CA1210727A - Process for removing metal contaminants from hydrocarbon feedstocks - Google Patents
Process for removing metal contaminants from hydrocarbon feedstocksInfo
- Publication number
- CA1210727A CA1210727A CA000452023A CA452023A CA1210727A CA 1210727 A CA1210727 A CA 1210727A CA 000452023 A CA000452023 A CA 000452023A CA 452023 A CA452023 A CA 452023A CA 1210727 A CA1210727 A CA 1210727A
- Authority
- CA
- Canada
- Prior art keywords
- feedstock
- hydrocarbon
- process according
- guard chamber
- arsenic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
PROCESS FOR REMOVING METAL CONTAMINANTS
FROM HYDROCARBON FEEDSTOCKS
ABSTRACT
A process for the removal of metal contaminants such as arsenic or iron from an oleagenous hydrocarbon feedstock is provided. Such a process involves contacting the feedstock in a high pressure guard chamber with a high surface area reactive metal absorbent such as nickel followed by subjecting the feedstock to a water wash desalting step.
FROM HYDROCARBON FEEDSTOCKS
ABSTRACT
A process for the removal of metal contaminants such as arsenic or iron from an oleagenous hydrocarbon feedstock is provided. Such a process involves contacting the feedstock in a high pressure guard chamber with a high surface area reactive metal absorbent such as nickel followed by subjecting the feedstock to a water wash desalting step.
Description
~Z ~Z7 F-21lO
PROCESS FOR REMOVING METAL CONTAMINANTS
FROM HYDROCARBON FEEOSTOCKS
_ This present invention relates to a method of removing metal contaminants such as arsenic or iron from oleagenous hydrocarbon feedstocks. This invention, more particularly, îs concerned with a sequential two-stage process for removing metal contaminants, the t~o-stage process comprising a guard chamber adsorption reaction followed by a water washing desalting step.
Retorted shale oil contains a large number of trace metals such as As, Fe, Ni, V, Co, Se and Zn. Arsenic and iron are the predominant trace elements ( > 2û ppm), and as such, these metals present several processing and product problems. For example, some arsenic compounds are water soluble and can cause pipeline corrosion. ~en shale oil is upgraded by delayed coking, most of the metals are rejected in the coke, resulting in a lower quality coke. Upgrading catalysts are irreversibly poisoned by metals deposition, substantially increasing upgrading costs. When burned directly as a fuel, shale oil poses potential As203 emission problem. The present invention is directed to eliminating all or most of the problem by removing substantially all or most of the arsenic and iron metal and other metal contaminants contained in hydrocarbon feedstocks, such as retorted shale oil.
5ubstantial prior art exists for using nickel-containing catalysts/adsorbents for shale oil dearsenation. Examples of this art are U.S. Patent No. 3,896,n49; U.S. Patent No. 3,876,533; U.S.
Patent No. 4,003,829; and U.S. Patent NoO 4,051,022. Further, the use of aqueous desalting is well established as are guard chamber or hydrotreating processes. However, it is believed that the prior art does not disclose nor suggest the instant invention involving a particular sequence of steps for demetalizing hydrocarbon feedstocks.
~Z~ 7;~7 lhe present invention provides a two-stage process for the removal of metal contaminants, at least one of which is arsenic, from a hydrocarbon feedstock. In the first step of such a process, the feedstock is contacted in a guard chamber reaction zone with a reactive metal adsorbent comprising a Group VIB or Group VIII metal dispersed on a porous inorganic oxide suppor-t having a surface area of at least 100 m2/9. Such contacting occurs in the presence of hydrogen under conditions such that less than 150 scf/B of hydrogen are consumed in the guard chamber. Such conditions include a temperature of from 250F to 750F, a pressure of from 1500 psig to 3000 psig, and a liquid hourly space velocity of from 105 to 3.
Treatment in the guard chamber reaction zone serves to remove at least 80% of said metal contaminant from said feedstock. After treatment of the feedstock in the guard charnber reaction zone, the feedstock is,in a second step of the process, contacted with water in a desalting zone under desalting conditions. Such conditions include use of a weight ratio of water to hydrocarbon of from 0.5:5 to 5:0.5 and a temperature which is above the pour point of the hydrocarbon feedstock and which further is within the range of from 100F to 300F. This two-stage process thus produces a demetalatea hydrocarbon product containing less than 1.0 ppm of arsenic contaminant.
An essential element of the present invention, as noted hereinbefore, involves the use of a particular reactive metal adsorbent in the guard chamber reaction zone under particular conditions. The Group VIB or Group VIII metal component of the reactive metal adsorbent can be employed in any suitable form.
Thus, the reactive metal may be present in the adsorbent as the element metal, the oxide, the sulfide or in ionic form. Preferred metals for use in the guard chamber adsorbent include nickel, molybdenum9 cobalt, iron and copper. Particularly preferred is nickel. Preferred reactive rnetal adsorbents will generally contain at least about 20% by weight of the reactive metal, more preferably at least about 40%.
The reactive metal is dispersed on a porous inorganic oxide support having a surface area of at least about lûO m2/g, preferably at least about 150 m /9. Examples of suitable inorganic oxide support materials include silica, alumina, magnesia, titania, and mixtures thereof. Especially preferred is a support comprising a mixture of silica and alumina, preferably in a weight ratio of from 3:1 to 1:3. The metal component can be dispersed on the inorganic oxide support by any conventional procedure including coprecipitation or physical admixing of the metal source and the inorganic oxide support.
The contacting of hydrocarbon feedstock with reactive metal adsorbent in the guard chamber occurs in the presence of hydrogen.
Conditions in the ~uard chamber are maintained so that very little hydrogen; e.g., less than 150 standard cubic feet of H2 per barrel of hydrocarbon (scf/B) [26.7 normal liters H2/liter of hydrocarbon (nl/l)] are consumed. Preferably no more than 100 scf/B
[17.8 nl/l)] of hydrogen will be consumed in the guard chamber.
Since hydrogen consumption in the guard chamber is so low, a low purity hydrogen source can be used such as retort off-gas.
Conditions in the guard chamber reaction zone include generally elevated temperatures and pressures. Temperatures will generally range from 250F to 750F (121C to 399C), more preferably from 300F to 600F (149C to 316C). Pressure will generally range from 1500 psig to 3000 psig (10443 kPa to 20786 kPa), more preferably from 1900 psig to 2500 psig (13201 kPa to 17338 kPa). Hydrocarbon feedstock is generally passed through the guard chamber with a liquid hourly space velocity (LHSV) of from 1.5 to 3, more preferably from about 1.8 to 2.5.
As noted hereinbefore, treatment of the hydrocarbon feedstock in the guard chamber reaction zone serves 'co remove at least about 80% by weight and more preferably at least about 90% by weight of the metal contaminants from the feedstock. This significantly demetalized hydrocarbon material is then passed to a desalting zone wherein the hydrocarbon is contacted with water, thus further removing metal contaminants in the form of their salts from the hydrocarbon in conventional known manner. Oesalting is 37~
described, for example, in Petroleum Refiner, "Chemical ~esalting,"
Vol. ~7, No. 9, Page 292.
In the desalting zone, intimate contact of hydrocarbon with water can take place at temperatures ranging from lû0F to 300F
(38C to 149C) provided that the temperature of the water is above the pour point of the hydrocarbon material being desalted. The weight ratio of hydrocarbon to water in desalting operations can vary from about 0.5:5 to 5:0.5. Contact times of one hour or more can be advantageously employed. The desalting operation is generally conducted at pressures substantially lower than those employed in the guard chamber reaction zone. Desalting ~one pressures of from about 1 to 10 atmospheres (101 kPa to 1014 kPa) are typically employed. Chemical additives can be employed in the wash water used in desalting and/or electrostatic potential can be applied across the desalting zone to facilitate transfer of salts of the metal contaminants from the oil phase to the wash water phase.
After the desalting treatment, the aqueous solution is separated from the hydrocarbon material by any convenient conventional method known to the art. The water is diverted to a
PROCESS FOR REMOVING METAL CONTAMINANTS
FROM HYDROCARBON FEEOSTOCKS
_ This present invention relates to a method of removing metal contaminants such as arsenic or iron from oleagenous hydrocarbon feedstocks. This invention, more particularly, îs concerned with a sequential two-stage process for removing metal contaminants, the t~o-stage process comprising a guard chamber adsorption reaction followed by a water washing desalting step.
Retorted shale oil contains a large number of trace metals such as As, Fe, Ni, V, Co, Se and Zn. Arsenic and iron are the predominant trace elements ( > 2û ppm), and as such, these metals present several processing and product problems. For example, some arsenic compounds are water soluble and can cause pipeline corrosion. ~en shale oil is upgraded by delayed coking, most of the metals are rejected in the coke, resulting in a lower quality coke. Upgrading catalysts are irreversibly poisoned by metals deposition, substantially increasing upgrading costs. When burned directly as a fuel, shale oil poses potential As203 emission problem. The present invention is directed to eliminating all or most of the problem by removing substantially all or most of the arsenic and iron metal and other metal contaminants contained in hydrocarbon feedstocks, such as retorted shale oil.
5ubstantial prior art exists for using nickel-containing catalysts/adsorbents for shale oil dearsenation. Examples of this art are U.S. Patent No. 3,896,n49; U.S. Patent No. 3,876,533; U.S.
Patent No. 4,003,829; and U.S. Patent NoO 4,051,022. Further, the use of aqueous desalting is well established as are guard chamber or hydrotreating processes. However, it is believed that the prior art does not disclose nor suggest the instant invention involving a particular sequence of steps for demetalizing hydrocarbon feedstocks.
~Z~ 7;~7 lhe present invention provides a two-stage process for the removal of metal contaminants, at least one of which is arsenic, from a hydrocarbon feedstock. In the first step of such a process, the feedstock is contacted in a guard chamber reaction zone with a reactive metal adsorbent comprising a Group VIB or Group VIII metal dispersed on a porous inorganic oxide suppor-t having a surface area of at least 100 m2/9. Such contacting occurs in the presence of hydrogen under conditions such that less than 150 scf/B of hydrogen are consumed in the guard chamber. Such conditions include a temperature of from 250F to 750F, a pressure of from 1500 psig to 3000 psig, and a liquid hourly space velocity of from 105 to 3.
Treatment in the guard chamber reaction zone serves to remove at least 80% of said metal contaminant from said feedstock. After treatment of the feedstock in the guard charnber reaction zone, the feedstock is,in a second step of the process, contacted with water in a desalting zone under desalting conditions. Such conditions include use of a weight ratio of water to hydrocarbon of from 0.5:5 to 5:0.5 and a temperature which is above the pour point of the hydrocarbon feedstock and which further is within the range of from 100F to 300F. This two-stage process thus produces a demetalatea hydrocarbon product containing less than 1.0 ppm of arsenic contaminant.
An essential element of the present invention, as noted hereinbefore, involves the use of a particular reactive metal adsorbent in the guard chamber reaction zone under particular conditions. The Group VIB or Group VIII metal component of the reactive metal adsorbent can be employed in any suitable form.
Thus, the reactive metal may be present in the adsorbent as the element metal, the oxide, the sulfide or in ionic form. Preferred metals for use in the guard chamber adsorbent include nickel, molybdenum9 cobalt, iron and copper. Particularly preferred is nickel. Preferred reactive rnetal adsorbents will generally contain at least about 20% by weight of the reactive metal, more preferably at least about 40%.
The reactive metal is dispersed on a porous inorganic oxide support having a surface area of at least about lûO m2/g, preferably at least about 150 m /9. Examples of suitable inorganic oxide support materials include silica, alumina, magnesia, titania, and mixtures thereof. Especially preferred is a support comprising a mixture of silica and alumina, preferably in a weight ratio of from 3:1 to 1:3. The metal component can be dispersed on the inorganic oxide support by any conventional procedure including coprecipitation or physical admixing of the metal source and the inorganic oxide support.
The contacting of hydrocarbon feedstock with reactive metal adsorbent in the guard chamber occurs in the presence of hydrogen.
Conditions in the ~uard chamber are maintained so that very little hydrogen; e.g., less than 150 standard cubic feet of H2 per barrel of hydrocarbon (scf/B) [26.7 normal liters H2/liter of hydrocarbon (nl/l)] are consumed. Preferably no more than 100 scf/B
[17.8 nl/l)] of hydrogen will be consumed in the guard chamber.
Since hydrogen consumption in the guard chamber is so low, a low purity hydrogen source can be used such as retort off-gas.
Conditions in the guard chamber reaction zone include generally elevated temperatures and pressures. Temperatures will generally range from 250F to 750F (121C to 399C), more preferably from 300F to 600F (149C to 316C). Pressure will generally range from 1500 psig to 3000 psig (10443 kPa to 20786 kPa), more preferably from 1900 psig to 2500 psig (13201 kPa to 17338 kPa). Hydrocarbon feedstock is generally passed through the guard chamber with a liquid hourly space velocity (LHSV) of from 1.5 to 3, more preferably from about 1.8 to 2.5.
As noted hereinbefore, treatment of the hydrocarbon feedstock in the guard chamber reaction zone serves 'co remove at least about 80% by weight and more preferably at least about 90% by weight of the metal contaminants from the feedstock. This significantly demetalized hydrocarbon material is then passed to a desalting zone wherein the hydrocarbon is contacted with water, thus further removing metal contaminants in the form of their salts from the hydrocarbon in conventional known manner. Oesalting is 37~
described, for example, in Petroleum Refiner, "Chemical ~esalting,"
Vol. ~7, No. 9, Page 292.
In the desalting zone, intimate contact of hydrocarbon with water can take place at temperatures ranging from lû0F to 300F
(38C to 149C) provided that the temperature of the water is above the pour point of the hydrocarbon material being desalted. The weight ratio of hydrocarbon to water in desalting operations can vary from about 0.5:5 to 5:0.5. Contact times of one hour or more can be advantageously employed. The desalting operation is generally conducted at pressures substantially lower than those employed in the guard chamber reaction zone. Desalting ~one pressures of from about 1 to 10 atmospheres (101 kPa to 1014 kPa) are typically employed. Chemical additives can be employed in the wash water used in desalting and/or electrostatic potential can be applied across the desalting zone to facilitate transfer of salts of the metal contaminants from the oil phase to the wash water phase.
After the desalting treatment, the aqueous solution is separated from the hydrocarbon material by any convenient conventional method known to the art. The water is diverted to a
2~ waste water treatment area, and the hydrocarbon material is passed to downstream processing such as to a coker preliminary to processing into such materials such as anode grade coke or petroleum asphalt. The effluent from the guard chamber/desalting process may, in fact, be used in any desirable downstream operation, for example, hydrotreater, FCC, TCC, coker, deasphalter, etc.
After being subjected to the particular two-stage process of the present invention, the water-washed oil typically contains less than 1.0 ppm arsenic. The sequence of the steps is extremely important and highly critical to the present invention.
After being subjected to the particular two-stage process of the present invention, the water-washed oil typically contains less than 1.0 ppm arsenic. The sequence of the steps is extremely important and highly critical to the present invention.
3~ Cesalting/guard chamber processing is only marginally better than the guard chamber alone, whlle guard chamber/desalting processing is significantly better than guard chamber alone.
The demetalizing process of the present invention can be illustrated by the following examples. In such examples, the reactive metal adsorbent used was a nickel commercially available ~2~ Z7 silica-alumina catalyst prepared by coprecipitation and designated herein "Nickel Catalyst A." Properties of this reactive metal adsorbent are given as follows:
Properties of Fresh Nickel Catalyst "A"
Extrudate Diameter l/16"
Real Density, g/cc 4.263 Particle Density, g/cc 1.411 Surface Area, m2g 168 Pore Volume, cc/g 0.474 Pore Diameter, A 113 Ni, wt % 50 4 A1203, wt ~0 10.7 SiO2, wt % 18.8 Example 1 A Paraho shale oil was processed over ln a guard chamber reaction zone containing the above described Nicekl Catalyst A and in a desalting zone in accordance with the present invention.
Properties of this Paraho shale oil are set forth in Table l as follows:
2~ Table 1 Shale Oil Proeerties (Paraho) API Gravity 20.6 ~, wt YO 11.77 N, wt % 2.05 S, wt % 0.65 Bromine No. 46.5 Paraffins, wt % 12.6 Naphthenes, wt % 13.3 Aromatics 9 wt % 74.1 As, ppm 26.5 Fe, ppm 47 Ni, ppm 3.2 V, ppm 0.4 Gistillation (D2887), F
5% 378 10% 427 30% 588 50% 734 ~0 90% 916 95% 1040 ~2~7Z~7 F-211n - 6 -Conditions in the guard chamber included temperatures ranging from 300F to 600F, hydrogen pressure of 220n psig, a LHSV
of 2 and a hydrogen circulation rate of approximately 500û scf/B.
Conditions in the water washing desalting zone included a temperature of 120F, a contact time of 1 hour and an oil/water weight ratio of 1:1. Dearsenation results of this treatment are shown in Figure 1.
The same shale oil material was also treated by contact with the Nickel Catalyst A without subsequent water washing and by water washing first followed by contact with Nickel Catalyst A.
Results of this testing are also set forth in Figure 1 wherein liquid product arsenic content is plotted as a function of guard chamber temperature.
From Figure 1, it can be seen that to reach a target of, for example, 2 ppm arsenic, a guard chamber temperature of 625F was required. When the guard chamber was operated at 575F9 however, the product arsenic level was only lowered to 4.0 ppm which is about twice the maximum level desired for feed to a hydrotreater. When, however, the 4.0 ppm arsenic-containing product obtained by 2~ treatment at 575F in the guard chamber is subsequently subjected to water washing (See the dashed line in Figure 1), the arsenic content of the product drops to 0.4 ppm. It can thus be seen that the combination of guard chamber processing followed by water washing generally requires lower guard chamber temperature conditions to reach a given desired arsenic level in the product in comparison with guard chamber processing alone. For comparison purposes, it can also be seen from Figure 1 that the treatment sequence which is the reverse of the present invention; i.e.~ water washing/guard chamber processing, is only marginally better that the guard chamber alone In addition to permitting lower guard chamber temperatures, the process of the present invention as illustrated in Example 1 uses less hydrogen than other combinations of processing steps.
Product arsenic levels vs~ hydrogen consumption for the Paraho shale oil demetalizing operating described above are plotted in Figure 2.
It can be seen from Figure 2 that very low levels of hydrogen 7:~
consumption are needed -to reduce product arsenic levels to less than 1.0 ppm when the particular guard ch~nber/water washing sequence of the present invention is employed.
Examp~e 2 The present invention i5 applied to making anode grade coke. As shown in Figure 3, raw shale oil is dearsenated by the guard chamber unit and a downstream desalter. The water from the desalter is sent to a waste water treatment (WWT) unit to remove water-soluble arsenic compounds and organics (e.g., phenols). The full range shale liquid effluent from the desalter is atmospheric and vacuurn distilled. The vacuum tower bottoms (e.g., 850~F+ or 95ûF+) fraction is delayed coked. The coker liquids are recombined with the straight-run distillable liquids for further upgrading.
The green coke is thereafter calcined to produce anode grade coke.
The two-stage dearsenation process illustrated hereinbefore can consume less than 50 scf H2/~ to lower the product arsenic content to 0.5 ppm or less. The first stage dearsenation step apparently converts arsenic compounds to water soluble forms enabling superior effectiveness compared to the reverse sequence and permitting lower temperature operation. Arsenic removal and other metal contaminant removal is needed prior to pipelining and/or upgrading. This invention improves the downstream upgrading and product quality in conjunction with such operations as hydrotreating.
Although the present invention has been described with reference to preferred embodiments, it is to be understood that modifications and variations may be resorted to, without departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such modifications and variations are considered to be within the preview and scope of the appended claims.
The demetalizing process of the present invention can be illustrated by the following examples. In such examples, the reactive metal adsorbent used was a nickel commercially available ~2~ Z7 silica-alumina catalyst prepared by coprecipitation and designated herein "Nickel Catalyst A." Properties of this reactive metal adsorbent are given as follows:
Properties of Fresh Nickel Catalyst "A"
Extrudate Diameter l/16"
Real Density, g/cc 4.263 Particle Density, g/cc 1.411 Surface Area, m2g 168 Pore Volume, cc/g 0.474 Pore Diameter, A 113 Ni, wt % 50 4 A1203, wt ~0 10.7 SiO2, wt % 18.8 Example 1 A Paraho shale oil was processed over ln a guard chamber reaction zone containing the above described Nicekl Catalyst A and in a desalting zone in accordance with the present invention.
Properties of this Paraho shale oil are set forth in Table l as follows:
2~ Table 1 Shale Oil Proeerties (Paraho) API Gravity 20.6 ~, wt YO 11.77 N, wt % 2.05 S, wt % 0.65 Bromine No. 46.5 Paraffins, wt % 12.6 Naphthenes, wt % 13.3 Aromatics 9 wt % 74.1 As, ppm 26.5 Fe, ppm 47 Ni, ppm 3.2 V, ppm 0.4 Gistillation (D2887), F
5% 378 10% 427 30% 588 50% 734 ~0 90% 916 95% 1040 ~2~7Z~7 F-211n - 6 -Conditions in the guard chamber included temperatures ranging from 300F to 600F, hydrogen pressure of 220n psig, a LHSV
of 2 and a hydrogen circulation rate of approximately 500û scf/B.
Conditions in the water washing desalting zone included a temperature of 120F, a contact time of 1 hour and an oil/water weight ratio of 1:1. Dearsenation results of this treatment are shown in Figure 1.
The same shale oil material was also treated by contact with the Nickel Catalyst A without subsequent water washing and by water washing first followed by contact with Nickel Catalyst A.
Results of this testing are also set forth in Figure 1 wherein liquid product arsenic content is plotted as a function of guard chamber temperature.
From Figure 1, it can be seen that to reach a target of, for example, 2 ppm arsenic, a guard chamber temperature of 625F was required. When the guard chamber was operated at 575F9 however, the product arsenic level was only lowered to 4.0 ppm which is about twice the maximum level desired for feed to a hydrotreater. When, however, the 4.0 ppm arsenic-containing product obtained by 2~ treatment at 575F in the guard chamber is subsequently subjected to water washing (See the dashed line in Figure 1), the arsenic content of the product drops to 0.4 ppm. It can thus be seen that the combination of guard chamber processing followed by water washing generally requires lower guard chamber temperature conditions to reach a given desired arsenic level in the product in comparison with guard chamber processing alone. For comparison purposes, it can also be seen from Figure 1 that the treatment sequence which is the reverse of the present invention; i.e.~ water washing/guard chamber processing, is only marginally better that the guard chamber alone In addition to permitting lower guard chamber temperatures, the process of the present invention as illustrated in Example 1 uses less hydrogen than other combinations of processing steps.
Product arsenic levels vs~ hydrogen consumption for the Paraho shale oil demetalizing operating described above are plotted in Figure 2.
It can be seen from Figure 2 that very low levels of hydrogen 7:~
consumption are needed -to reduce product arsenic levels to less than 1.0 ppm when the particular guard ch~nber/water washing sequence of the present invention is employed.
Examp~e 2 The present invention i5 applied to making anode grade coke. As shown in Figure 3, raw shale oil is dearsenated by the guard chamber unit and a downstream desalter. The water from the desalter is sent to a waste water treatment (WWT) unit to remove water-soluble arsenic compounds and organics (e.g., phenols). The full range shale liquid effluent from the desalter is atmospheric and vacuurn distilled. The vacuum tower bottoms (e.g., 850~F+ or 95ûF+) fraction is delayed coked. The coker liquids are recombined with the straight-run distillable liquids for further upgrading.
The green coke is thereafter calcined to produce anode grade coke.
The two-stage dearsenation process illustrated hereinbefore can consume less than 50 scf H2/~ to lower the product arsenic content to 0.5 ppm or less. The first stage dearsenation step apparently converts arsenic compounds to water soluble forms enabling superior effectiveness compared to the reverse sequence and permitting lower temperature operation. Arsenic removal and other metal contaminant removal is needed prior to pipelining and/or upgrading. This invention improves the downstream upgrading and product quality in conjunction with such operations as hydrotreating.
Although the present invention has been described with reference to preferred embodiments, it is to be understood that modifications and variations may be resorted to, without departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such modifications and variations are considered to be within the preview and scope of the appended claims.
Claims (7)
1. A two-stage process for the removal of metal contaminants, at least one of which is arsenic, from a hydrocarbon feedstock, said process comprising:
(a) contacting said feedstock in a guard chamber reaction zone with a reactive metal adsorbent comprising a Group VIB or Group VIII metal dispersed on a porous inorganic oxide support having a surface area of at least 100 m2g, said contacting occurring in the presence of hydrogen under conditions such that less that 150 scf/B
of hydrogen are consumed, said conditions including a temperature of from 250°F to 750°F, a pressure of from 1500 psig to 3000 psig and a liquid hourly space velocity of from 1.5 to 3, said contacting serving to remove at least 80% of said metal contaminants from said feedstock, and thereafter.
(b) further contacting said feedstock with water in a desalting zone under desalting conditions which include use of a weight ratio of water to hydrocarbon of from 0.5:5 to 5:0.5 and a temperature which is above the pour point of the hydrocarbon feedstock and which further is within the range of from 100°F to 300°F, to thereby produce a demetalated hydrocarbon product containing less than 1.0 ppm of arsenic contaminant.
(a) contacting said feedstock in a guard chamber reaction zone with a reactive metal adsorbent comprising a Group VIB or Group VIII metal dispersed on a porous inorganic oxide support having a surface area of at least 100 m2g, said contacting occurring in the presence of hydrogen under conditions such that less that 150 scf/B
of hydrogen are consumed, said conditions including a temperature of from 250°F to 750°F, a pressure of from 1500 psig to 3000 psig and a liquid hourly space velocity of from 1.5 to 3, said contacting serving to remove at least 80% of said metal contaminants from said feedstock, and thereafter.
(b) further contacting said feedstock with water in a desalting zone under desalting conditions which include use of a weight ratio of water to hydrocarbon of from 0.5:5 to 5:0.5 and a temperature which is above the pour point of the hydrocarbon feedstock and which further is within the range of from 100°F to 300°F, to thereby produce a demetalated hydrocarbon product containing less than 1.0 ppm of arsenic contaminant.
2. A process according to claim 1 wherein the metal component of the reactive metal adsorbent is nickel, cobalt, molybdenum, iron, or copper.
3. A process according to claim 1 or claim 2 wherein the inorganic oxide support component of the reactive metal adsorbent is selected from silica, alumina, magnesia, titania or combinations thereof.
4. A process according to claim 1 wherein the reactive metal adsorbent comprises nickel combined with silica-alumina.
5. A process according to claim 1 wherein hydrogen consumption in the guard chamber reaction zone is less than 100 scf/B.
6. A process according to claim 5 wherein reaction conditions in the guard chamber reaction zone include a temperature of from 300°F to 600°F.
7. A process according to claim 1, 4 or 6 wherein the hydrocarbon feedstock is shale oil.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US46585383A | 1983-04-15 | 1983-04-15 | |
| US465,853 | 1983-04-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1210727A true CA1210727A (en) | 1986-09-02 |
Family
ID=23849438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000452023A Expired CA1210727A (en) | 1983-04-15 | 1984-04-13 | Process for removing metal contaminants from hydrocarbon feedstocks |
Country Status (2)
| Country | Link |
|---|---|
| AU (1) | AU564818B2 (en) |
| CA (1) | CA1210727A (en) |
-
1984
- 1984-04-13 AU AU26826/84A patent/AU564818B2/en not_active Ceased
- 1984-04-13 CA CA000452023A patent/CA1210727A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU2682684A (en) | 1984-10-18 |
| AU564818B2 (en) | 1987-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2198623C (en) | A process for removing essentially naphthenic acids from a hydrocarbon oil | |
| US4179361A (en) | Sorbent regeneration in a process for removing sulfur-containing impurities from mineral oils | |
| US4431525A (en) | Three-catalyst process for the hydrotreating of heavy hydrocarbon streams | |
| US8323479B2 (en) | Converting heavy sour crude oil/emulsion to lighter crude oil using cavitations and filtration based systems | |
| US3716479A (en) | Demetalation of hydrocarbon charge stocks | |
| US3988238A (en) | Process for recovering upgraded products from coal | |
| US3696027A (en) | Multi-stage desulfurization | |
| MXPA97001483A (en) | A process to remove essentially nafetyanic acids from a hydrocarbon oil | |
| US3732155A (en) | Two-stage hydrodesulfurization process with hydrogen addition in the first stage | |
| CA1218321A (en) | Integrated process for the solvent refining of coal | |
| US3306845A (en) | Multistage hydrofining process | |
| US4414102A (en) | Process for reducing nitrogen and/or oxygen heteroatom content of a mineral oil | |
| US3766054A (en) | Demetalation of hydrocarbon charge stocks | |
| US5817229A (en) | Catalytic hydrocarbon upgrading process requiring no external hydrogen supply | |
| US4585546A (en) | Hydrotreating petroleum heavy ends in aromatic solvents with large pore size alumina | |
| US5746907A (en) | Method to remove metals from residuals | |
| EP0433026B1 (en) | Process for removing metallic contaminants from a hydrocarbonaceous liquid | |
| EP0143401B1 (en) | Hydrofining process for hydrocarbon containing feed streams | |
| CA1210727A (en) | Process for removing metal contaminants from hydrocarbon feedstocks | |
| US4102779A (en) | Processes for treating a heavy petroleum hydrocarbon stream containing metals and asphaltenes | |
| KR100193001B1 (en) | Process for removing mercury and/or arsenic from charges of aromatization or dearomatization units | |
| US4510043A (en) | Process for dewaxing of petroleum oils prior to demetalation and desulfurization | |
| US20090246108A1 (en) | Method For Removing Ammonia From Fluid Streams | |
| US4188280A (en) | Method for removing arsenic from shale oil | |
| US3487012A (en) | Processes for the improvement of initial color and long-term color stability of aromatic concentrates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |