NL8203363A - METHOD FOR REMOVING MERCAPTANS FROM HYDROCARBONS. - Google Patents

Description

V V 4 - 1 - Ν.Ο. 31 296

Method for removing mercaptans nitrocarbons ·

The invention is in the field of hydrocarbon purification. More particularly, the invention relates to a method of removing mercaptans from hydrocarbon feeds using a particular copper-containing catalyst therefor.

Yele hydrocarbon feeds contain minor amounts of mercaptans, which impart to the feed a bad odor and corroding effect. Such feeds are generally referred to as "acidic" and are usually treated to convert the mer-10 captans into non-odorless, non-ear disulfides. Under appropriate conditions, the respective total chemical reaction is in the reaction

2ESH + '1/2 02 -> ESSE + HgO

wherein E is a hydrocarbon group, usually an alkyl group. Such a treatment is commonly referred to as "sweetening" and a sweet hydrocarbon feed will usually contain less than about three parts by weight per million mercaptan sulfur. The mercaptan removal process is usually catalyzed by a sweetening catalyst and, as indicated, requires molecular oxygen to proceed.

Copper chloride and copper sulfate-sodium chloride complexes are among the more widely used sweetening catalysts.

These catalysts are effective but have serious deficiencies. First, they are generally not suitable for removing mercaptans from feeds containing significant amounts of unsaturated (cracked) hydrocarbons because they tend to form gums with such feeds. They are usually limited in use with supplies with neutralization numbers greater than 0.005 mg EOH / g due to the formation of copper naphthenates, which cause thermal instability and increase the likelihood of gum formation. Second, these catalysts are highly corrosive and must be contained in coated reactors. In addition to the fact that 8203363 4 1 - 2 - such reactors are expensive, they usually have a limited operating temperature range. Finally, these catalysts contain water-soluble copper compounds after consumption, making them difficult and costly to get rid of in areas ^ 5 that do not have access to a Class A chemical store.

U.S. Pat. No. 3 * 907 * 666 describes a sweetening catalyst consisting of a Cu / Ee / θ spinel, optionally applied to a refractory metal oxide. The stated advantage of this catalyst over the copper chloride-10 catalyst is the increased processing life.

U.S. Patent 2,361,651 discloses a vapor phase naphtha sweetening process in which the sulfur compounds in the naphtha are oxidized to sulfur dioxide at elevated temperatures. The patent indicates that this reaction is catalyzed with copper oxide on a clay support and that the efficiency of sweetened naphtha could be increased by incorporating a Group II metal oxide, hydroxide or carbonate of the periodic system into the catalyst. take.

US Patent 3,454,488 discloses a sweetening process using a catalyst prepared by ionically bonding a copper salt to an ion exchange material with a high base exchange capacity, such as a zeolite or a sulfonate resin, and converting the material. - bonded salt to the elemental metal, sulfide or oxide.

A primary object of the present invention is to provide a catalyst other than the copper chloride and copper sulfate / sodium chloride catalysts for removing mercaptans from liquid phase hydrocarbons at mild temperatures, which can be used in existing equipment, to reduce operating costs. and do not require special waste disposal facilities.

The invention is a method for removing mercaptans from an acidic hydrocarbon, characterized in that the liquid phase hydrocarbon is used under conditions for removing mercaptans from hydrocarbons and in the presence of a gas containing molecular oxygen. contacting a catalyst containing at least 4 component of the group consisting of copper metal, copper oxide and copper sulfide, which component is applied to a refractory porous inorganic support, whereby the mercaptans in the acid hydrocarbon are disulfides. - 3 - converted.

Hydrocarbon supply.

The acidic hydrocarbon feeds from which the mercaptans can be removed by the method of the invention are usually of petroleum, oil containing slate, coal or tar sands origin. These feeds will usually have a boiling range from about 10 ° C to about 350 ° C at 101.3 kPa, more usually from 30 ° C to 300 ° C at 101.3 kPa. Petroleum fractions that fall within this range are gasoline, light and heavy naphtha, petroleum, jet fuel, diesel fuel and light fuel oils. These fractions can be directly obtained or cracked. These acid feeds usually contain between about 10 and 500 parts by weight per million, more usually 50 to 300 parts by weight, per million mercaptan sulfur catalyst.

The catalyst used in the process of the invention is currently used as a sorbent or cleanser to remove mercaptans and other sulfur-containing compounds from naphtha, petroleum distillates, or other hydrocarbons. U.S. Patents 4 * 165 * 708 and 4 * 259 * 213 The catalyst may be used fresh, after regeneration as a sulfur sorbent or after being consumed as a sulfur sorbent. In other words, the catalyst used in the current process for the removal of mercaptans from hydrocarbons is the fresh, regenerated or spent sulfur sorbent of U.S. Pat. Nos. 4 * 163 * 708 and 4 * 259 * 213 * The copper component of the catalyst is copper metal and / or copper oxide in the case of fresh or regenerated material and copper sulfide (primarily copper (il) sulfide) in the case of consumed material. As a result, the copper component of the catalyst used in the present invention may be copper metal, copper oxide, copper sulfide or mixtures thereof. * The copper component will be about 5 to 35% by weight, preferably 10 to 40% by weight of the catalyst, calculated as copper metal. The copper component is supported and dispersed in finely divided form on a natural or synthetic refractory oxide of a metal of groups II, III or IT of the periodic table or mixtures thereof. There is no substantial ionic bond between the copper component and the refractory oxide support. Examples of such oxides are alumina, silicon oxide, silica-alumina, boron oxide, attapulgite clay, diatomaceous earth and pumice. The carriers used in the catalyst do not have high base exchange capacities, although some may have limited ion exchange capacity. The carrier is not activated. Preferably, the porous support forms the remainder of the catalyst. The catalyst is in a particulate, for example, granular or extruded form and will usually have a specific surface (measured by the BET method) in the range of about 30 to 300 m / g, preferably 50 to 200 m / g. . The average size of the catalyst granules will usually range from about 0.08 to about 0.3 cm in diameter and about 0.3 to about 1 cm in length.

The catalyst is prepared by either (a) impregnating the support with an aqueous solution of a water-soluble copper salt, the anionic part of which can be easily removed or converted to the oxide form after drying and calcination, or (b) jointly grinding and mixing a suitable copper compound with a peptized carrier, extrusion of the resulting mixture in particulate form and calendering of the extruded particles. The catalyst preparation techniques are described in detail in U.S. Patent Nos. 4-163-708 and 4 * 259-213 * 25 Process Conditions.

The oxidative process for the removal of mercaptans nitrocarbons can be fed into fixed bed reactors in either the up or down direction by passing the acid feed through έέη or more catalyst beds. A gas containing free molecular weight oxygen, such as air or other oxygen mixtures. with nitrogen or other inert gases, it is usually admixed with the feed in amounts which provide at least a stoichiometric amount of hydrogen in connection with the mercaptan content of the acid feed. Less than geometric amounts of oxygen will result in conversion of a less than desired portion of the mercaptans to disulfides. Preferably, the oxygen to mercaptan sulfur molar ratio is in the range from about 1: 4 to about 10: 1. In other words, usually 1 to 40 times the stoichiometric amount of oxygen will be used. Even a larger excess of oxygen can be used, but is not necessary and may cause an unwanted amount of oxidation of the hydrocarbon feed itself ·

The amount of oxygen in the gas component of the reaction mixture can vary considerably (for example, a few preys up to 5 100 vqL? 0). However, air is preferred for convenience.

Mild reaction temperatures are used, which usually range between about 35 ° C to 200 ° C, preferably 50 ° C to 150 ° C. The pressure should be such that the hydrocarbon feed is maintained in the liquid state at a given reaction temperature. Usually pressures in the range of atmospheric to 2100 kPa, preferably 170 to 700 kPa will be used.

The space velocity is generally between about 1 to 10, preferably 1 to 5. The method of removing meraptans from hydrocarbons of the invention will usually produce a sweetened hydrocarbon, which is less than about 5 parts by weight per million mereaptan sulfur. contains. It is noted that the process does not remove any substantial amount of sulfur from the hydrocarbon, but only converts mercaptans to disulfides.

The behavior of the catalyst can be monitored by determining the amount of mercaptans in the effluent from the process using the usual analytical methods. These include the B0C test, AS5M B484 or more complex analytical methods, which determine the complete breakdown of sulfur types, as indicated below in Tables A and B. When the amount of mereaptan sulfur in the effluent exceeds 3 parts by weight per million, the temperature can be raised to recover the activity. However, the catalyst may eventually become so inactive that it must be replaced or regenerated. Catalyst regeneration.

Liquid is believed to be the primary deactivating agent which affects the behavior of the catalyst. As a result, when the catalyst is consumed, it can be regenerated by removing residual carbon with an oxidizing environment, eg air, at elevated temperatures *

The following examples further illustrate the method of the invention. These examples are not intended to limit the invention in any way.

Example I.

40 An acidic arabic distillate (boiling range 150-260 ° C) 8203363 w - 6 - with a total sulfur content of 2600 parts by weight per million (0.26%) and a mercaptan sulfur content of 134 parts by weight per million was liberated from mercaptans using a catalyst prepared by the joint milling and mixing process of U.S. Patent 4,259,214. The catalyst composition and properties were as follows:

CuO 32.5 wt.% Calculated 26% as Cu metal

Aluminum oxide 67.5 10 Pore volume · 0.50 cm 3 / g

Average pore size 10 nm

Average particle size 1.6 x 6.35 nm grain length

For testing purposes, the catalyst was comminuted to 2 16-32 mesh and twenty cm3 of this catalyst was placed in a fixed bed, downflow nanoreactor. The distillate, mixed with air at the air flow rates shown in Table A, was passed through the catalyst-filled nanoreactor for a total of 1044 hours. The rate of speed was 3.0, the pressures ranged from 410 to 590 kPa, and the temperatures ranged from 107 to 127 ° C. The sweetened product was periodically analyzed for the sulfur and mercaptan content. Table A summarizes the process conditions and the acidic feed and the sweetened product analyzes.

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Example II

A second run was performed on the same middle distillate of Example 1. The same catalyst and equipment used in Example I were also used in this second run. label B lists the process conditions and the results of this second run.

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8203363 - 10 -

Compared to removing mercaptans from hydrocarbons from similar feeds under similar conditions with a copper sulfate / sodium chloride catalyst sold by Perco, the results of Example B indicate that the catalyst life, based on the barrel throughput per catalyst, the catalyst of the process of the invention is at least about twice that of the Perco catalyst *

Example III

10 A directly obtained light arabic naphtha (LSS) (boiling range 55-138 ° C, 500-600 parts by weight pa: million total sulfur and about 50-300 parts by weight per million mereaptan sulfur) was freed from mercaptans using the catalyst and the device as described in Example L The dryness was 414 kPa and the space velocity was 3. Other process conditions are listed in Table G below. Samples of the feed and product were taken periodically and analyzed for mercaptan content.

Table C lists the results of these analyzes. At the end of this run, the catalyst was not consumed and was still operating satisfactorily.

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Compared to the removal of mercaptans nit LSR with Pereo catalyst, the results of Example III, for which the catalyst had not been used up and which can last for several hours, indicate that the catalyst of the present invention The invention has at least a two-fold longer catalyst life.

Example 17.

The acidic light directly obtained Arabian naphtha (LSR) of Example III was freed from mercaptans using a catalyst of the same original composition as Example I, but which had previously been used to remove mercaptans from hydrocarbon feeds in a technical sulfur sorbing operation. This previously used sulfur sorbent contained 3> 9 wt% sulfur and 6.0 wt% carbon residue. The same equipment and pressure were used as in Example III. Other operating conditions, as well as feed and product analyzes are listed in Table D below.

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The data set forth in Table D indicate that it is possible to use a material which has hitherto often been withdrawn as a catalyst to efficiently liberate the hydrocarbon feeds from mer captanes.

The preceding examples prove that the present invention provides longer catalyst life than competitive processes for removing mercaptans from hydrocarbons using the Perco catalyst. Also, as noted above, there are fewer discharge problems with the present process and the catalyst used therewith is non-corrosive.

8203363

Claims (10)

1. Process for the removal of mercaptans from an acidic hydrocarbon, characterized in that the liquid phase hydrocarbon is contacted under conditions for the removal of mercaptans and in the presence of a gas containing molecular oxygen with a catalyst containing at least άέη component from the group consisting of copper metal, copper oxide and copper sulfide, which component is applied to a refractory porous inorganic support, the mercaptans being converted into the acidic hydrocarbon disulfides. 2. Process according to claim 1, characterized in that an acidic hydrocarbon is used with a boiling range from about 10 ° C to about 350 ° C at 101.3 kPa, which is between about 10 and about 500 parts by weight per million mercaptan sulfur. and the hydrocarbon from which the mercaptans have been removed contain less than about 3 parts by weight per million mercaptan sulfur. 3 * Process according to claim 1 or 2, characterized in that the component constitutes 5 to 50% by weight of the catalyst * 4 * Process according to claims 1 to 3, characterized in that a catalyst with a specific surface area in the range of about 30 to 300 m / g is used. 5 * Process according to claims 1 to 4, characterized in that an amount of molecular oxygen is used which is at least stoachiometric with respect to the mercaptan sulfur content of the acidic hydrocarbon. 6. Process according to claims 1 to 5, characterized in that a molar ratio of oxygen to mercaptans is used in the range from about 1: 4 to about 10: 1- Method according to claims 1 to 6, characterized in that air is used as the gas. 8. Process according to claims 1 to 7, characterized in that aluminum oxide is used as the carrier. 35 Method according to claims 1 to 7, characterized in that attapulgite clay is used as the carrier. 10. Process according to claims 1 to 9, characterized in that there is no substantial ionic bond between the component and the carrier. 8203363