DE1212662B - Process for removing metallic and nitrogenous impurities from hydrocarbon oils - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

Clog

German KL: 23 b-1/05

Number: 1212 662

File number: U 8939IV d / 23 b

Filing date: May 9, 1962

Opened on: March 17, 1966

The invention relates to a method for treating hydrocarbon oils, in particular crude oils, for the purpose of removing certain metallic and nitrogenous impurities that are necessary for the The catalysts used in their conversion processes are harmful.

It is known that certain heavy metals as impurities in crude oil masses in the form of highly stable, refractory, metal-containing complexes, such as vanadium, nickel and cobalt porphyrins, and also certain nitrogenous compounds in crude oil and its distillate fractions, both in low and high boiling cuts, occurrence. These nitrogenous impurities occur in the form of organically bound, naturally occurring nitrogen compounds, as asphaltenes and heterocyclic nitrogen compounds, ζ. B. as indoles, <pyrroles and pyridines. These metallic and nitrogenous impurities Although they have high boiling points, they still appear in the distillate fractions, especially in those that boil above the gasoline range because they contain the desired hydrocarbon constituents be carried away during the distillation of the crude oil. At high temperatures during the exothermic cracking and reforming reactions in the presence of a reducing hydrogen atmosphere and in the presence of the conversion catalyst, said impurities tend to be for cleavage into simpler molecular structures or into the metals themselves, which are then on the catalyst deposit in ever larger quantities. So despite their extremely small amounts in the crude oil, it is theirs Influence on the activity of the cracking or reforming catalyst considerable. In the case of catalysts such as silica-alumina masses, this increases metallic nickel and vanadium rapidly reduce the destructive cracking activity, resulting in a rapidly increasing Formation of hydrogen and light gases, such as methane, propane, leads and the yield of more valuable ones Products. The catalyst itself is expensive, and its replacement is not limited to the cost of the new catalyst, but also associated with a significant loss of production, because the reactor has to be taken out of service. In the case of reforming catalysts that have a contain acidic constituent essential for hydrocracking activity also reduces the presence nitrogenous compounds in the feed indicate the activity for hydrocracking.

The main purpose of the process is to remove these heavy metals and nitrogenous substances

Process for removing metallic
and nitrogen-containing impurities
Hydrocarbon oils

Applicant:

Universal Oil Products Company,

Des Piaines, JIl. (V. St. A.)

Representative:

Dr. H.-H. Willrath and Dipl.-Ing. H. Roever,

Patent attorneys, Wiesbaden, Hildastr. 18th

Named as inventor:

John George Gatsis, Des Piaines, JIl. (V. St. A.)

Impurities by means of a simple precipitation process from crude oils or obtained from them Factions. In particular, the present process aims to reduce the concentration of these impurities in the petroleum charge to a value as low as that of most

a5 Cracking and reforming catalysts tolerated without causing an unduly rapid deactivation or change in its catalytic properties Properties is coming. The present procedure provides a method of treating Hydrocarbon fractions intended for cracking and refining conversions, whereby metal contamination to less than 0.0001% (1.0 parts per million) heavy metals and less than 0.1 weight percent nitrogen is reduced.

Although the treatment of petroleum in the liquid phase with hydrogen fluoride to remove various Impurities are known to have already been carried out to a large extent the previously used processes actually in liquid-liquid phase extractions, the impurities being in the separated liquid hydrogen fluoride or the hydrofluoric acid phase solve, which is decanted from the hydrocarbon material as a separate phase. These procedures depend on the solution transfer factors, which are between an essentially hydrocarbon existing phase and a phase consisting essentially of hydrofluoric acid, each phase taking a substantial portion of the other phase with it. Actually extracts the liquid hydrofluoric acid phase has an unusual

609 538/354

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proportion of the hydrocarbon feed, and low paraffinic hydrocarbon (propane or although generally from 10 to 30% depending on the η-butane) in a volume ratio of 1: 1 to Concentration of acid, and usually 12: 1 wins of this solution to hydrocarbon oil one less than 85%> of the original coal avoidance of the formation of a liquid two phase hydrogen feed. The cost of the coal system takes place and that the resulting low hydrogen recovery from the extract phase and remove the treated hydrocarbon oil Change in the molecular breakdown. - ■ - ■ settlement as a result of the conversion of these coals In contrast to the previously known costly Hydrogen in the presence of concentrated fluorine extraction methods leads the process according to the Hydrogen acid do not make the use of this Ex io invention to form a two phase liquid traction principle to remove contamination system, with only sufficient hydrogen fluoride genes from these raw materials are uneconomical. in the system for reaction with the impurities

This also applies in the event of a reasonable inconvenience; the separation of the solid Lich well-known process in which the coal precipitate, which contains the impurities, Hydrogen treatment items initially for the purpose of poly-15 of the treated items are carried out by simple merization of metal compounds up to 5 hours recovery without excessive loss of re-heated, then the oil with gaseous water chloride agents or feed and without the necessary materials saturated under pressure, with aliphatic! or the ability to recover the hydrogen fluoride reagent, naphthenic hydrocarbon with 5 to 10 carbon atoms as in the liquid-liquid phase extraction carbon atoms mixed and carried out after a dwell time of 20 method.

from 5 to 100 minutes or more expediently, the preferred application of the method still exists is treated with gaseous sulfur dioxide. in the treatment of crude oil, d. H. before the Fraktio-Die The recovery of the oil here is about 85 renation or other treatment. In particular up to 89%, and the content of the treated oil in cases it may be necessary to use a fraction of beNickel and vanadium will not be used as a charge below 5 parts per 25 million special boiling range degraded. The distances are also known. For example, are for catalytic cracking The light oil and gas oil fraction hydrocarbon oils are particularly suitable for removing metallic impurities from light with boron trifluoride coordina- tions, for example above about 204 ° C sietionsverbindungen, but these have to be done first. In other cases the invention can be applied separately are produced and are expanded in the heat of certain circulatory fractions of the product legal. that can be derived from a previous cataly-

The process is also used to remove table cracking gains, or one can use the Lead and arsenic from hydrocarbon treatment on the lubricating oil fraction of a crude oil good. Use another known method. Of course, crude oils are made of certain the one with hydrogen halide, ζ. B. Hydrogen fluoride in 35 sources stronger with metallic and nitrogenous gaseous forms, works and a preheating of the oil results in compounds contaminated as crude oils from requests, It only works a distance of about 72 to their sources, but generally all crude oils have one 88% of the nickel and about 62 to 73% of the Vana- harmful concentration of these contaminants, which are present as impurities. With gen. Therefore, all crude oils are used by one Another known method is hydrogenation of the present method of treatment either gaseous or aqueous in one considerably improved.

Concentration from 3 to 37 percent by weight applied to the carrier liquid for the hydrogen fluoride, and the amount of acid is 50 to 300 vol. from propane, normal butane or mixtures of lum percent of the treated oil. Propane and normal butane, which practically do not work with

The treatment of lubricating oil in the hydrogen fluoride will also react. Isoparaffins are in

at least two successive stages generally unsuitable because they are condensation and

next subject to 50 to 200 volume percent liquid fluorine polymerization reactions. Higher north

Hydrogen and then with liquid fluoromal paraffins as normal butane are not sufficient

hydrogen borofluoride described, one being selective for the purpose provided here. So is

clear liquid phase forms. The known Ver 50 normal pentane is sufficiently inert in the presence of

drive work with amounts of hydrogen fluoride that are far from being hydrogen fluoride, but not sufficiently selective

over 1 percent by weight of the material to be treated - deasphalting agent to remove the metal contaminants

go out. the hydrocarbon feed to less

In contrast, the process is characterized by lowering than 2 parts per million,
the invention through the use of anhydrous 55. In particular, the invention works with hydrogen fluoride in an amount not exceeding the kind that the treatment agent with the coal is about 1 percent by weight when using an in natural hydrogen oil at a temperature of about 0 to oil treatment plant available standing Ver about 150 ° C, preferably from about 30 to about thinning agent and by the extraordinarily far 100 ° C under sufficient pressure to remove the fluorine, in particular the hydrogen component of the system and the lighter nickel and vanadium compounds Keeping liquid with normal paraffin constituent results in a loss of crude oil yield. mixes. In general, pressures are up to

The claimed method for removing metat is sufficient.

Metallic and nitrogen-containing impurities from the process claimed, one brings the Be hydrocarbon oils with anhydrous fluorine to handle with the light normal paraffin, the hydrogen is characterized in that the bed contains dissolved hydrogen fluoride, in liquid Act with a solution of not more than 1 Ge phase in contact by adding the weight percent hydrogen fluoride the treatment agent in a flüs- solution the material to be treated z. B. a mixer

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klav or in a closed pressure vessel. The physical and chemical properties that can be shaken. shafts of the crude oil as it was delivered

Following the above treatment, the following: one the precipitate of insoluble fluoride salts

mixed with precipitated asphalt sludge of 5 properties and analysis

the supernatant liquid hydrocarbon phase of ^{the raw feedstock}

drop. The resulting phases are then Specific gravity at 15.6 ° C 0.8939

for example, by pouring off the upper treated sulfur in percent by weight 1.50

th hydrocarbons from the lower solid or mercaptan sulfur in% 0.0034

Separated sludge phase. Because of the presence of ίο hydrogen sulfide in ° / o 0 _S 0002

dissolved excess hydrogen fluoride in the carbon nitrogen content in% 0.32

Hydrogen phase is the treated carbon basic nitrogen, parts per million /

hydrogen layer on it expedient, z. B. with specific gravity 861

Water, washed or over an adsorbent such as basic nitrogen, parts per million 963

Tableted clay, or clay, passed to the small 15 ash content in parts per million 137

To remove the amount of dissolved hydrogen fluoride, whether-, ». <

equal to the main part of the viscosities in the hydrocarbons

contained hydrogen fluoride in general fully kinematic at 38 ° C, cSt 8.770

constantly by stripping (distilling) the light universal at 38 ° C, seconds .... 54.7

paraffin carrier of the treated hydrocarbons ao vapor pressure in mm Hg 224

Substances are removed that were originally negative as a residue in the Ab-Oliensis test

Strip column remain. The top product, negative from the ab-oliensis test after 24 hours

striped hydrogen fluoride excess and slight pentane insolubles in percent by weight .. 1.70

n-paraffin carrier, is generally condensate

and immediately in the circuit for contact or ^distillation > ¹⁰ ° ^ml bp in ° C

Mixing stage for reuse at initial boiling point 73

handling of additional loading after adding 5% 112

Supplementary hydrogen fluoride returned. 10% 142

The 20% 202 containing the dissolved hydrogen fluoride

Carrier medium is used in a sufficient ratio 3 ° 30% 263

added at 1: 1 to about 12: 1, preferably about 40% 324

5: 1 to about 7: 1 parts by volume of liquefied paraffin - 50% 351

Thinning agent per part of the load before- 60% 366

watch. 70% 378

The treatment showed that the proportions were 35 80% 386

of heavy metals present in the feed 90% 397

to well below about 0.00005% (0.5 parts 95% 404

per million) and the nitrogenous asphaltenes o / _o gained 95.0

or other undesirable originally in the o / _o coke (weight) 4.7

Loading existing nitrogen compounds loading 40 o / ₀ at 204 ° C 20.5

be considerably reduced. Such a weight o / _o obtained at 274 ° C 32.0

action goes to charge in the event of a net loss

less than about 15% and generally less. A spectrographic analysis of the by moisture Less than 10% of their volume in front of them, in their so-obtained ashes of the crude oil (moist In the purified form, the charge can be carried out immediately in a catalytic cracking process, substance of the oil is used by treatment with concentrated, without the long duration of activity of the trated sulfuric acid) showed that the oil was 0.31 parts Deactivates catalyst due to accumulation of iron per million, 27 parts per million nickel, 65 parts the metal in the cracking catalyst is noticeably reduced - per million vanadium and small amounts (im used will. The 50 items produced by the present process vary from 0.01 to 0.6 parts per million) Treated hydrocarbons can also be called manganese, tin, copper, magnesium, calcium and Used for a reforming process, containing sodium.

In the following test runs, the Roheinem Catalyst are brought into contact, the oil feed with various paraffin carbons Hydrogenation component in association with a hydrogen diluent and / or hydrofluoric acid carrier, e.g. B. platinum on a carrier made of fabric of different origins mixed to the active clay with bound halide. ability of the reactants and applied Me-Such Catalysts can be used to identify methods in the process. Where needed enough acid limited when the nitrogen was left to form a separate acid phase impurities in the feed, which affect the catalyst, the latter being separated from the treated upper one Deactivate sator, be removed. Deposit the hydrocarbon layer by standing.

The invention is particular in terms of its emphasis on the lower acid layer from the upper

Embodiments in the following examples withdrawn hydrocarbon phase and the latter with

explained in more detail. Washed water to remove unreacted acid

For example, ^6s removers I ^{Q in} those cases where there are no

^v separated acid layer formed, the metallic fell

In the following example, a Velma crude oil was used as and nitrogenous impurities were used as the primary feed for a catalytic cracking process were originally present in the crude oil with which

Asphalt from which the hydrocarbon was poured off and the analysis was carried out on the treated crude oil to determine the extent of impurity removal. The treated crude with the paraffinic hydrocarbon diluent was then distilled until the original paraffin volume was recovered was leaving a residue consisting of the treated crude oil.

In each of the following runs, 200 grams of crude oil was used as a feed. The hydrogen fluoride was either mixed with a paraffinic hydrocarbon diluent and the resulting - solution mixed with the crude oil, or the hydrogen fluoride was a mixture of Crude oil and η-paraffin added. The mixture was then thoroughly shaken and then broken down into the resulting phases.

In the following experiment No. 1, 200 g of the aforementioned Velma crude oil was mixed with 1020 g of liquid Propane was mixed and the mixture was then shaken to mix the ingredients intimately to effect. After standing, two liquid phases separate, an upper one with propane treated oil phase and a lower precipitated asphalt phase that is under the upper propane layer was withdrawn. The propane solution of the treated crude oil was then heated to evaporate the propane, and left 166 grams of recovered oil, which is 83% of the feed mass. That Reclaimed oil contained 1.6 parts per million nickel, 3.4 parts per million vanadium and 1120 parts per million Total nitrogen. Analysis of the asphalt residue showed it was 172 parts per million nickel and contained 480 parts per million vanadium.

When pentane was used as a light paraffin for deasphalting purposes, it was 88% of the original Crude recovered by evaporation of the pentane, but contained the treated crude 20 parts per million nickel and 45 parts per million vanadium.

In Experiment No. 2 that follows, 200 g of Velma crude oil was used with the above properties with 1000 g normal pentane and 200 g liquid anhydrous hydrogen fluoride mixed which was added to the mixture. The liquids were then stirred and the resulting layers separated. 150 g of treated crude oil (75% of the charge) with 0.1 parts per million nickel, 0.35 parts per million vanadium and 374 parts per million total nitrogen were obtained from the pentane layer. It should be noted that in this treatment with a Liquid phase extraction the loss from feed to extract is excessive, namely 25% by weight of the initial charge, which was also the case for Experiment No. 3 below.

Trial # 3 was 200 grams of Velma crude oil mixed with 1000 g of propane and 200 g of anhydrous hydrogen fluoride in the liquid phase. The mixture was then stirred and left to stand until the two phases settled separately. 59 g treated Crude oil was made from the propane solution (29.5% of the original charge) at 0.07 parts each 1 million nickel and 0.1 part per million vanadium mined. In a separate experiment in which 175 g anhydrous hydrogen fluoride, 200 g crude oil and 1000 g liquid n-pentane used and then the resulting hydrogen fluoride sludge phase was separated off, 114 g of treated crude oil could be obtained (57% of the feed) and the oil contained 0.9 parts per million nickel, 3.2 parts per million Vanadium and 476 parts per million total nitrogen. In the following experiment no. 4, 200 g of des Velma crude oil specified above with 1000 g normal pentane and 200 g of a hydrogen fluoride sludge mixed, obtained in the hydrogen fluoride-catalyzed alkylation of isobutane with butylene had been. The sludge contains 96 weight percent hydrogen fluoride, 1.2 weight percent Water and 0.9 weight percent * hydrocarbons. The mixture was in a pressure cylinder 10 Mi- ' wells shaken, and the resulting phases were separated from each other by decanting. 120 g treated Crude oil (60.5% by weight of the original crude oil charge) became from the pentane layer recovered and the oil recovered contained 0.43 parts per million nickel, 0.83 parts per million Vanadium and 500 parts per million total nitrogen.

In experiment no. 5, 200 g of Velma crude oil were used

1000 g of propane containing 2 g of anhydrous hydrogen fluoride, mixed. It was not a liquid acid phase present, although a precipitate formed which emerged from the hydrocarbon phase and from the propane solution was recovered by filtration. 169 g (84.5% of the original crude) were obtained from the hydrocarbon phase after evaporation of the propane; the treated crude oil contained 0.22 parts per million nickel, 0.56 parts per million vanadium and 537 parts per million total nitrogen. In the same way, but replacing the 1000 g propane with 1000 g normal pentane, were 172 g (86% of the original crude) of treated oil recovered from the pentane solution, and this oil contained 2.2 parts per million nickel, 5.0 parts per million vanadium and 973 parts per million total nitrogen. Ordinary butane is practically as effective as propane for treatment purposes; because 87% of the crude oil was recovered. The treated oil contained about 0.3 parts per million nickel, 0.6 parts • per million vanadium and less than 500 parts per million nitrogen.

These results show that precipitation with a normal paraffin diluent such as Propane and normal butane with a small content of anhydrous hydrogen fluoride (less than for Formation of a separate acid phase is sufficient), which is the only effective measure to keep metallic and nitrogen-containing impurities of the crude oil when hydrofluoric acid is used as Separate extraction agent. 84% or more of the original crude oil is obtained in this way, and the total content of nickel and vanadium in the oil is reduced to a value of less than 1 part each A million reduced. Although also the use of a separate phase of anhydrous hydrogen fluoride extractant which lowers metal contamination of the oil results in the presence of a separate liquid phase of the extractant there is an excessive loss of crude oil feed through the extractant and it becomes less than 80% of the original crude oil obtained by this treatment method. It should also be noted that that only propane and normal butane as hydrocarbon diluents for the treatment of the crude oils are practical and usable, while normal pentane, for example, leads to a

keeping excessive amounts of heavy metals in crude oil.

Claims (1)

Claim: Process for removing metallic and nitrogenous impurities from hydrocarbon oils with anhydrous hydrogen fluoride, characterized in that the treatment with a solution of not about 1 percent by weight of the treating agent in a liquid paraffinic hydrocarbon (Propane or η-butane) in a volume ratio of 1: 1 to 12: 1 of this solution to Hydrocarbon oil takes place while avoiding the formation of a liquid two-phase system and that the resulting precipitate is separated from the treated hydrocarbon oil. Considered publications:
U.S. Patents Nos. 2926129, 2941939, 2971905,2564071;
British Patent Nos. 860 304, 292 932, 292933;
French patent specification No. 1213 475.