DE1167471B - Coarse copper chloride catalyst for sweetening acidic petroleum distillates - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Kl .: ClOg

German class: 23 b-1/05

Number: 1167471

File number: St 11124IV d / 23 b

Filing date: April 25, 1956

Opening day: April 9, 1964

The invention relates to a special catalyst which is used for sweetening by the copper chloride process can be applied.

This has found wide application in the petroleum industry for sweetening sour virgin gasoline. The acidic gasoline is passed through a fixed bed of the catalyst or with a dispersion of Catalyst particles brought into contact in the presence of free oxygen until the mercaptans in the gasoline have been converted into disulfides. The usual catalyst consists of copper chloride and water on an adsorbent such as fuller's earth. The copper chloride sweetening process is on thermally cracked gasolines can be used, but the life of the catalyst is generally the same very briefly because catalyst is lost with the sweet oil. The presence of copper in the sweet oil is very disadvantageous for its color fastness. When sweetening distillate fuels with high Total sulfur content, the sweet oil is extremely unstable and can even be added in large quantities Copper metal deactivator cannot be stabilized.

The catalyst proposed here can be used for acidic, split distillates and acidic distillate fuels can be used without losing large amounts of copper.

The new copper chloride catalyst for sweetening sour petroleum distillates consists of adsorption earth, 4 to 15, preferably 6 percent by weight copper (II) chloride and 35 to 45, preferably 40 percent by weight Water, based on the total amount of the catalyst, and is characterized in that the adsorption earth is soaked with a solution of copper (II) chloride in water, which is attached to the adsorption earth already adsorbed water has to be taken into account in the total water content of the catalyst.

A preferred catalyst consists of attapulgus clay, the mesh size of which is less than about 80 mesh is. For the so-called "pulp sweetening process", the mesh size is generally between 80 and 200 meshes, that is 0.177 or 0.074 mm clear mesh size. Coarser grains are used for fixed bed catalysts used.

The copper (II) chloride can be technically or chemically pure and can be used in anhydrous or hydrated form. It can also be made from copper (II) sulfate and ammonium chloride or sodium chloride by dissolving these substances in the required amount of water. To prepare the catalyst, the copper (II) chloride is dissolved in water at room temperature and the solution is added to the calculated amount of fuller's earth. The granular copper chloride catalyst for sweetening
acidic petroleum distillates

Applicant:

Standard Oil Company, Chicago, JIl. (V. St. A.)

Representative:

Dr.-Ing. H. Ruschke, patent attorney,

Berlin 33, Auguste-Viktoria-Str. 65

Named as inventor:

Russell H. Brown,

William P. Fairchild, Hammond, Ind.,

Fred K. Kawahara, Chicago, JIl. (V. St. A.)

The amount of water absorbed in fuller's earth is taken into account when determining the amount of water used for the solution. The catalyst obtained by impregnating the fuller's earth with the CuCl _{2 solution is}

as a free-flowing, granular mass that is "dry" feels.

Under the usual process conditions, the use of the catalyst described above results with certain acidic distillates, which are described below, noticeably lower Loss of copper and, in the case of certain distillates, a noticeable improvement in color stability of the sweetened oil.

One can -with the claimed catalyst thermally cracked distillates (Kp. 38 through 315 ° C), virgin distillates (bp. 38-315 ⁰ C), which contain significant amounts of the thermally cracked distillates and virgin distillates having high sulfur content (Kp . 162 to 315 ° C) sweeten. The thermally split distillates can be gasoline or higher-boiling oils known as cycle stocks. The presence of significant amounts of these split distillates mixed with virgin distillates can cause large losses of copper and discoloration when using the usual copper chloride catalyst. Even 5 percent by volume, often even less, of fission distillate show a harmful effect when mixed with crude distillate. The virgin distillates generally contain at least 0.3 percent by weight of total sulfur and boil between about 162 and 315 ^° C. If a sweet, virgin distillate is used

409 558/400

If high color fastness is required, the sulfur content of the distillate fed should be in the range from 0.3 to 1.2 percent by weight and the mercapt number should not exceed 40. High quality distillate heating oils boil between 162 and 289 ⁰ C.

The catalyst according to the invention is intended for the treatment of such petroleum distillates oxygen-containing polar compounds, e.g. B. phenols, contained in such amounts that they can be used

usual copper chloride catalyst / the at technical Method used on a large scale is compared. The different catalysts were like is made as follows:

Procedure A

Procedure C

1 g of cupric chloride dihydrate became 9 g of the finely divided attapulgus clay used in method A. given. These ingredients were intimately mixed and then 4 g of water were added to the mixture. It was mixed until a free flowing grainy

Method D

A catalyst according to the invention was prepared as follows: 1 g of copper (II) chloride dihydrate was dissolved in 4 g of water. This solution was added to 9 g of fine customary copper chloride catalysts, not sweetened, one-part attapulgus clay which, according to analysis, contained 15% by weight of adsorbed water without major copper losses. The standing and inadequate color fastness of the solution and the clay were mixed until a freely sweet oil occurs. The usual copper chloride catalyst was obtained, which looked "dry" and consisted of about 1 to 25 percent by weight and also felt that way; this catalyst consisted of copper (II) chloride, about 5 to 30 percent by weight of 5.7 percent by weight CuCl ₂ , 39.7 percent by weight water, with the remainder almost entirely fuller's earth H ₂ O and 54.6% clay.
or pumice stone.

The results obtained with the new catalyst B

obtained, on the basis of the following embodiment, 4 g of water became 9 g of that in process A

examples explained. A continuous 3 ° used, finely divided attapulgus clay was given. The laboratory-scale copper chloride sweetener water and clay were mixed until the water uses up. It contained a preheater to saturate the completely adsorbed material. Then 1 g of cupric acid oil with water, which was kept at about 35 ° C. chloride dihydrate, was added to the water-containing clay, a reactor in which the acid oil was mixed with a mixture until all of the copper - Slurry of granular catalyst at about 38 ° C in 25 chloride had penetrated the clay and a dry mass flowing in the free presence of free oxygen in contact was obtained,
was brought, the content of free oxygen
was slightly above the theoretical amount required for
complete conversion of the mercaptans to disulfides
was required. Devices were in place, 30
to a pulp of catalyst and oil from the
To remove from the reactor and to put this pulp in the
To be mixed with sour oil, as used in technical brewing units. That

sweet oil was continuously withdrawn from the reactor 35 mass was obtained,
and washed with water to remove entrained catalyst and the so-called "product oil"
to win. In all cases the acidic oil was used with a common copper chloride catalyst,

aqueous caustic alkali solution - usually by two - as used in refining processes, hergemalige Treatment with 5 percent by volume 20% 40 represents. This catalyst contained 18% water, 8% Sodium hydroxide solution · - brought into contact, copper (II) chloride; the rest was finely divided attapulgus clay.

The sour oil was a homogeneous mixture of virgin distillate obtained by distillation from a central continental crude oil with low sulfur content (70%)> ^from a heating oil distillate with high sulfur content obtained by distillation from a West Texas crude oil ( 11%) ^and from a young layer of water and turned out to be the copper salt 50 womanly very heavy gasoline, which contained a small amount of an oxygen-containing, polar compound (true amount of cracked gasoline (19%) · the mercaptan probably alkylphenol). number of this mixture was 22.6 and the total

To determine the desulphur content from the catalyst, about 0.3 percent by weight,
The removed amount of copper was the reactor outlet and the acid oil was with each of these catalysts

the "product oil" was brought into contact with the content of oil-soluble copper and the reactor outlet passed through analyzed. A sample of the reactor effluent that was not filtered through filter paper to remove entrained catalyst Washed with water was removed by filter paper. In each case the reactor outlet was granules sent to be carried away catalyst to the doctor test sweet. The copper content of the remove. A sample of the water-washed filtered reactor effluent was made in parts of copper each Oil was designed to remove water through filters- 60 million. The color fastness of the filpapier directed. The oil samples were then determined on the treaded, sweet reactor outlet

after the oil 0.001 percent by weight copper metal deactivator, namely, N, N'-disalicylidine-1,2-diaminopropane, had been added. This matches with 65 0.9 kg metal deactivator per 1600001 sweet oil and is the usual dosage for commercially available oils. The Saybolt color of the filtered reactor outlet was determined and then the oil was

to remove hydrogen sulfide. The hydrogen sulfide-free one Oil was washed with water to make up aqueous caustic alkali, which is the copper chloride catalyst is harmful to remove.

If a phenol-containing oil is sweetened with the usual catalyst, it is also obtained when washing Water a yellowish precipitate. This occurred as a foam at the interface between sweet oil and

Soluble copper content analyzed and the copper content in parts copper metal per million (T / M) certainly.

example

In this example the method of making the catalyst is examined and with a

aged examination. In this study, were heated 100 cc of the oil in an open beaker for 20 hours at 93.3 ⁰ C. The "aging color" in connection with the original color represents a good measure of the shelf life of the individual oils. The greater the difference between the original color and the aging color, the worse the color stability of the oil when stored in excess. The results of this example are then shown in the table below.

production method

A.
B.
C.
D.

Color of the filtered oil
according to Say bolt *)
after

originally

+ 13
+ 18
+ 8
+15

Aging

+ 13

-12

Copper content
of the filtered oil

σ / Μ)

0.3 3.5 4.4 3.0

*) All oils were sweet compared to the doctoral test.
**) darker than —16 Saybolt.

Only the catalyst prepared according to A, which is the catalyst of this invention, produces an oil with sufficient color fastness, in addition, the reactor outlet contained less than 10% of the dissolved Copper that was contained in the reactor outlets for which either the known catalyst according to Process D or high water content catalysts made by other processes, were used.

The product oil or the filtered reactor discharge was as usual by adding Ν, Ν'-disalicylidin-1,2-diaminopropane stabilized.

Any known copper metal deactivator can be added to the sweet oil. Numerous examples for known copper metal deactivators are in "Industrial and Engineering Chemistry", 41, p. 918 (May 1949).

35

40 Of course, the term "cupric chloride sweetening conditions" is intended to include all conditions known in the art for treating acidic distillates that use a supported cupric chloride catalyst. Numerous patents and publications describe a large number of variations of the underlying copper chloride sweetening process developed by Hoover. These conditions relate to the pretreatment of the acidic distillate, the time, temperature and oxygen utilization in the sweetening reactor, and the methods used to remove entrained catalyst from the reactor effluent.

Claims (2)

Patent claims: 1. Granular copper chloride catalyst for sweetening sour petroleum distillates, which is made from adsorption earth, 4 to 15, preferably 6 percent by weight copper chloride and 35 to 45, preferably 40 percent by weight Water, based on the total amount of the catalyst, is characterized by that the adsorption earth is soaked in a solution of copper chloride in water, the water already adsorbed on the adsorption earth in the total water content of the catalyst is to be considered. 2. Catalyst according to claim 1, characterized in that the earth is made of attapulgus clay consists, the screen size of which is smaller than about 80 mesh. Considered publications: U.S. Patent No. 2,094,485; British Patent Nos. 502 752, 513 934, 768 847; French Patent Nos. 830 031, 1,061,759; Kalichevsky and Stager, Chemical Refining of Petroleum, New York, 1942, p. 208, para. 2; Chemisches Zentralblatt, 1940, II, p. 2706. 409 558/400 3.64 © Bundesdruckerei Berlin