US2944965A

US2944965A - Method of treating metal containing hydrocarbon oils

Info

Publication number: US2944965A
Application number: US738021A
Authority: US
Inventors: Frank A Mirabile
Original assignee: MW Kellogg Co
Current assignee: MW Kellogg Co
Priority date: 1958-05-27
Filing date: 1958-05-27
Publication date: 1960-07-12
Anticipated expiration: 1977-07-12

Description

METHOD OF TREATING METAL CONTAINING HYDROCARBON OILS Frank A. Mirabile, Belleville, N.'J., assignor to The M. W1 Kellogg Company, Jersey City, NJ., a corporation of- Delaware No Drawing. Filed May 27, 1958, Ser. No. 738,021

11 Claims. 01. 208-284) The present invention relates to demetallization processes. In one of its aspects, the invention relates toa. process for the demetallization of hydrocarbon oils. More particularly, in this aspect, the invention relates to an improved process for the removal of metal contamibeen found that this condition is largely due to the deposition of metallic contaminants, present in the feed,

upon the catalytic material. These metallic contaminants which are harmful to catalytic activity have been found to comprise unfilterable metals or metallic compounds, particularly those of nickel, vanadium, ironand copper. In addition, it has also been found that organic metal salts are present in these hydrocarbon oils which may have been formed by the corrosion of refinery equipment by organic acids present in the feed. These metallic contaminants tend to accumulate upon the catalyst, and their removal is extremely difficult because of the relatively small amounts of the metal contaminants present in the feed, these amounts being in the order of from to 100 parts per million. 7

Various methods have heretofore been suggested for removing or loweringthe metallic contaminant-content of hydrocarbon oils or feed stocks, to reduce catalyst contamination. Among these methods are those which embody treating such feeds with strong mineral acids to react with the metal contaminants, and subsequently separating the resulting metal salts by conventional methods. Such procedures, however, have been found to result in hydrocarbon decomposition; and in instances where oxygenated organic compounds may also be present in the aforementioned feeds, there is a tendency for these compounds to react with the acid treating agent, thus effecting their subsequent recovery in a state of unchanged composition. Other proposed methods embody treating the aforementioned metal-containing hydrocarbon oils with varying concentrations of alkali-treating agents. Such methods have alsobeen found to be undesirable, inasmuch as they are limited to only a partial recovery of the metal contaminants present. This result is encountered where a sufficient amount of alkalitreating agent isused to neutralize the free organic acids which may be present in such metal-containing hydrocarbon mixtures, and it is desired to remove the metal as its oxide or hydroxide. Where such quantities of alkali-treating agent are employed, there is a tendency of the alkali to promotehndesirable side-reactions, such as the condensation and/ or polymerization of carbonyl compounds (e.g., aldehydes or ketones), unsaturated products, and materials containing polyfunctional groups. Such action is more apt to occur in the presence of alkali-treating agents ateint l atented July 12, 1960 than in the presence of mineral acids, when the latter are employed as treating agents. Still other methods for removing dissolved metal impurities in admixture with hydrocarbons have been unsuccessfully attempted in the past. For example, distillation by conventional methods has proved undesirable because of hydrocarbon decomposition caused by the application of heat. Similarly, molecular distillation has been shown to be ineifective in separating metallic impurities from'the aforementioned hydrocarbon oils.

Itis, therefore, an objectof the present invention to provide an improved method for the demet-allization of hydrocarbon oils. 1

Another object .of the invention is to provide an proved method for the removal of metal contaminants present in hydrocarbon oils, such as are employed in catalytic cracking operations.

Still another object of the invention is to provide an improved, efiicient and economical method for substantially complete removal of metal contaminants present in hydrocarbon oils, such as are employed in catalytic cracking operations.

Various other objects and advantages inherent in the invention will become apparent from the following more detailed disclosure and description.

In accordance with the improved process of the present invention, as more fully hereinafter described, metal contaminants, present in varying concentrations,

may be substantially completely removed from the aforementioned hydrocarbon oils by treating these oils with strong halogenating agents containing chlorine or bromine substitution, to convert these metal contaminants to their metallic halides. The metallic halides thus produced are thereafter readily separated from the hydrocarbon oil so that the metal-free hydrocarbon mixtures are obtained. The halogenating agent which is employed for the removal of the aforementioned metal contaminants, is, as indicated above, one in which the halogens are selected from the group consisting of chlorine and bromine. Preferred balogenating agents comprise sulfuryl chloride, sodium hypochlorite, chlorine, bromine or N-bromosuccimide.

The treatment of the aforementioned hydrocarbon oils, such as, for example, employed in catalytic cracking operations, is carried out with the halogenating agent in either a batch-wise or continuous operation. In a given treatment, it is found that the mole ratio of the halogenating agent to the quantity of metallic contaminants present in the feed stock treated, in general, may vary from about 1 to about 5 moles of chlorinating agent to the quantity of metal contaminants present. Greater quantities of the chlorinating agent with relationship to the quantity of metal contaminants present may, however, be employed in the process of the invention, but such increased quantities are not desirable since they do not result in any improvement in metal removal, from an economic standpoint. Preferably, mole ratios of halogenating agent to metal contaminants present ranging from about 1:1 to 3:1 are preferred, since such ratios result in obtaining optimum (i.e., substantially complete metal removal) conditions employing minimum quantities of the halogenating agent.

It hasbeen found, in accordance with the process of the present invention, that the rate ofchlorination or bromination is favored by an increase in temperature. However, if the temperature employed is excessive, too high a rate of halogenation takes place and too large a quantity of the halogenating agent is consumed. This maybe followed by halogenation of the hydrocarbon 3 components themselves. entthe possibility of hydrocarbon decomposition where the temperature employed is exceedingly high. In general, temperatures between about 60 F. and about 300 F. are satisfactorily employed. While temperatures below 60 F. may also be employed, it is nevertheless found that the rate of reaction proceeds too slowly so that economic and efficient metal removal is not obtain'ed. Where elevated temperatures are desired to be emloyed, in order to hasten the rate of metal removal, ranges between about 200 F. and about 300 F. are satisfactorily employed. In general operation, however, a temperature between about 60F. and about 200 F. is normally utilized. Y

employed in carrying out the halogenation reaction, it

is found that pressures between about 1 atmosphere and about atmospheres are satisfactorily employed. In instances where the halogenating agent is employed in a liquid state and the operation is carried out within the uppermost limits of the temperature range (e.g., between about 200 F. and about 300 F.), it is preferred to carry out the reaction at pressures which are significantly :above atmospheric pressure in. order to maintain the halogenating agent in a liquid phase condition.

As previously indicated, the metal contaminants which are effectively removed, in accordance with the process of the present invention, comprise such metals as nickel, vanadium, iron, copper and their compounds. Employing nickel oxide as representative of metal contaminants present in the aforementioned hydrocarbon oils or petroleum feed stocks, the complete removal of this metal from the feed, employing sulfuryl chloride as representative of the aforementioned halogenating agent, may be illustrated by the following equation:

Similar reactions take place when any of the other metal contaminants are present in the feed, such as vanadium, iron, copper, etc., employing either sulfuryl chloride or any other of the other aforementioned halogenating agents.

As indicated above, the metal contaminants removed from the hydrocarbon oils, in accordance with the present invention, may be present either in the form of the ele- Qmental free metal or in the form of metallic compounds. In this respect, it has been found that in ceitain feed materials, particularly heavier crude oil fractions containing relatively large quantities of metal contaminants, such as nickel, vanadium, iron, copper or mixtures thereof, these metals are present in the form of metal porphyrins. lThese metal porphyrins, when present in feeds employed in hydrocarbon conversion processes, e.g., catalytic crackling operations, tend to deposit on the catalyst, as previously indicated, during cracking. With the above in mind, the effect of a number of halogenating agents for effecting demetallization of the aforementioned hydrohalogenating agents upon solutions containing nickel etio- In each run a 10 cc. solution of nickel porphyrin. etioporphyrin, comprising 12.1 p.p.m. Ni in pyridine, was treated with the halogenating agent for a period of :16 .hours. The data in the table disclosesthe quantities :of halogenating agent employed and the degree of metal .contaminant finally removed after the 16 hour period.

In addition, there is also pres- Table I Mg. of Final Percent Run Halogenating Agent Halogen- Temp. p.p.m. Ni N o. atlug Ni removed Agent l 1 sulfurylchloride {i312 5833 .5: 8 i88:8 2 sodium hypochlorite. 50. 0 reflux. 0 100. 0 chlorine 1 room...- 0 100. 0 50.0 reflux. 0 V 100. 0 22.0 reflux- 0 100. 0 {30. 9 room..-. 8 34. 0 30. 9 reflux. 8 34. 0 1 {24. 9 room... 9 26. 8 24. 9 reflux. 9 26. 8 {20. 9 room I8. 6 29. 0 20. 9 reflux. 8. 6 29. 0 50.0 reflux. 5. 3 56.0 62. 0 reflux. 12. 1 0

1 Room temperature=68 F. 9 Reflux temperature=reflux temperature of pyridine, viz., 221 F.

From Table I above, it will be noted that the halogenating agents of the present invention, viz., sulfuryl chloride, sodium hypochlorite, chlorine, bromine and N- bromo succinimide, were extremely effective in complete removal of the nickel contaminant present, as evidenced from the data in runs 1 through 5. On the other hand, it will be noted that other halogenating agents were not effective in the total removal of nickel contaminants, as is evidenced from runs 6 through 10 in the table.

The following table illustrates the effect of various halogenating agents upon solutions containing vanadyl etioporphyrin. In each run, a 10 cc. solution of vanadyl etioporphyrin, comprising 12.8 p.p.m. vanadium in benzene, was treated with the halogenating agent for a period of 15 hours. The data in the table discloses the quantities of halogenating agent employed and the de- Table II Mg. of Final Percent Run Halogenatlng Agent Halo en- Temp, p.p.m. V N o. ating F. V removed Agent sulfuryl chloride 50.0 68 0 100.0 N-brornosuccinimide 20.0 81 0 100.0 HF 50.0 81 12.8 0 HI 50.0 81 12.3 4. 0 HBr 50.0 81 10. 6 '17. 0

From the data disclosed in Tables I and II, it will be noted that the halogenating agents of the present invention, viz., sulfuryl chloride, .sodium hypochlorite, chlorine, bromine and N-bromosuccinimide are outstandingly effective in obtaining substantially complete metal removal, 'by converting the aforementioned metal contaminants to their metallic halides. On the other hand, it will also be noted that other halogenating agents are not effective in obtaining a total metal removal as shown in the aforementioned runs. With reference to Table II,

' it will be noted therefore, that while the aforementioned V(etioporphyrin) +5SO Cl V01 +etioporphyrin)Cl +5SO As indicated above, the present invention is directed to an improved process for the removal of metal contaminants present in hydrocarbon oils, and has particular applicability to the treatment of hydrocarbon oils employed in catalytic cracking operations. However,

. while the invention has been described as having a particular applicability to the separation of metal impurities from hydrocarbon mixtures obtained from such sources, it should be noted that the process of the invention is not necessarily restricted to efiect the desired metal separation from such hydrocarbon mixtures. The process of the present invention may also be successfully applied to the separation of metal impurities from any mixtures of hydrocarbon oils without regard to the source from which these mixtures may have been derived. It should also be noted that while a particular embodiment of the process of this invention has been described for the purposes of illustration, various modifications and adaptations thereof, which will be obvious to those skilled in the art may also be made within the spirit of the invention.

I claim:

1. A method for treating a hydrocarbon oil containing metal contaminants which comprises contacting said oil with a halogenating agent selected from the group consisting of sodium hypochlorite and N-bromosuccinimide to convert said metal contaminants to their metallic halides.

2. The process of claim 1 in which the halogenating agent comprises sodium hypochlorite.

3. The process of claim 1 in which the halogenating agent comprises N-bromosuccinimide.

4. A method for treating a hydrocarbon oil containing metal contaminants which comprises contacting said oil with a halogenating agent selected from the group consisting of sodium hypochlorite and N-bromosuccinimide at a temperature between about 60 F. and about 300 F. to convert said metal contaminants to their metallic halides.

5. A method for treating a hydrocarbon oil containing metal contaminants which comprises contacting said oil with a halogenating agent selected from the group consisting of sodium hypochlorite and N-bromosuccinimide at a temperature between about 200 F. and about 300 F. to convert said metal contaminants to their metallic halides. I

6. A method for treating a hydrocarbon oil containing metal contaminants which comprises contacting said oil with a halogenating agent selected from the group consisting of sodium hypochlorite and N-bromosuccinimide at a temperature between about F. and about 300 F. and at a pressure from about 1 atmosphere to about 10 atmospheres to convert said metal contaminants to their metallic halides.

7. A method for treating a hydrocarbon oil containing metal contaminants which comprises contacting said oil with a halogenating agent selected from the group consisting of sodium hypochlorite and N-bromosuccinimide at a temperature between about 200 F. and about 300 F. and at a pressure from about 1 atmosphere to about 10 atmospheres to convert said metal contaminants to their metallic halides.

8. A method for treating a hydrocarbon oil containing .metal contaminants which comprises contacting said oil with a halogenating agent selected from the group consisting of sodium hypochlorite and N-bromosuccinimide in an agentzmetal mole ratio between about 1 and about 5 and at a temperature between about 60 F. and about 300 F. to convert said metal contaminants to their metallic halides.

9. A method for treating a hydrocarbon oil containing metal contaminants which comprises contacting said oil with a halogenating agent selected from the group consisting of sodium hypochlorite and N-bromosuccinimide in an agentzmetal mole ratio between about 1 and about 5 and at a temperature between about 200 F. and about 300 F. to convert said metal contaminants to their metallic halides.

10. The process of claim 6 in which the halogenating agent comprises sodium hypochlorite.

11. The process of claim 6 in which the halogenating agent comprises N-bromosuccinimide.

References Cited in the file of this patent UNITED STATES PATENTS