Composition formed of Bitumen Bases for the Manufacture of Bitumen Comprising a Slurry Residue

Abstract

The invention relates to a composition formed of bitumen bases which comprises at least from 70% to 99% by weight of at least one bitumen base having a penetrability at 25 C. of less than or equal to 220.10-1 mm and a softening point of greater than or equal to 35 C. and from 1% to 30% by weight of at least one slurry residue resulting from a slurry-phase hydroconversion process. The slurry residue may have a penetrability at 25 C. of less than or equal to 50.10-1 mm and a softening point of greater than or equal to 50 C. Embodiments of the invention make it possible to upgrade a final vacuum residue slurry for use in the manufacture of a road bitumen.

Claims

1-10. (canceled)

11. A composition formed of bitumen bases comprising at least: a) from 70% to 99% by weight of at least one bitumen base having a penetrability at 25 C. of less than or equal to 220.10.sup.1 mm and a softening point of greater than or equal to 35 C.; and b) from 1% to 30% by weight of at least one slurry residue resulting from a slurry-phase hydroconversion process, the at least one slurry residue having a penetrability at 25 C. of less than or equal to 50.10.sup.1 mm and a softening point of greater than or equal to 50 C.

12. The composition according to claim 1, comprising at least: from 75% to 99% by weight of at least one bitumen base as defined in a); and from 1% to 25% by weight of at least one slurry residue as defined in b).

13. The composition according to claim 11, comprising at least: from 85% to 99% by weight of at least one bitumen base as defined in a); and from 1% to 15% by weight of at least one slurry residue as defined in b).

14. The composition according to claim 11, comprising from 1% to 30% by weight of at least one slurry residue exhibiting a content of catalyst particles of 0% to 3% by weight.

15. The composition according to claim 13, comprising from 1% to 15% by weight of at least one slurry residue exhibiting a content of catalyst particles of 0% to 5% by weight.

16. The composition according to claim 1 wherein the at least one bitumen base defined in a) is a base resulting from the atmospheric distillation and/or vacuum distillation of crude oil.

17. The composition according to claim 1 wherein the at least one slurry residue defined in b) results from a slurry-phase hydroconversion process of a feedstock having an H/C ratio of at least 0.25, the said process operating at temperature conditions of 400 to 500 C., with a hydrogen pressure of 90 to 250 bar and an HSV of 0.05 to 1.5 h.sup.1, a catalyst comprising at least one metal being added in the form of a precursor, and dispersed in the feedstock.

18. The composition according to claim 1 wherein the at least one bitumen base defined in a) exhibits a penetrability at 25 C. of from 5.10.sup.1 to 220.10.sup.1 mm, for example from 10.10.sup.1 to 100.10.sup.1 mm or from 35.10.sup.1 to 100.10.sup.1 mm.

19. The composition according to claim 1 wherein the at least one bitumen base defined in a) exhibits a softening point of greater than or equal to 43 C.

20. The composition according to claim 19 wherein the at least one bitumen base defined in a) exhibits a softening point of greater than or equal to 50 C.

20. A method comprising using a slurry residue resulting from a slurry-reactor hydroconversion process as a bitumen base for a road bitumen, wherein the bitumen base comprises: a) from 70% to 99% by weight of at least one bitumen base having a penetrability at 25 C. of less than or equal to 220.10.sup.1 mm and a softening point of greater than or equal to 35 C.; and b) from 1% to 30% by weight of at least one slurry residue resulting from the slurry-phase hydroconversion process, the slurry residue having a penetrability at 25 C. of less than or equal to 50.10.sup.1 mm and a softening point of greater than or equal to 50 C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0072] Other advantages and characteristics will emerge more clearly from the description which will follow and for which specific embodiments of the invention are given as non-limiting examples.

[0073] The present invention consists in providing a composition formed of bitumen base comprising a conventional bitumen base (other than a slurry residue) mixed with a slurry residue.

[0074] According to the invention, a composition formed of bitumen bases is prepared which comprises at least:

[0075] a. from 70% to 99% by weight of at least one bitumen base having a penetrability at 25 C. of less than or equal to 220.10.sup.1 mm and a softening point of greater than or equal to 35 C.

[0076] b. from 1% to 30% by weight of at least one slurry residue resulting from a slurry-phase hydroconversion process, the said slurry residue having a penetrability at 25 C. of less than or equal to 50.10.sup.1 mm and a softening point of greater than or equal to 50 C.

[0077] The slurry residue defined in b) can exhibit a penetrability at 25 C. of greater than or equal to 5.10.sup.1 mm and a softening point of less than or equal to 90 C.

[0078] Advantageously and non-limitingly, the composition formed of bitumen bases according to the invention can comprise at least:

[0079] a. from 75% to 99% by weight of at least one bitumen base as defined in a) above;

[0080] b. from 1% to 25% by weight of at least one slurry residue as defined in b) above.

[0081] The composition formed of bitumen bases according to the invention can comprise at least:

[0082] a. from 85% to 99% by weight of at least one bitumen base as defined in a) above;

[0083] b. from 1% to 15% by weight of at least one slurry residue as defined in b) above.

[0084] The slurry residue or residues defined in b) can comprise catalyst fines (catalyst particles) in a variable content. Generally, the content observed is from 0.05% to 5% by weight and can be reduced, for example, from 0% to 0.25% by weight, for example as a result of a filtration or any other treatment which makes it possible to separate the catalyst particles from a slurry residue.

[0085] Advantageously, the composition formed of bitumen bases can comprise from 1% to 30% by weight, for example from 1% to 25% by weight, of at least one slurry residue exhibiting a content of catalyst particles of 0% to 3% by weight.

[0086] Advantageously, the composition formed of bitumen bases can comprise from 1% to 15% by weight of at least one slurry residue exhibiting a content of catalyst particles of 0% to 5% by weight.

[0087] The sum of the percentages by weight of the bitumen bases defined in a) and b) can be equal to 100%. In other words, the composition formed of bitumen bases according to the invention can be composed of one or more bitumen bases as defined in a) and of one or more slurry residues as defined in b). In particular, the composition formed of bitumen bases according to the invention can be composed of a single bitumen base as defined in a) and of a single slurry residue as defined in b).

[0088] The bitumen base mentioned in a) can be a normal bitumen base produced by refining a crude oil homologated to produce bitumen, as described above. In other words, the said at least one bitumen base defined in a) can be a base resulting from the atmospheric distillation and/or vacuum distillation of crude oil, in particular of a crude oil homologated to produce bitumen.

[0089] The slurry residue mentioned in b) is a slurry residue as described above. It is in particular a final vacuum residue of a slurry-phase hydroconversion process. It can thus result from a process for the slurry-phase hydroconversion of a feedstock having an H/C ratio of at least 0.25, the said process operating at temperature conditions of 400 C. to 500 C., with a hydrogen pressure of 90 to 250 bar and HSV of 0.05 to 1.5 h.sup.1, a catalyst comprising at least one metal being added in the precursor form and dispersed in the feedstock. A separation in three stages as described above can make it possible to recover the said slurry residue (final vacuum residue).

[0090] The composition formed of bitumen bases according to the invention can be produced by simple mixing of the bitumen bases defined in a) and b), in particular with stirring, at a temperature sufficient to ensure a homogeneous mixture of these bases. This temperature is generally greater by 80 C. than the softening point of each of the bases (bitumen base and slurry residue).

[0091] The said at least one bitumen base defined in a) can exhibit a penetrability at 25 C. of from 5.10.sup.1 to 220.10.sup.1 mm, for example from 10.10.sup.1 to 100.10.sup.1 mm or from 35.10.sup.1 to 100.10.sup.1 mm.

[0092] Whatever its penetrability, the said at least one bitumen base defined in a) can exhibit a softening point of greater than or equal to 35 C., as already mentioned, for example of greater than or equal to 43 C., indeed even greater than or equal to 50 C. In particular, the softening point can be from 35 C. to 78 C., for example from 43 C. to 78 C. or from 43 C. to 58 C. or from 58 C. to 78 C.

[0093] In particular, the said at least one bitumen base defined in a) can exhibit the following characteristics: [0094] a penetrability at 25 C. of 5.10.sup.1 to 70.10.sup.1 mm and a softening point of greater than or equal to 54 C., for example of 54 C. to 78 C. By way of example, the penetrability at 25 C. can be from 15.10.sup.1 to 25.10.sup.1 mm and the softening point can be greater than or equal to 55 C., for example from 55 C. to 71 C.; or also the penetrability at 25 C. can be from 10.10.sup.1 to 20.10.sup.1 mm and the softening point can be greater than or equal to 58 C., for example from 58 C. to 78 C.; or also a penetrability at 25 C. can be from 5.10.sup.1 to 15.10.sup.1 mm and the softening point can be greater than or equal to 60 C., for example from 60 C. to 76 C.; or also the penetrability at 25 C. can be from 20.10.sup.1 to 30.10.sup.1 mm and the softening point can be greater than or equal to 54 C., for example from 54 C. to 63 C.; or also the penetrability at 25 C. can be from 35.10.sup.1 to 50.10.sup.1 mm and the softening point can be greater than or equal to 57 C., for example from 57 C. to 66 C.; or also the penetrability at 25 C. can be from 50.10.sup.1 to 70.10.sup.1 mm and the softening point can be greater than or equal to 63 C., for example from 63 C. to 72 C.; or [0095] a penetrability at 25 C. of 35.10.sup.1 to 50.10.sup.1 mm and a softening point of greater than or equal to 50 C., for example from 50 C. to 58 C., or [0096] a penetrability at 25 C. of 70.10.sup.1 to 100.10.sup.1 mm and a softening point of greater than or equal to 43 C., for example from 43 C. to 51 C.

[0097] The said at least one bitumen base defined in a) can in particular belong to one of the bitumen categories 1 to 3 defined above.

[0098] The invention also relates to the use of a residue resulting from a hydroconversion process in a slurry reactor as bitumen base for a road bitumen.

[0099] For example, a process for the preparation of a bitumen base for a road bitumen can comprise: [0100] a stage of treatment of a crude oil by a slurry-phase hydroconversion process in at least one reactor, [0101] a stage of separation, in particular in three substages, of an effluent exiting from the said at least one reactor in order to separate a slurry residue, [0102] a stage of recovery of the slurry residue.

[0103] As described above, the slurry residue then forms a bitumen base which can be used to produce a road bitumen.

EXAMPLES

[0104] For the record, throughout the present patent application, the following properties of the bases are measured as indicated in Table 2 below:

TABLE-US-00002 TABLE 2 Measurement Property Abbreviation Unit standard Needle P25 1/10 mm EN 1426 penetration at 25 C. Ring and ball RBT C. EN 1427 softening temperature Fraass breaking Fraass C. EN 12593 point Kinematic KV135 mm.sup.2/s EN 12595 viscosity at 135 C. Dynamic DV60 Pa .Math. s EN 12596 viscosity at 60 C. Pfeiffer index PI without EN 12591

Bitumen Bases

[0105] Base A: Hard base grade 20/30, the properties of which appear in Table 3 below:

TABLE-US-00003 TABLE 3 Characteristics Values P25 18 RBT 61.4 Fraass 0 PI 0.8

[0106] Base B: Slurry residue (VR Slurry)

[0107] A vacuum residue resulting from the vacuum distillation of a Ural crude is mixed with catalyst based on molybdenum and hydrogen upstream of an oven in which it is heated. The mixture is subsequently sent to a perfectly stirred reactor where the slurry-phase conversion reaction is continued. A separation in three stages, as described above, is carried out so as to obtain the final vacuum residue, which corresponds to the 525 C..sup.+ cut.

[0108] The analysis of the slurry residue obtained is described in detail in Tables 4 and 5 below:

TABLE-US-00004 TABLE 4 Unit Value Xylene insolubles % <3% Density 15 C. kg/m.sup.3 1087.8 Softening point T C. C. 68.2 Viscosity 135 C. mm.sup.2/S 1103 Viscosity 150 C. mm.sup.2/S 496 Hydrogen % w 9 Carbon % w 86.4 Oxygen % w 0.71 Sulphur % w 2.3

TABLE-US-00005 TABLE 5 Characteristics Values P25 10 RBT 69 Fraass 11 PI 0.51

[0109] Base C: Soft base grade 160/220, the characteristics of which appear in Table 6 below.

TABLE-US-00006 TABLE 6 Characteristics Values P25 185 RBT 39.6 Fraass <-15 PI 0.55

[0110] Base D : vacuum residue, corresponding to a base of grade 10/20, the characteristics of which are collected in below table 7.

TABLE-US-00007 TABLE 7 Characteristics Values P25 14 TBA 64.1 Fraass 1 IP 0.83 VC135 1882 Solubility(% masse) 100 Cleveland Eclair 374 Point ( C.)

[0111] Production of the Mixture of the Bases A and B: Preparation of a Composition Formed of Bitumen Bases

[0112] Before mixing, the bases A and B are preheated in a ventilated oven at 140 C. The preheating time is estimated at 1 h 30 for 1 kg of base in order to obtain a fluid and homogeneous base.

[0113] In order to produce each of the mixtures, 500 g of the bases A and B are withdrawn while observing the weight percentages below: [0114] Mixture 1: 25% B-75% A [0115] Mixture 2: 50% B-50% A [0116] Mixture 3: 75% B-25% A

[0117] The mixture is heated by a heating mantle system with an electrical resistance, thermostat and thermocoupled PT100 temperature probe. Stirring is carried out with a system of Rayneri type which is a metal centripetal turbine coupled to a stirring system provided with a system for adjusting the speed (0 to 2000 rev/min).

[0118] The mixture is heated at 160 C. with stirring (250-300 rev/min) for a duration of 45 min so as to obtain a homogeneous mixture.

[0119] Penetrability, RBT and Fraass measurements are carried out on each of the mixtures according to the standardized methods. The results are collated in Table 8.

TABLE-US-00008 TABLE 8 Mixture 1: Mixture 2: Mixture 3: Mixture 0: 25% B - 50% B - 75% B - Characteristics 100 A 75% A 50% A 25% A P25 18 13 11 10 RBT 61.4 63.8 65.2 67.4 Fraass 0 NM NM NM PI 0.80 0.92 0.95 0.75 NM: not measured

[0120] Manufacture of a Bitumen of 35/50 Grade from the Compositions Formed of Bitumen Bases Prepared Above (Mixtures 1 to 3)

[0121] Before mixing, the base C is preheated in a ventilated oven at approximately 120 C. The preheating time is estimated at 1 h 30 per 1 kg of base in order to obtain a fluid and homogeneous base.

[0122] The mixing of the base C and of the A/B mixture is carried out similarly to the preparation of the A/B mixture.

[0123] Penetrability, RBT and Fraass measurements are carried out on each of the mixtures according to the standardized methods. The results are collated in Table 9.

TABLE-US-00009 TABLE 9 Test 1: Test 2: Test 3: Test 4: Mixture 0 + Mixture 1 + Mixture 2 + Mixture 3 + Characteristics 36% Base C 44% Base C 47% Base C 49% Base C P25 33 36 37 35 RBT 53.6 53 52.6 52.4 Fraass 5 4 2 1 PI 1.22 1.18 1.22 1.37 KV135 654 534 453 400 DV60 567 448 409 383 RBT after 5.4 6.2 8.0 10.4 RTFOT ageing % VR slurry in 0% 14% 26.5% 38.25% total mixture

[0124] Test 2 shows that it is possible to incorporate VR slurry without damaging the properties of the bitumen. Specifically, these properties are in accordance with the compulsory properties expected by the EN 12591 specification both as regards to the penetrability at 25 C. and the softening point (RBT).

[0125] Likewise, it is observed that the impact on the variation in RBT after RTFOT ageing (NF EN 12607-1), which is a limiting constraint in the formulation of a bitumen, is less than or equal to 8 for Tests 2 and 3, that is to say in accordance with the EN 12591 specifications.

[0126] Even more, it is apparent that the incorporation of VR slurry has a positive impact on the kinematic viscosity at 135 C. and the dynamic viscosity at 60 C. This is because the kinematic viscosity at 135 C. decreases by 18% with 14% of VR slurry in the finished product. This decrease in the viscosity makes it possible to render the bitumen pumpable at lower temperatures and makes it possible to apply the bitumen at a lower temperature.

[0127] It is thus demonstrated that the incorporation of 525.sup.+ slurry residue resulting from the hydroconversion process in a slurry reactor is possible in the category 1 road grades according to Standard EN 12591.

[0128] The incorporation can thus be envisaged at a level of: [0129] 14% (by weight) approximately on taking into account the portion of catalyst fines present in the residue in order to meet the minimum specification with regard to the solubility of 99%, [0130] 25% (by weight) approximately for the road grades on reducing the amount of catalyst fines, for example by a filtration process.

[0131] Following the same reasoning, the incorporation of 525.sup.+ residue is also possible for the categories 2 and 3 which exhibit compulsory properties according to the NF EN 13924-1 and NF EN 13924-2 specifications which are less restricting than the category 1 defined according to Standard EN 12591.