SU910733A1 - Process for demercaptilazation of hydrocarbon feedstock - Google Patents

Description

(5L) METHOD FOR DEMERCAPTANIZING HYDROCARBON

RAW MATERIALS

This invention relates to the liquid phase oxidation of mercaptans to disulfides. This process is widely used in the production of disulfides, the purification of hydrocarbons from mercaptans, and the regeneration of mercaptic alkaline reagents and effluents. There is a known method for demercaptanization of a hydrocarbon feedstock by contacting it with an oxygen-containing gas in the presence of cobalt phthalocyanine disulfonate 1. The demercaptanization of a hydrocarbon feedstock is closest to the proposed method by contacting it with an oxygen-containing gas in the presence of cobalt-ficano cyanine in the flow of the sample, I will try to treat the hydrocarbon feedstock by contacting oxygenated gas with oxygen-containing gas in the presence of cobalt phthalocyanine. cobalt tetraminophthalocyanine. However, this method provides for the conversion, for example, n-butylmercit sodium sodium for 10 minutes not higher than kQ% and the purification rate with an effective KO speed effect not higher than 8.0. This leads to a long stay of the raw material in contact with the phthalicyanine catalyst and reduces the efficiency of the catalytic oxidative demercaptanization process. The purpose of the invention is to increase the degree of purification of hydrocarbons and accelerate the process. This goal is achieved in that according to the method of demercaptanization of a hydrocarbon feedstock in the presence of a phthalocyanine catalyst by contacting the feedstock with an oxygen-containing gas, bromine cobalt phthalocyanine derivatives are used as the phthalocyanine catalyst. Bromine derivatives of phthalocyanine cobalt, Pre-deposited on a porous carrier, are used.

331

The process according to this method is conducted at atmospheric pressure up to 10 atm and 25-50 ° C,

Disulfides obtained during the oxidation of mercaptans can be removed from the raw material being purified or left in it. In the first case, the mercapts are extracted from the hydrocarbon feedstock in the form of mercaptids by contacting the Moro hydrocarbon feedstock without storing oxygen-containing Raza in the extractor with the catalyst complex, which, after saturation with mercaptides, is subjected to oxidative demercaptanisation with oxygen-containing gas at 25-60 C. they do not dissolve in the catalyst complex and are separated from it by a simple lag. Regenerated catalyst complex is fed again to the oxidation of mercaptans "

In the case when disulfide removal is not required and a negative plumbit sample of the raw material being cleaned is needed (for example, gasoline, kerosene, jet fuel), the oxidation is carried out with an oxygen-containing gas in an amount sufficient to oxidize the mercaptides to disulfides in the presence of phthalocyanine catalysts supported on solid carrier.

The method is carried out as follows.

Prepare an alkaline solution of sodium mercaptide by dissolving the mercaptan in 10% aqueous sodium hydroxide solution. The catalyst is also pre-dissolved in an aqueous solution of sodium hydroxide. The sodium mercaptide and catalyst solutions with a total volume of 200 mp are mixed in a glass cylindrical reactor with a centrifugal stirrer at a speed of 2.000 rpm. The sodium mercaptide concentration is 0.3 mol / L. The oxidation is carried out with molecular oxygen fed to the reactor through a sparger in an amount of 0.3 l / min for 15 minutes. During the test, samples were taken to determine the concentration of Mercaptide, which was analyzed by potentiometric titration on a pH-340 instrument. The reaction is carried out at atmospheric pressure and 30 ° C. Upon oxidation, the mercaptides are converted to disulfides, which are removed. Cata07334

The lyser is suitable for the oxidation of new portions of mercaptides.

Example 1 Oxidation of sodium n-propyl mercaptide in the presence of disulfonic, k k, | -tetrabromphtapocyanin cobalt.

The concentration of disulfo-4, 4, i,

I. /

V-tetrabromophthalocyanine cobalt 2.58-10 mol / l.

88.0 /: -N-propyl mercaptide sodium is oxidized in 5 minutes.

Example 2 Oxidation of sodium n-propyl mercaptide in the presence of dibromo-3,6,3, b, U.b ,, b octoxyphthalocyanine cobalt.

The concentration of dibromo-3,6, h, 3,6-octaoxyphthalocyanine cobalt is 2.58-10 mol / l.

20 In 80 minutes, 80.2 n-propyl mercaptide sodium is oxidized.

Example 3 Oxidation of sodium n-propyl mercaptide in size

V- f., / G

hexabrom-3,0, -3,0, 3,6, 3, pocta-oxyphthalocyanine cobalt.

The concentration of hexabrom-3,6,3 (6, 3.6, h, b-octa-oxyphthalocyanine cobalt 2.5810 mol / l.

85.85 n-propyl mercaptide sodium is oxidized in 5 minutes.

Example k. Oxidation of m-g; oilmercaptide sodium in the presence of r.:.: And hectabrom-3.6, h, b. 3, 3 b. Ok; aoxyphthalocyanine cobalt.

Concentration by hectare-3,6, 3

3 fi. , 0, 3, and octoxyphthalocyanine cob. Alt. 2.58-10 mol / l.

In 5 minutes, 89.1% of sodium n-propylmerciptide is oxidized.

PRI me R 5. Oxidation of n-propyl mercaptide sodium in the presence of .. f -I f V x JUflll

octabromo-3,6, 3,6, 3,6, 3, 6 of cobalt oxyphthalocyanine. 5 Concentration with octane 3,6,3,6,

- / „II / X /

3,6., 3,6 -octaoxyphthalocyanine cobalt 2, 5B 00 mol / l.

98.3 n-propyl mercaptide sodium is oxidized in 5 minutes.

The test results for the catalytic oxidation of n-propyl mercaptide sodium in the presence of proposed and well-known catalysts (phthalocyanine-cobalt disulfonic acid disodium salt and cobalt disulfates with disulphate lot) are listed in the table below.

Famous

Disodium salt of disulfonic acid phthalocyanine cobalt

Disulfonic acid 4, C granite roftalocyani on cobalt

Disulfonic acid, V, V-tetroxyphthalocyanine cobalt

Disulfonic acid +, C, C (C-tetramine phthalocyanine cobalt

Proposed

Disulfo i, 4, t, C -tetrabromophthalocyanine cobalt

(- and -II Jl-df Dibrom 3,6,3,6,3,6,3,6,6-octa-oxyphthalocyanine cobalt

I .1 II (I t- / II Hexabrom 3,6,3,6,3, b, 3, o-octo-oxyphthalocyanine cobalt

Heptabrom-3,6,3,6,3,6,3,6,6-octaoxyphthalocyanine cobalt

Octabrom 3,6,3,6,3,, 6 -OKTaoxyphthalocyanine cobalt 1 - effective formula Example 6. Oxidation of sodium n-butylmercaptide in the presence of disulfo, k, k, k, tetrabro phthalocyanine cobalt., Disulfo concentra tion, A, k, tetalbromo alocyanine cobalt 2, mol / L. 5b, 8 n-bu sodium mercaptide is oxidized in 10 minutes. EXAMPLE 7 Sodium n-butylmercaptide is oxidized in the presence of: -, 7 (, - due to dibrom-3, b, 3, t, J, 0 octoxyphthalocyanine cobalt.

Table 1

5.35

20.70

37.50

39, "O

70.78

83.0

5.00

80.2

65.10

85,8

73.80

89.1

136.00

9 ", 3 I reaction rate," Dibromo-3,6,3,6 concentration, 6, 3,6 -octo-oxyphthalocyanine cobalt 2, mol / l o "7.6% n-butylmercaptide sodium is oxidized in 10 min. . PRI me R 8. Oxidation of sodium n-butyl mercaptide in the presence of; hexabrom-3,6,3, b, 3, b, /; b - octo-oxyphthalocyanine cobalt. The concentration of hexabrom-3,6,3,6, U, b, s, b-octa-oxyphthalocyanine cobalt 2, mol / L. 53, -8 n-butyl mercaptide sodium is oxidized in 10 minutes.

7

Example 9. Oxidation of sodium n-butyl mercaptide in the presence of heptabrom-3, b, 3, b, 3, b-octaoxyphthalocyanine cobalt o

Heptar concentration, 3i6

-Their jllylll.

3,6, -octaoxyphthalocyanine cobalt. , 5-needle / l.

5% of n-butyl mercaptide sodium is oxidized in 10 minutes.

Example 10. Oxidation of sodium n-butyl mercaptide in the presence of octabrom-3,6, h, b ,, b, 3b-octaoxy phthalocyanine cobalt. As the sodium mercaptide, n-butylmercaptide sodium KonIzvestny is tested.

Disodium salt of disulfonic acid phthalocyanine cobalt

/ Ii .14

Disulfo acids a h, h, h, h - tetranitrophthalocyanine cobalt

I I 1 I Disulfonic acid h, h, h, h - tetraoxyphthalocyanine cobalt

1 I, Disulfonic acid h, h, h, h-tetraminophthalocyanine cobalt

Proposed

1 and III

Disulfo, k, k, k -tetrabromophthalocyanine cobalt

Dibromo-3,6,3,6,3% i3, octoxyphthalocyanine cobalt

 / "I x J / Hex-3,0,3,0,3,6,3, f-octaoxyphthalocyanine cobalt

 f / / (/ Hepta-3,6,3, b, 3, ь, 3, b-octa-oxy-phthalocyanine cobalt

Octa 3,6, 3, 3, b, z.b-octaoxy phthalocyanine cobalt

Purification of diesel fuel from mercaptan sulfur (0.02 masd)

9107338

 cent of a roentry abrom - 3,6, 3i (3,, -octaoxyphthalocyanine cobalt 2.5 40 mol / l.

  80.2% of n-butyl mercaptide sodium is oxidized in 10 minutes.

The results of the catalytic oxidation of n-butylmercaptide sodium in the presence of proposed and known catalysts (disulfonic acid phthalocyanine cobalt disulfonic acid salt and tetranitro-, tetraoxy- and tetraminophthalocyanine cobalt disulfonic acid) are given in Table 2,

table 2

1.05

, 09 7.2

7.79

1.00 10.68

12.88 U, 60 27.0

by oxidation of mercaptans to disulfides in a glass reactor 9 with a volume of 50 ml with a fixed layer of catalyst (bromine-substituted cobalt phthalocyanine derivatives deposited on activated carbon). Applying catalysts to activated carbon of the AG-5 grade by circulating solutions of bromo-substituted derivatives of phthalocyanine cobalt (5g / l) in 10; -th aqueous sodium hydroxide solution through activated carbon at room temperature for 90-120 minutes until the concentration of catalyst on the carrier 1 , May 7, D. Diesel fuel is placed in the reactor and oxygen is passed through for 5 min, the flow rate of which is 0.1 l / min, at the temperature in the reactor. Then the oxygen supply is stopped and the diesel fuel is analyzed for the content of mercaptans. PRI me R 11. Purification of diesel fuel from mercaptan sulfur in the presence of disulphonic,,, V cobalt tetrabromium phthalocyanine, carried on activated carbon. Diesel fuel is placed in a reactor with a fixed layer of disulfo, A, i, i-tetrabromophthalo cyanine cobalt, deposited on activated carbon, and oxygen is passed. On the 3rd-5th minute the degree of purification reaches 87. Example 12. Purification of diesel fuel from mercaptan sulfur in the presence of. dibromo 3 .6, 3, 3, 3, 6, 3, b -rktaoxyphthalocyanine cobalt supported on activated carbon B reactor with a fixed layer of dibromo-3, 6, c, b, 3, b, 3 b -octaoxyphthalocyanine cobalt coated on activated carbon, put diesel fuel and pass oxygen. For 5 minutes the degree of purification reaches 78. Example 13. Purification of diesel fuel from -meocaptan sulfur 310 in the presence of hexabrom -3.6,3,6 /, b, 3 b -oct-oxyphthalocyanine cobalt, applied activated carbon. In a reactor with a fixed layer of hexabrome -3.6, 3, b, 3, b, 3, b-octo-oxyphthalocyanine cobalt deposited on activated carbon is placed in diesel fuel and oxygen is passed. For 5 minutes the degree of purification reaches 83%. Example} C. Purification of diesel fuel from mercaptan sulfur in the presence of heptabrom-3,66,6,6, 6,3,6, -octo-oxyphthalocyanine cobalt, applied on activated -. ny y g. In the reactor with a fixed layer of -1 -1 x J fH.-Htfiii heptabil-3, b, 3, b, 3, o, 3, b octaoxyphthalocyanine cobalt supported on activated carbon is placed in diesel fuel and passes; uT oxygen., For 5 minutes the degree of purification is reached. Example 15. Purification of diesel fuel from mercaptan sulfur in the presence of octabr -3,6,3,6 ,, 3,6 -oct-oxy-phthalocyanine cobalt supported on activated carbon. Diesel fuel is placed in a reactor with a fixed layer of octabrom -3,6 ,, 6,3,6-octaoxyphthalocyanocyanine cobalt supported on activated carbon, and oxygen is passed through. For 5 minutes, the degree of purification reaches 97. The results of the tests carried out as well as the results of the purification of diesel fuel from mercaptan sulfur under the same conditions in the presence of limestone. Table 1 shows the available catalysts (disulfonic acid phthalocyanine cobalt disulfonic acid and tetranitro-, tetraoxy - and tetraminophthalocyanine cobalt disulfonic acid). 3-P91073312

Catalyst

Famous

Disodium salt of disulfonic acid phthalocyanine cobalt.

I / I I Disulfonic acid h, h, h, h - tetranitrophthalocyanine cobalt

I I 1 I Disulfonic acid H, h, h, h - tetraoxyphthalocyanine cobalt

I I | I Disulfonic acid h, h, h, h tetraminophapocyanin cobalt

Proposed

1 I 1 1 Dmsulfoch, h, h, h - tetrabrophthalocyanine cobalt

1,1, - III, 111 Dibromo-3,, 6,3,6,3,6-octaoxyphthalocyanine cobalt

II II II III III Hexabrom -3,6,3,6,3,6,3,6-octa-oxy-naphthopocyanin cobalt

II II II III, hi

Heptabrom-3,6,3,6,3,6,3,6,6 octaoxyphthalocyanine cobalt

;. fi, 11 111,111

Octabrom -3,6,3,6,3,0,3,6. Octa-oxyphthalocyanine cobalt The proposed method, using bromo-substituted cobalt phthalocyanine derivatives as a phthalocyanine catalyst, allows the oxidation of mercaptans to be accelerated and the degree of purification of hydrocarbon feedstock from mercaptans (1.3-2.2 times), which makes it possible to significantly increase the efficiency of catalytic demercaptanization (the catalytic activity of bromine derivatives of phthalocyanine cobalt 1, -3.5 times

Table 3

The degree of purification of diesel fuel from mercaptan

.. | higher catalytic activity of the best known catalysts). An important characteristic of a catalyst is its stability. Testing this method by the example of the oxidation of sodium n-propyl mercaptide using hexabrom -3,6,3,6, and 3,6 -octo-oxyphthalocyanine cobalt as a catalyst shows that the degree of purification of the model solution from sodium n-propyl mercaptide remains almost unchanged. 60 minute cycles.

13

The degree of purification of the model solution,% .8986

The proposed method can be used in the gas processing, oil refining and petrochemical industries in the production of disulfides, purification of a wide fraction of hydrocarbons, gasolines, kerosene, diesel fuels, etc. from mercaptans and regeneration, mercapto-containing alkaline reagents and effluents obtained from the purification of natural and liquefied gases from mercaptans, stabilization gases of thermal cracking and coking and other similar products of high-sulfur crude oils and gas condensates.

Claims (2)

1. The method of demercaptanization of hydrocarbons by contacting 910733It i: i; :: :: r: i: 3 ::::; :: i :: i 85 86 88 vanishing it with an oxygen-containing gas in the presence of phthalocyanine catalyst, characterized in that, in order to increase the degree of purification and accelerate the process, bromo-substituted cobalt phthalocyanine derivatives are used as a catalyst. 2. The method according to claim 1, using the brominated cobalt phthalocyanine derivatives previously deposited on a porous support. Sources of information taken so attention in the examination 1. Patent ClJA No. 2921020, cl. 208-205, published. I960. 2. USSR author's certificate No. 687065, cl. C 07 C 143/2 (prbtotip),