DD147365A1 - METHOD FOR PRODUCING SULFUR-PACKED PETROLEUM AND PETROLEUM FRACTIONS - Google Patents

Abstract

The invention relates to a process for sulfur removal from Eroel and Erdoelfarktionen, which finds application in the petroleum industry. The object of the invention is to produce low sulfur petroleum or petroleum fractions without direct contact with microorganisms. Petroleum oil or an oil-petroleum fraction is treated with a buffer phase comprising 40 to 70 Me.% To 40 to 70 Me.% At a Ph value of 7.5 to 8.5 .mu.m, containing a buffer substance, iron (II) chloride and desulphurizing enzyme systems dispersed, with Reynoids numbers in the range of 3 x 10 & exp 2! up to 4 x 10 & exp 4! be generated, a gasification erfogt with technical hydrogen erfogt and contact times of 1200 to 7200 s are respected. The content of iron (II) chloride in the wet phase is 0.5 to 1.5 g / l. As desulfurizierendes enzyme system, which is obtained from a mixed culture of obligate anaerobic bacteria of the genus Desulfovibrio, using a crude enzyme extract with an activity of at least 2 moles of hydrogen consumption per gram of enzyme nitrogen and 3800 s.

Description

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Process for the preparation of low-sulfur petroleum and petroleum fractions. _.

IPK: C 10 G 31/12

The invention relates to a process for removing sulfur from crude oil and petroleum fractions. The process is used in the oil-producing industry *

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ϊΐα petroleum and petroleum fractions are more or less extensive admixtures of undesirable compounds such as organic sulfur compounds of. Type JVierkaptan _} containing sulfide and thiophene.

With the use of petroleum and iSrdölfaulktionen these Mchtkougenwasserstoff compounds corrosive, reduce the activity of catalysts of petroleum and petroleum chemistry and. lead to high air pollution through the formation of sulfur dioxide when using the petroleum fractions for energy production. "Usually, the removal of these undesirable substances takes place by catalytic hydroenthing at high temperatures, high pressure and in corrosion-resistant plants."

However, the cost of such hydrocatalytic processes is "too high. Moreover, the application of hydrocatalytic desulfurization is not possible for all petroleum fractions."

Furthermore, microbiological processes for aerobic and anaerobic desulfurization with direct involvement of microorganisms are known (US Pat. No. 2,975,103, Japanese Patent No. 70.23831, USP No. 108583, USP No. 2641564, WO WT-SO).

In the known patent specifications, the petroleum compounds which contain sulfur in the molecule are removed by microbiological means by oxidation or hydrogenation. The end products of the microbial metabolism are predominantly sulfates or hydrogen sulfide. Pure microbiological desulphurization in the known patent specifications is given under the following conditions: a temperature range of 298-348 K, a pH range of 6, o-8.5 _; a pressure range of 0.98-294 bar, an iiedox potential of -200 to -400 mV and the use of a synthetic nutrient medium of different composition.

The activity of the microorganisms used in these processes is influenced by certain additives to the nutrient medium, such as growth stimulators, calcium carbonate, carbohydrates and the like, depending on the given fermentation regime. To improve the contact between the microorganism, nutrient medium and the product to be desulphurised, one also works with surfactants. The previously known methods for microbiological

Brit Sulfurization of crude oil and petroleum rock chemicals. have the Mach part; that & ⁱ microorganisms to grow and maintain their Stoffwechselvorga & ge a .be ~ agreed liienge consume in to entschwefelndem product and soioit a loss aa petroleum or "petroleum fraction eintri ^- tt!. In addition to this, the separation of the desulphurised product from the aqueous feed medium and the microorganisms is associated with a high level of technical complexity. "One of the essential characteristics of Hansel microbiological processes is the low rate of desulfurization per unit time."

Object of the invention

The aim of the invention is low-sulfur oil or ErdöIfraktionen with the least possible technical. To gain effort.

The problem solved by the invention is that low-sulfur egg oils or petroleum fractions are produced without direct contact with the microorganisms.

According to the invention, low-sulfur petroleum oils or petroleum fractions are obtained when a biochemical reaction is carried out between the petroleum or a petroleum fraction and a desulphurizing enzyme system, petroleum or a petroleum fraction being treated with an aqueous solution containing buffer substances with addition of sulfur-free surfactant and iron (II). Thus, with the desulphurizing enzyme system dispergiei-t becomes that Reynolds-Zahloa in the range

from 3 x 10 to 4 x 10 at the same time as gassing with industrial hydrogen. The contact time between the enzyme system and the petroleum or petroleum fraction must be from 12oo to 7200s. The desulfurizing enzyme system is preferably obtained from a mixed culture of obligate anaerobic bacteria in particular of the genus Desulfovibrio in a known manner. The use of the enzyme system takes place as a crude enzyme extract. The biochemical reaction, carried out at atmospheric pressure and at normal temperature, is carried out in a reactor which is simple in terms of process, and the following reaction conditions are to be observed:

PH of the aqueous buffer solution containing 7f5-8.5

• Concentration of ferrous chloride o, 5-1.5 g / l

• Activity of the desulphurizing crude enzyme extract when used in the reactor at least 2 moles of hydrogen consumption per gram of enzyme nitrogen and 36oo a

• Ratio of petroleum or petroleum fraction to total aqueous phase 40-70 Ma% to 6Ο-3Ο Ma%

• Use o, 1-o, 8 kg of crude enzyme extract per 100 kg of petroleum or petroleum fraction

After completion of the enzymatic reaction, the low-sulfur petroleum or petroleum fraction is separated from the aqueous phase by separation at temperatures of 333-342 K. The exhaust gases formed in the biochemical reaction still contain a substantial portion unreacted Wasserstoffs.Dieser hydrogen, after separation of the Sulfur-containing associated gases are used again in the enzymatic process.

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The method according to the invention will be explained in more detail with reference to the following example.

In an under normal pressure and at normal temperature continuous-working biochemical reactor petroleum ₉ is a buffer substances containing aqueous solution with addition of o _t 5 kg / m · ^ type surfactant of polyethylene-propylene oxide adduct, 1.27 kg / m ^ iron ™ Il- chlsjrid and o, 2 kg / loo kg oil desulfurizieraiider Rohenzjmextrakt so that a emulsified _s EöynoIds ™ number of 6 x 1O ^ could be produced _β vmrden as desulfurizie'rendes enzyme system, intracellular enzymes from bacteria of the genus Desulfovibrio used. The crude enzyme extract was obtained in a known manner from a .Mischkultur containing predominantly the obligate anaerobic bacteria of the genus Desulfovibrio, which had been isolated from Abwassersedimentea »The activity of desulfurizierenden Rhenzymextraktes when used in the reactor was 2 _S 4 moles of hydrogen verb smoke per gram of enzyme nitrogen and 3600 s »

By the composition of the Pufferaubstanzen containing aqueous solution, a concentration of 0.186 kg / rn ^ potassium dihydrogen phosphate 1jO97 kg / m ^ disodium hydrogenphosphate and a pH of 7 »β was established.

The ratio of petroleum to aqueous phase was 65-35% by mass. The technical hydrogen required for the biochemical reaction was fed to the system by fumigation, the fumigation intensity being 90% by weight of crude oil and 3600 s.

The contact time of the petroleum with the crude enzyme containing aqueous phase in the reactor was 3δοο s.

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The two-phase system leaving the reactor has been separated at 338 K in a separation stage. The unreacted hydrogen was separated off from the exhaust gases produced in the biochemical reaction and redispersed

used in the Bsaktion. '

Under these conditions, the used petroleum could be desulfurated to 63 % .

Claims (2)

5992 A process for the production of sulfurous Noise oil or ^ ErdÖIfraktionen at normal pressure and Norma! Temperature characterized in that the oil or oil fraction with a buffer substances, Eisexi II chlo "RID and desulfurizierenden Enzyiasystem _s is an aqueous solution containing dispersed so that Reynolds payment • p Il lea. be produced in the Boreich of 3 "10 to 4» 10, a fumigation with technical hydrogen takes place and maintained contact times between enzyme system and petroleum or Erdölraktion from 12oo to 72oo s Process according to item 1, characterized in that a ratio of petroleum or petroleum fraction to aqueous solution of 4060 Ma% to 60-30 Ma%, a pH of 7.5 ~ 8.5, a content of iron (II) chloride of ο , 5 ~ Ί> 5 δ / 1 Vv'äßriger phase and the .dasulfurizierende enzyme system, which is obtained from a mixed culture of obligate anaerobic bacteria of the genus Desulfovibrio, as a crude enzyme extract of at least 2 kg of hydrogen consumption per gram of enzyme nitrogen and 3% is used.