US 2758060 A
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2,758,060 Patented Aug. 7, 1956 REMOVAL OF VANADIUM AND/OR SODIUM" FROM PETROLEUM BY HYDROGENATION IN THE PRESENCE OF BAUXITE Frederick William Bertram Porter and John Welford Hyde, Sunbury-on-Thames, England, assignors to The British Petroleum Company Limited 7 a No Drawing. Application December 28, 1951, Serial N0. 263,956
Claims priority, application Great Britain January 15, 1951 5 Claims. (Cl. 196-35) This invention relates to the removal of vanadium and/or sodium from petroleum and petroleum products.
In the specification of our co-pending British application No. 16540/49, we have described a process for the removal of vanadium from petroleum products wherein thepetroleum product is subjected to treatment with hydrogen in the presence of a sulphur-resistant hydrogena tion catalyst and under conditions of temperature and pressure such that the vanadium is deposited on or'in corporated with the catalyst. we have now discovered a process bymeans of which vanadium and/or sodium may be substantially or completely removed from petroleum or petroleum products. The process may be successfully applied to crude petroleum, uses a comparatively cheap catalyst, and may be operated with substantially complete removal of vanadium and sodium for operating periods of at least 600 hours.
According to invention, sodium is removed from pcprocess which increases rapidly at temperatures above 750 F. so that in practice it has been found advantage- 7 ous to operate at a maximum temperature of 780 F.
The pressure is 800-1000 'lb./sq. in
It has been found that about 70% of the vanadium in a Kuwait crude oil containing 22 p. p. m. of vanadium may be removed during a catalyst life of at least 650 hours with a hydrogen consumption of 65 C. F./B., under the preferably maintained in the range following conditions.
Space velocity v./v./hr 1.0 Temperature F 7 80 Hydrogen recycle rate C. F./B 4000 Pressure p. s. i. g' '1000 Under these conditions 90-95% of the sodium originally present in the crude oil is removed.
Little advantage is gained by increasing the recycle rate above 6000 C. F./B. but when the recycle rate is reduced below 2000 C. F./B. the residual vanadium content increases considerably.
' troleum or a petroleum product by contact with bauxite under conditions of temperature and pressure such that the sodium is deposited on or incorporated with the bauxite.
The degree of sodium removal is appreciable at a temperature of 650 F. and increases progressively with in- The process of the invention is particularly advantageous as applied to the treatment of crude petroleum. The application of the so-calledhydrofining process to crude petroleum has been describedin the specification of co-pending British'application No. 22050/50, corresponding to U. 8. application No. 245,046 filed September 4, 1951, now abandoned, the use of cobalt molybdate type catalysts beingpreferred. The higher boiling. fractions of crude petroleum often contain traces of vanadium and sodium and it has been shown that in the hydrofining of petroleum and petroleum residues substantial proportions of the vanadium and sodium are removed by and deposited on the cobalt molybdate catalyst, and that this deposition causes a steady decline in catalyst activity with hours on stream which is not wholly recovered on regeneration in the conventional manner. The treatment of the crude petroleum or residue in accordance with the present invention will therefore result in considerable improvement in the hydrofining process as applied to'these materials. A two-stage process consisting of the treat- At 780 F. the degree of sodium removal is appreciable even at atmospheric pressure and increases with increase of pressure until an apparent maximum of approximately 85% is reached in the range 100-200 p. s. i. g.
If the feedstock contains vanadium in addition to sodium, it has been found that the degree of vanadium re- 15% at 800 F. At 850 F. there is an increased removal of vanadium but increased decomposition of the feedstock results in short process period due to deposition of carbon. At a temperature of 780 F. the removal of vanadium increases with pressure from 10% at atmospheric pressure to an apparent maximum of 28% in the range 100-200 p. s. i. g.
It has been found that the degree of sodium removal" may be maintained and the degree of vanadium removal considerably increased by contacting the feedstock with bauxite in the presence of hydrogen.
According to a further feature of the invention, therefore, both sodium and/ or vanadium is/ are removed from petroleum or a petroleum product by contact with bauxite 700800 F. There is a consumption of hydrogen i'ri tli' moval is small rising from nil at 650 F. to approximately ment of a crude petroleum or residue in accordance with the present invention followed by the hydrofining of the treated crude petroleum or residue forms the subject of co-pending British application No. 6619/51.
Traces of vanadium and sodium also occur in petroleum.
'feedstocks, such as wax distillates, which are subjected to cracking in the presence of a cracking catalyst, which may be a natural clay, such as montmorillonite, or a synthetic material, of which silica-alumina gel is typical, for the production of lower boiling products. In this case, the presence of the vanadium and sodium in the feedstock causes a slow decline in catalyst activity which is not recovered on regeneration andwhich eventually necessitates the replacement of the catalyst. The present invention therefore includes within its scope a process which comprises subjecting a'catalytic cracking feedstock to treatment for the removal of vanadium and/or sodium as hereinbefore described, followed by catalytic cracking of the treated feedstock.
The invention will now be described with reference to the following examples.
Iranian crude oil was passed over roasted Indian bauxite at a space velocity of 1.0 v./v./hr. and at temperatures of 650, 700, 750, 800 and 850 F. Each run was of 50 hours duration except the last one, at 850 R, which had to be terminated owing to excessive coke formation.
The results are set out in Table I.
n A. i: i
TABLE I Hours on stream since regeneration Feed -50 0-50 0-50 0-50 0-6 Operating Conditions:
Catalyst Charge, Vol ml Catalyst Charge, Wt g. No. of regenorations-.. n Direction of flow Downwards. Nominal catalyst bed temp Reactor pressure.....p. s. 1. ga: Atmos Space Velocity v/v/hr. 1.00. Product Gas Make -.O. I*./B.. Sulphur Percent wt.. 1.65. Sulphur removal... ....Percent.. 250. Sodium content .p. p. m.. 3.5. Sodium removal... erccnt.- 97. Vanadium content... -...p. p. m.. 9. Vanadium removal ..Percent.. 85. Kinematic Viscosity, 140 F.....cs.. 5.44. Kinematic Viscosity, 170 F ....es.- 3.80. Kinematic Viscosity, 210 F. ...cs.. 2.60.
1 H18 tree.
Example 2 Example 4 under the following nominal conditions.
crude oil A Kuwait wax distillate representing approximately 50-77 per cent by volume on crude with a boiling range of approximately 380 to 590 C. T. B. P. and a sul- Feedrate phur content of 2.84 per cent by weight was treated at Tem erature F 780 P so 1000 p. s. 1. g., 780 F. and 1.0 v./v./hr., over an act:- Pressure Atmosphemf 100409 vated Indian bauxite with 4000 C. F./B. of recycle catallfst Roasted Indlan bauxlte hydrogen. Analyses of the feedstock and product after Duration 50 treatment are given in the following Table IV.
The results are set out in Table II.
TABLE II Test Period No Feed 1 Feed 2 Feed 3 Hours on stream since regeneration... 0-50 0-50 050 Operating Conditions:
Reactor pressu g 199 Space Velocity ..v./v./hr 1. 02 Exit Gas Mol. Percent Ii: (:h 46.
(H free). Exit Gas M01. Percent H23 1. 0 Gas Make (HIS free)...-0. F./B.. 28 Sodl p.11. m.. 0.2 Sodium Removal. percent... 85 Vanadium .p. 15.5 Vanadium Removal .percent.. 28
Example 3 TABLE IV A Kuwait crude oil was passed over a catalyst conslstmg of roasted Indian bauxite at a space velocity of Feedstock Produc 1.0 v./v./hr., a temperature of 780" F., and a pressure of 1000 p. s. i. g., together with hydrogen to the amount guipgun ..percentW.- 2.84 2. 78
' up 111' BHIOVE B10611 of 4000 C. F./B. The process was continued for 600 Tom Ash Content" L wt" M041 M02 hours and the results obtained are set out in the follow- T otal ash 1mmvs1. .5 percent. 31. 811D ump. .II1.W. mg Table 111' Vanadium'Rer oval .percent 70.0 Sodium, p. p. :11. (wt.). 0.15 Sodium Removal percent 90 TABLE III Experiments were conducted using an Indian bauxite sample Feed 333%? gffi as catalyst to ascertain the effect when operating in the presence of hydrogen of varying temperature, space veva, p. m n 24 3 5 7 locity and recycle rate. The conditions employed in these N 9 I m 6 0- 2 0- 0 1 experiments and the results obtained are set out in Tables .7 V-.-V1I respectively.
- 517m of temperature Test Period No Feed 1 Feed 3 Average Hours on stream since regeneration. -50 100-160 F Hydrogen Consumption .::.0: F. B
Percent wt. on 1eedstock.
odium p ur Sulphur Removal ..percent.
I Corrected for H: content of stablliser gas.
TABLE VI Test Period No Hours on stream since regeneration Operating Conditions:
atalyst Charge, vol mil. Catalyst Charge, wt. g.. No. of regenerations Total life of catalysthr.. Direction of flow Av. catalyst bed temperature.. F--
Reactor pressure...- -.p. s. i. ga.. Space Velocity... ..v/v/hr Recycle gas rate --C Hydrogen Consumption LC. Liquid Product:
Percent wt. on feedstock. 98. 3 .1 95. 8
Specific Gravity, 60 F./60 F 0.871 0.875 0. 8685 0. S725 Sodium 2. 2 3. 9 1.
Sodium Remov 31 62 Vanadium. 16. 5 23. 8 16. 9
Vanadium 39 29 Sulphur... 2. 42 2. 48 2. 41
Sulphur Removal -perccnt.. 3. 2 2.8
I Corrected for hydrogen content of stabiliser gas.
TABLE V'H Efiect of recycle rate Test Period No Feed 1 2 3 4 Hours on stream since regeneration 0-25 50 50-75 -100 Operating Conditions:
Catalyst Charge, Vol ml.. Catalyst Charge, wt.. No. of regenerations. Total life of catalyst. Direction of flow....
Hydrogen 00 Liquid Product:
Percent wt. on feedstock percent Wt.
Sulphur Sulphur Removal ..percent 1 Not corrected for H1 content 0! stabiliser gas.
1. A process for removing sodium and vanadium from a petroleum hydrocarbon selected from the group consisting of crude petroleum, petroleum residue, and wax distillate, which comprises contacting said hydrocarbon with a catalyst consisting essentially of bauxite and in the presence of hydrogen at a temperature within the range from about 700 to 800 F. and at a pressure within the range of about 800 to 1000 p. s. i. gauge, whereby the sodium and vanadium contained in the hydrocarbon are contained on the bauxite catalyst, and recovering a substantially sodium and vanadium-free hydrocarbon.
2. \A process in accordance with claim 1 in which the hydrogen is passed in at a rate of about 2000 to'6000 C. F./B. and the space velocity of the hydrocarbon is between 1 and 3 v./v./hr.
3. A process in accordance with claim 1 wherein the petroleum hydrocarbon is a petroleum residue.
4. A process in accordance with claim 1 wherein the petroleum hydrocarbon is crude petroleum.
5. A process in accordance with claim 1 wherein the petroleum hydrocarbon is a wax distillate.
References Cited in the file of this patent UNITED STATES PATENTS 2,355,366 Conn Aug. 8, 1944 2,371,298 Hudson et al Mar. 13, 1945 2,383,972 Jones Sept. 4, 1945 2,487,466 Nahin Nov. 8, 1949 2,537,620 Brandon Jan. 9, 1951 2,604,436 Adey et a1. July 22, 1953 QTHER REFERENCES Mills, Ind. and Eng. Chem., 42, pp. 182-187 (1950).
Houdry Jan. 23, 1940