NL: normal liter) of hydrogen per liter of hydrocarbon feed stock. In the dearomatisation reactor, the temperature is 245? C., under a pressure of 160 barg, a hydrogen/feed stock ratio of 250 Nl of hydrogen per liter of hydrocarbon feed stock and an HSV of 0.4 h.sup.?1. The characteristics of the products from the beginning to the end of the reaction chain are shown in Table 1 here below.
(23) TABLE-US-00001 TABLE 1 GO before DF (Gas 300? C. + Fraction Oils before After R2 Fractional and Characteristics Distillation Before R1 (2) After DA2 DA1 % by weight 17.5 9.8 13.8 127 ppm Aromatic Hydrocarbons % by weight 21.5 27.7 6.3 4.5 n-paraffins % by weight 35 38.4 42.7 47.1 Isoparaffins % by weight 25.8 24.1 34.4 48.3 Total Naphthenes % by weight 20.8 23.2 35.8 Mono naphthenes % by weight 0.52 0.35 0.7 <0.05 olefins ASTM D2710 (gBr.sub.2/100 g sample) % by weight <0.09 0 <0.1 <0.1 Saturated Hydrocarbons <C9 Viscosity at 4.5 7.7 8.7 8.7 40 ? C. (mm.sup.2/g), ASTM D445 Sulfur (ppm) 2 2.4 3.9 <1 ASTM D5453 Nitrogen (ppm) <0.5 <0.5 <0.5 <0.5 by Chemi- luminescence Distillation 236-365 296.8- 369.3 327.9- 371.4 314-367.3 Fraction (? C.) ASTM D86 Pour Point (? C.) ?4 +12 ?40 ?40 ASTM D5950 with reference to D97 (3 degree points) Aniline Point 98.7 (? C.) ASTM D-611
(24) Thus it is found that by the method of the invention, it is possible to obtain hydrocarbon fluids free of aromatic hydrocarbons and all kinds of pollutants, which may be used as solvents, with distillation fraction at a temperature above 300? C. and whose pour point is well below ?30? C. It should be noted that the amount of naphthenes is significantly greater than 40% by weight in these hydrocarbons, the amount of mononaphthenes is significantly greater than 20% by weight. The said pollutants correspond in particular to the olefins, sulfur compounds and nitrogen compounds.
EXAMPLE 2
(25) This example compares the characteristics of the products obtained in Example 1 referenced as X with those of the products obtained from hydrodewaxing mainly by isomerisation of gasoil fractions or a hydrocracked and hydrodearomatised gas oil. These products resulting from the prior art are respectively referenced as T1 and T2.
(26) The comparative characteristics are presented in Table 2 here below.
(27) TABLE-US-00002 TABLE 2 Characteristics X T1 T2 ppm by weight of 127 264 70 Aromatic Hydrocarbons % by weight 4.5 0.1 16 n-paraffins % by weight 47.1 74.2 59.9 Isoparaffins, % by weight 48.3 24.8 24.1 Total Naphthenes % by weight 35.8 18.9 22.4 Mono naphthenes Sulfur (ppm) by <1 <1 <1 UV method Viscosity at 8.7 10.3 6.1 40? C. (mm2/g), ASTM D445 Distillation 314-367 334-378 305-347 Fraction (? C.) ASTM D86 Pour Point (? C.), ?40 ?35 0 ASTM D5950 with reference to D97 (3 degree points) Aniline Point (? C.) 98.7 108 101 ASTM D611
(28) It should be noted that with respect to the fraction with boiling above 300? C., the dewaxing provides the ability to reduce the pour point to lower than ?30? C. It should also be noted that comparatively between the fractions X and T1, the content of mono naphthenes is very different, for X this is greater than 20% and even greater than 30% by weight, while that it remains significantly lower than 20% by weight for T1. The reduction of the aniline point for the fraction X indicates an improvement of the solvent power.