JPH0132277B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for treating sour petroleum products (petroleum distillates) to convert the mercaptans contained therein. Processes for the treatment of sour petroleum products, in which sour petroleum products are contacted with a catalyst in the presence of an oxidizing agent under alkaline reaction conditions, are already well known and widely practiced in the petroleum refining industry. This process involves the oxidation of the unpleasant and harmful mercaptans normally found in sour petroleum products to produce harmless disulfides (generally
(a method called sweetening). Depending on the type of crude oil used to derive the sour petroleum product, the boiling range of the product itself and the method of processing the petroleum for the production of this product, the petroleum product can contain the amount (concentration) of mercaptans it contains; Varies widely with respect to molecular weight and complexity. For example, in light mercaptan-containing petroleum products such as straight-run gasoline, the mercaptans are primarily lower alkyl mercaptans that can be easily oxidized to disulfides. On the other hand, mercaptan-containing gasolines obtained from fluid catalytic cracking (FCC) processes often have a relatively high olefin content and are susceptible to conversion to disulfides, such as aromatic and higher molecular weight branched alkyl mercaptans. Contains mercaptans, which are more difficult to assemble. It has now been found that mercaptans, particularly those present in FCC gasoline, can be advantageously converted to disulfides by contacting the gasoline with a novel catalyst complex in the presence of an oxidizing agent. Ta. Utilization of the catalyst complex of the present invention provides operators of FCC equipment with another useful option for converting common mercaptans into oil effluent from the equipment to produce doctor sweet products. Let's provide a treatment method. It is an object of the present invention to provide a new process for the conversion of mercaptans contained in sour petroleum products, in particular sour gasoline obtained from fluid catalytic cracking operations. The present invention involves bringing sour petroleum products into contact with a catalyst complex formed by impregnating a basic anion exchange resin with a metal chelate type mercaptan oxidation catalyst and an oxidizing agent in order to convert the mercaptans contained therein. A method of processing sour petroleum products consisting of: One more specific embodiment is to convert the sour petroleum product into a porous styrene-divinylbenzene cross-linked polymer.
The present invention relates to a method comprising bringing a catalyst composite formed by impregnating an amine-type anion exchange resin composed of a matrix with a metal phthalocyanine into contact with air. In a more specific embodiment, a catalyst composite is formed by impregnating cobalt phthalocyanine monosulfonate into an amine-type anion exchange resin composed of a porous styrene-divinylbenzene crosslinked polymer matrix and a tertiary amine functional group, and air. The present invention relates to a process for the conversion of mercaptans contained in sour petroleum products, comprising contacting the petroleum product with a petroleum product. Other objects and aspects of the invention will become apparent from the more detailed description below. The catalyst composite of the present invention is a basic anion exchange resin impregnated with a metal chelate type mercaptan oxidation catalyst. There are a wide variety of basic anion exchange resins suitable for use with the present invention. Basic anion exchange resins generally have primary, secondary and/or tertiary amine functionality. Anion exchange resins containing primarily tertiary amine functionality (eg, dimethylaminomethyl functionality) are more effective as anion exchange resins. In addition, certain basic anion exchange resins composed of cross-linked monoethylenically unsaturated monomer polyvinylidiene monomer copolymer matrices have desirable surface area and high pore diameter properties, making it possible to allows more access to functional groups. Crosslinked styrene-polyvinyl copolymers are one notable example. Other monoethylenically unsaturated monomers, such as α-methylstyrene, mono- and polychlorostyrene, vinyltoluene, vinylanisole, vinylnaphthalene, etc., may also be used, such as other polyvinylidiene monomers, such as trivinylbenzene, divinylnaphthalene, divinylthene, It has been disclosed in the literature that it can be copolymerized with trivinylpropene and the like, thereby forming desirable crosslinked copolymer matrices. Amberlyst A-21 is an example of a suitable anion exchange resin, which is a weakly basic anion exchange resin consisting of a crosslinked styrene-divinylbenzene copolymer matrix with tertiary amine functionality. It is stated that. Amber List A-29
and Duolite A-7 are also examples of commercially available anion exchange resins that may be used. The former are designated as medium strength anion exchange resins and the latter are designated as weakly basic anion exchange resins containing secondary and tertiary amine functionality. Those skilled in the art will appreciate that the metal chelate-type mercaptan oxidation catalyst used as a component of the catalyst composite of the present invention is effective as a catalyst for the oxidation of mercaptans contained in sour petroleum products to produce polysulfide oxidation products. Any of the various metal chelates known in the art may be used. Such chelates include metal compounds of tetrapyridinoporphyrazines (e.g., cobalt tetrapyridinoborphyrazine) as described in U.S. Pat. No. 3,980,582; porphyrin and metalloporphyrin catalysts (e.g., as described in U.S. Pat. , cobalt tetraphenylporphyrin sulfonate); corrinoid catalysts (e.g. cobalt choline sulfonate) as described in U.S. Pat. No. 3,252,892; chelate organometallic catalysts (e.g. condensation products). Metal phthalocyanines are a preferred type of metal chelate mercaptan oxidation catalyst. Metal phthalocyanines used as mercaptan oxidation catalysts are generally magnesium, titanium,
Hafnium, vanadium, tantalum, molybdenum, manganese, iron, cobalt, nickel, platinum,
Contains metals such as palladium, copper, silver, zinc and tin. Particularly preferred are cobalt phthalocyanine and vanadium phthalocyanine. Metal phthalocyanines are particularly frequently used as their derivatives, and commercially available sulfonated derivatives such as cobalt phthalocyanine monosulfonate, cobalt phthalocyanine sulfonate or mixtures thereof are particularly preferred. Sulfonated derivatives can be prepared, for example, by reacting cobalt, vanadium or other metal phthalocyanines with fuming sulfuric acid. Although sulfonated derivatives are preferred, it will be appreciated that other derivatives, especially carboxylated derivatives, can also be used. Carboxylated derivatives can be easily produced by reacting metal phthalocyanine with trichloroacetic acid. Metal chelate mercaptan oxidation catalysts are easily adsorbed onto the basic anion exchange resins of the present invention.
Generally, up to about 25% by weight of the metal phthalocyanine can be adsorbed onto the anion exchange resin and still form a stable catalyst complex. Amounts ranging from 0.1 to about 10% by weight generally form suitably active catalyst complexes, although the activity benefits obtained from concentrations above about 2% by weight have so far been limited. This did not justify the use of higher concentrations. The metal chelate mercaptan oxidation catalyst used can be impregnated into the anion exchange resin from its aqueous or alcoholic solution and/or dispersion by any conventional or convenient method.
The anion exchange resin is advantageously washed with alcohol before impregnation with the metal chelate mercaptan oxidation catalyst used. Alcohol cleaning is
It has been found to be an important factor in the production of suitably active catalyst complexes for the conversion of mercaptans contained in sour petroleum products. Methyl alcohol is a preferred cleaning agent, primarily because of its ready availability and relative stability. Impregnation is otherwise suitably carried out in a conventional manner.
That is, the anion exchange resin is immersed in an aqueous or alcoholic impregnating solution and/or dispersion liquid by dipping, suspending, soaking, etc. one or more times to adsorb a predetermined amount of the metal chelate component onto the resin. One preferred method utilizes a steam jacketed rotary dryer. Anion exchange resin is added to the impregnating solution and/or in the dryer.
Alternatively, it is immersed in a dispersion and the resin is tumbled therein by the rotating motion of a dryer. Application of steam to the dryer jacket promotes evaporation of the solution in contact with the tumbled anion exchange resin. In any case, the resulting composite is dried under room temperature conditions or with a stream of hot gas or by any other suitable method. Another convenient method for adsorbing metal chelates onto anion exchange resins is to pre-position the anion exchange resin as a fixed bed in a sour petroleum product processing zone or chamber, and then add the metal chelate impregnating solution and/or Alternatively, the dispersion may be passed through the resin bed to form the catalyst complex in situ. This method involves applying the solution and/or dispersion once or twice.
By recycling more than once, it is possible to achieve the desired concentration of metal chelate component on the anion exchange resin. In yet another method, an anion exchange resin is pre-positioned in the treatment zone or chamber, and the zone or chamber is filled with an impregnating solution and/or dispersion to soak the resin for a predetermined period of time. put. In the sweetening operation of sour petroleum products, conventional practice has been to oxidize the mercaptans contained therein in the presence of alkaline reagents. An alkaline reagent (usually an aqueous caustic solution) is applied continuously or intermittently as needed.
It is delivered in contact with the catalyst complex and mixed into the sour petroleum product. However, it is a feature of the catalyst complex of the present invention that this additional alkaline reagent is not essential, which further simplifies the sweetening process since the addition and subsequent separation of alkaline reagents can be eliminated. Although the conversion of mercaptans contained in sour petroleum products can be carried out according to the method of the invention at room temperature conditions, it is preferable to use temperatures up to about 105°C, commensurate with the thermal stability of the anion exchange resin. It is. Although pressures up to about 70 atmospheres or more can be carried out, atmospheric or substantially atmospheric pressures are most likely sufficient. Contact times corresponding to liquid hourly space velocities of 0.5 to 10 or more are effective to achieve the desired reduction in mercaptan content of sour petroleum products. The optimum contact time will vary depending on the size of the treatment zone, the amount of catalyst loaded therein, and the nature of the product being treated. As already mentioned, sour petroleum products are also processed in contact with oxidizing agents. The oxidizing agent is preferably air, but oxygen or other oxygen-containing gases can also be used. Although sour petroleum products may contain sufficient agitated air, they are generally mixed with air in the chemical amount necessary to harmlessly convert their mercaptan content to disulfides by oxidation. stoichiometric approx.
Supply 1.5 to 2 times more oxygen. The process of the present invention is carried out in a continuous operation in which a substantially water-free sour petroleum product is mixed with air and processed by passing it upwardly or downwardly through a fixed bed of catalyst arranged in a vertical processing column. It is preferable to do so. However, the flow properties of the catalyst composites of the present invention also allow them to be advantageously used in moving bed or slurry operations. The following examples are intended to illustrate some preferred embodiments of the invention and are not intended to unduly limit the scope of the invention. Example 1 To prepare a mercaptan oxidation catalyst supported on an anion exchange resin, 100 c.c. of a weakly basic anion exchange resin (Amberlyst A-21) containing a tertiary amine functional group was prepared in advance. After washing with methanol, the sample was impregnated with a caustic aqueous solution of cobalt phthalocyanine monosulfonate. This aqueous caustic impregnation solution was prepared by dissolving 150 mg of cobalt phthalocyanine monosulfonate in a 7% by weight aqueous caustic solution. Anion exchange resin beads of 0.4 to 0.55 mm were immersed in the impregnating solution, and the solution was stirred for about 5 minutes while in contact with the anion exchange resin. The resin was then kept in solution under static conditions for about 1 hour, after which
The solution was evaporated to dryness in a steam bath while in contact with the resin. The impregnated resin was then dried in a dryer at about 100°C for 1 hour. The catalyst of this example is referred to as catalyst A.
shall be. Example 2 The anion exchange resin used was substantially as described in Example 1, except that the anion exchange resin used was a strongly basic anion exchange resin containing quaternary ammonium hydroxide functionality (Amberlyst A-26). , Catalyst B was produced. The above catalysts A and B have a boiling point range of 40 to 235
An evaluation test was performed on debutanized crude FCC gasoline containing 58 ppm mercaptan-type sulfur at 10°C. In both cases, 13.3cc catalyst and
100 c.c. of gasoline was placed in a closed glass container with air at room temperature and atmospheric pressure, and the glass container was attached to a mechanical shaking device. The gasoline was shaken while in contact with the catalyst and analyzed for residual mercaptan sulfur content and gum content after 5, 15 and 30 minutes. The results are summarized in the table below.

[Table] Comparative Example 3 In this example, an activated carbon-supported cobalt phthalocyanine monosulfonate catalyst was produced by adsorbing this cobalt phthalocyanine monosulfonate onto an activated carbon support from a methanol dispersion of cobalt phthalocyanine monosulfonate using a conventional method. did. Thus, 150 mg of cobalt phthalocyanine monosulfonate was mixed with 50 mg of methanol and stirred for about 5 minutes. The resulting dispersion was then diluted to 300 ml with methanol and stirred for an additional 5 minutes. About 100 c.c. of activated carbon particles having an average bulk density of about 0.25 g/cc and a particle size in the range of 10 x 30 mesh are immersed in a methanol dispersion, and the dispersion is stirred for about 5 minutes to contact the particles, It was then left to stand and contact with the particles for 1 hour. The methanol dispersion was then evaporated and dried in a steam bath while in contact with activated carbon, and the resulting impregnated particles were then
It was dried at 100°C for 1 hour. The catalyst of this example is designated as catalyst C. As in Examples 1 and 2, Catalyst C was evaluated using unrefined debutanized FCC gasoline with a boiling point of 40°C to 235°C containing 58 ppm mercaptan sulfur. 13 c.c. of catalyst and 100 c.c. of gasoline were shaken in a glass container, and the residual mercaptan sulfur and gum in the gasoline were analyzed at 5, 15, and 30 minute intervals. For Catalyst C, the catalyst was wetted with 5 c.c. of a 7% by weight aqueous sodium hydroxide solution prior to mixing the catalyst with gasoline. The results are shown in Table 2.

[Table] From the above table, it can be seen that the resin-based catalysts A and B of Examples 1 and 2, which were evaluated without alkali washing, are comparable to the carbon-based catalyst C that was washed with alkali. Comparative Example 4 This example illustrates that the catalyst of the present invention is as effective as a conventional carbon-based catalyst, but that the conventional catalyst requires alkaline washing to be effective. That is clear. In this way, an activated carbon-supported catalyst was prepared in the same manner as in Comparative Example 3. The first portion of the catalyst (Catalyst D) was wetted with a 7% by weight aqueous sodium hydroxide solution prior to mixing with gasoline. A second portion of this catalyst (Catalyst E) was not treated with sodium hydroxide prior to mixing with gasoline. These catalysts were each treated in the same manner as in the previous example.
Mixed with FCC gasoline. The test results are shown in Table 3.

Table 3 shows that conventional carbon-based catalysts that are not treated with alkali do not remove mercaptan sulfur as effectively as conventional catalysts that are treated with alkali. Because the catalysts of Examples 1, 2, and 3 are used to treat different feedstocks than Example 4, these data are expressed in percent conversion for ease of comparison. That is the best thing to do. The following table converts Tables 4 and 5 into percent conversion. Table 4 is a combination of Tables 1 and 2, and Table 5 shows Table 3.

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Claims (1)

[Claims] 1. A basic anion exchange resin having an amine functional group selected from the group consisting of primary, secondary, tertiary and quaternary amine functional groups is impregnated with a metal chelate mercaptan oxidation catalyst. A method of processing a sour petroleum product for the conversion of mercaptans contained in the sour petroleum product, comprising contacting the sour petroleum product in a single step with a catalyst complex comprising: 2. Claim 1, wherein the anion exchange resin is composed of a porous styrene-divinylbenzene crosslinked polymer matrix, and the metal chelate oxidation catalyst is a metal phthalocyanine.
The method described in section.