DE1545239A1 - Process for the complete or partial removal of straight-chain hydrocarbon compounds from hydrocarbon mixtures - Google Patents

Description

Dr. Expl.

PATENT LAWYERS

DR.-ING. BY KRE IS LE R DR.-ING. SCHDNWALD DR.-ING. TH. MEYER DR. FUES

COLOGNE 1, DEICHMANNHAUS

Cologne, December 10th, 1965 Fu / Ax / Fa

The British Petroleum Company Limited, Britannic House, Finsbury Circus, London, S.C.2 (England).

Procedure for total or partial removal of straight-chain hydrocarbon compounds aUi3 hydrocarbon mix.

(Trennannieldung 17)

(Separation from patent. Patent application 3 74 -f. 51 IVa- ⁷

-6a))

The invention relates to a method of manufacture of microorganisms, e.g. yeast, in particular to a process for the complete or partial removal of straight-chain Hydrocarbons from mixtures with other hydrocarbons.

Certain petroleum fractions, in particular gas oils, are known to contain straight chain hydrocarbons, mainly paraffins, which are waxes and adversely affect the Affect the flow point of the fraction. In other words, if all or part of these hydrocarbons are removed, the flow point of the fraction is lowered. The wax is usually removed by precipitation with the aid of solvents. This is what originally existed in the parliamentary group Wax as such, i.e. without being converted into more valuable ones Products won.

The petroleum fractions boiling under gas oils, e.g. heavy Naphthenes and kerosene also contain straight-chain Hydrocarbons, which are potentially valuable for conversion to other products, however, have heretofore been exploited these hydrocarbons are made more difficult

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separated from the petroleum fractions in which they are contained must be converted before being converted into other products can be.

In a process in which a microorganism is used for the complete or partial removal of straight-chain hydrocarbons from hydrocarbon mixtures, it has been found that in this process i,:. general by-products containing carbon, hydrogen and oxygen, e.g. esters, are formed. These by-products can remain in the hydrocarbon fraction which ν j; :: microorganism is separated off, and represent impurities. In particular, in cases where an i / ac .-.;. _; & Itijoj gas oil is used as the feedstock, the rev / onnene Jas "! As a result of the presence of these by-products a.: U." Above have a cloud point.

It has now been found that this vine product / te euro :, ο Ine LcugenwäscL-i can be removed or converted into less detrimental pr: rJ-; kue . Subject of the Γ.ν-ί'indrin ^ l..zt 'Je, ..- according to a process for the "/ complete or partial separation of straight-chain hydrocarbons, from Ge: .. iocnen with other hydrocarbons, which thereby gekerjrizelcr.net is that one cultivates a microorganism in the presence of e-ineo hydrocarbons, which consists of a mixture of straight-chain hydrocarbons with other hydrocarbons, in the presence of an aqueous nutrient medium and a gas containing free oxygen, then the microorganism from the rest The hydrocarbon is separated off and this residue is subjected to an alkaline wash.

Appropriately obtained from crude oil serve as input material

to hydrocarbon fractions.

öo.

- * The method gernäss the invention is particularly vjertvoll - * included for the treatment of Gaso1fraktionen from crude oil, the _{straight-w-chain} hydrocarbons in Porm ^ of waxes, as obtained by the method according to the invention a gas oil with an improved pour point, while the Waxes can be converted into a valuable product.

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The straight hydrocarbons are usually in the According to the invention, the feedstock used as peraffins available. However, they can also be present as olefins. Furthermore, mixtures can be used, the straight-chain Contains paraffins and olefins.

IJs is an important feature of the invention that when Zuchtung'von yeast in the presence of those described above Sinsatzuiateriallen under conditions conducive to the growth of the Favor yeast at the expense of the straight-chain hydrocarbons, the other hydrocarbons, e.g. isoparaffins, Naphthenes and aromatics, are not split or their split fraction is at best very low. Further In contrast to the usual chemical processes, which obey the law of action, the speed of removal of straight-chain hydrocarbons with smaller The increasing proportion of these hydrocarbons in the total mixture of hydrocarbons is not significantly lower (except of course in the final stages of removal). If desired, the achieved percentage conversion of the straight-chain hydrocarbons kept at a fourth approaching 100 without a disproportionately high expenditure of contact time is required to low Achieve improvements. Furthermore, in a continuous process, this high conversion can be achieved without the Use a long reaction path to help.

By using this process under conditions that limit the breakdown of the straight chain hydrocarbons, it is possible to work in such a way that only a desired part of these hydrocarbons is removed.

Suitable input materials for the process according to the invention are kerosene, gas oils and lubricating oils. These Feedstocks can be unrefined or subjected to some refining treatment, however

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they must contain straight chain hydrocarbons in order for to be suitable for the purposes of the invention. The content of straight-chain hydrocarbons in the petroleum fraction is expedient 3-45 wt .- ^.

As microorganisms that are grown according to the invention, yeast, fungi or bacteria are possible.

If you are using yeast, it will preferably be part of the family Cryptococcaccae, especially to the subfamily Cryptococcoidae. However, if appropriate, for example, ascosporogenic Yeasts of the subfamily Saccharomyceloidae can be used. The preferred genera of the sub-farnily Cryptoj ^ coccoidae are Torulopsis (also known as Torula) and Candida. The preferred yeast strains are listed below. The strains and their depository numbers are particularly preferred are mentioned in the following table, which are used to designate tribes that are present at the Centraal Bureau Schimmelculture, Baarn, Holland.

Candida lipolytica CBS 610 Candida pulcherrima Candida utilis CBS 841 Candida utilis, Variati major CBS 2317 Candida tropicalis CBS 133 Torulopsis collisculosa CBS 110 Hansenula anomala Oidium lactis Neurospora sitophila

Of the above-mentioned strains, Candida lipolytica is particularly preferred.

Bacteria can also be used as microorganisms. The order Pseudomonales, Eubacteriales and Actinomycetales used. Preferably

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bacteria used are the families Baoillaceae and Pseudomonadaceae »Preferred species are Bacillus megatherium,

Bacillus subtilis and Pseudomonas eeruginosa. More suitable Tribes are:

Bacillus amylebacter Pseudomonas natriegens Arthrobacter sp.
Micorcoccus sp.
Corynebacterium michiganense Pseudomonas syringae Xanthomonas begoniae Plavobacterium sp. devorans Acetobacter sp.
Actinomyces sp.
Agrobacterium sp.
Aplanobacter sp.

Of the mushrooms come those of the Aspergillaceae family in question. A suitable genus is Penicillium. Preferably Penicillium expansum is used. As another usable Genus Aspergillus comes into question.

The cultivation is usually carried out in an aqueous nutrient medium carried out. If necessary, certain solid nutrient media can also be used. In both cases, a gas that contains free oxygen. Penicillium expansum is suitable for cultivation in an aqueous nutrient medium, which contains hydrocarbon, Penicillium roqueforti, Penicillium notatum, Aspergillus fussigatus, Aspergillus niger and Aspergillus versicolor can be grown on solid medium containing hydrocarbons.

In addition to the feedstock, an aqueous nutrient medium and an oxygen source, preferably in the form of air, are required for the growth of the microorganisms. A typical nutrient for the cultivation of Nocardia has the following composition = 9 09831/1 1S8 _BAD ORIGINAL

-S- Ammonium sulfate 15A5239 ι g Magnesium sulfate 0.20 g Iron (II) sulfate heptahydrate 0.005 E Hangan sulfate monohydrate 0.002 g Monopotassium phosphate 2 g Disodium phosphate 3 pp Calcium chloride 0.1 g sodium 0.1 g Yeast extract o, oo8 c

Distilled // water (to make up to 1000 nl).

For other bacteria, a nutrient medium of the following is suitable Composition:

Monopotassium phosphate 7 g

Magnesium sulfate heptahydrate 0.2 g

Sodium chloride 0.1 g

Ammonium chloride £ 2.5,

Drainage water (trace elements) 100 ml

Yeast extract 0.025 g distilled water (to make up to 10OC ml)

A suitable nutrient medium for yeast (and mushrooms) is as follows Composition:

Diammonium phosphate 2 g

Potassium chloride 1.15 g

Magnesium sulfate heptahydrate 0.65 ß

Zinc sulfate 0.17 U

Manganese sulfate monohydrate "0.045 g

Iron (II) -su.lfatheptahydrate 0.0c8 g

Tap water 200 g

Yeast extract 0.025 g

Distilled water (to make up to 1000 al)

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Microorganisms, especially yeast, sometimes just grow with difficulty when first using Hydrocarbon fractions grown as a starting material will. Sometimes e.3 is required, for inoculation one To use microorganism which has previously been adapted for growth on the hydrocarbon fraction to be used is. It is also possible that the microorganisms in spite of the cultivation in the presence of an aqueous mineral Medium containing the appropriate nutrients grow with difficulty because the hydrocarbon fraction does not contain the growth factors found in carbohydrate feedstocks unless these growth factors are added.

The growth of the microorganisms used is favored, if you add a very small amount of a yeast extract to the nutrient medium (an industrial product rich in group B vitamins obtained by the hydrolysis of yeast) or in general to vitamins of group B and / or biotin. This amount is preferably in the order of magnitude of 25 parts per million, based on the aqueous fermentation medium. It can be higher or lower depending on the incubation chosen conditions.

The growth of the microorganism takes place at the expense of the fraction used with intermediate formation of bodies - mainly fatty acids - with acid function, so that the pH value of the aqueous mineral medium decreases progressively. Without correction, growth comes to a standstill fairly quickly, and the concentration of the microorganism in the medium or the cell density no longer increases, so that a so-called stationary Phase is reached.

The aqueous medium is therefore preferably made of high by gradually or continuously adding an aqueous medium pH held at the desired pH. Usually the pH of the nutrient medium when using mushrooms or

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Yeasts, especially when using Candida lipolytica, are kept in the range of 3-6, preferably 4-5 * (bacteria require a higher pH value of usually 6.5-ö) Sodium hydroxide is suitable as alkaline substances for adding to the seasoning, Potassium hydroxide, disodium hydrogen phosphate and Ammonia in free form or in aqueous solution.

The optimum temperature of the growth medium will vary depending on the type of yeast used and will usually be in the range of 25-35 ° C. When using Candida lipolytica, a temperature range of 28-32 ⁰ C is preferred.

The uptake of oxygen is essential for yeast growth essential. The oxygen is usually supplied as air. In order to keep the growth rate high, the air, which supplies the oxygen, can be broken up into fine bubbles by stirring. The air can be introduced through a frit however the system of ventilation known as "vortex ventilation" can also be used.

It has been found that when yeast of the Candida lipolytica strain is used in a method according to the invention, in which the ventilation takes place by "vortex ventilation", a high growth rate is achieved, with the generation time is in the range of 2-5 hours and the cell concentration is increased by a factor of up to 12 in 2 days.

In batch operations, the microorganisms initially grow with them slow increase in cell density. (This growth period is hereinafter referred to as the "inertia phase".) Thereafter

co the growth rate increases to a higher value.

to The period with the higher growth rate is than

* Denotes "exponential phase". Then the cell - * density constant again (the "stationary phase"). A certain _ * Amount of the microorganism for the start of the next batch ^ is preferably taken before the end of the exponential phase. Incubation is usually done before stationary Phase canceled. In this phase the microorganism becomes

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usually from the main mass of the aqueous nutrient medium and from the main mass of the unused feed fractions severed.

Optionally, the microorganism can before the other Cleaning of the product can be subjected to autolysis.

(j After one of the reconditioning methods of the product, first the greater part of the closed aqueous phase is separated off, This is preferably done by centrifuging or decanting. The separated aqueous phase usually contains one higher concentration of ions that are not nutrients than can be tolerated in the ice flow. If it does 1st, only part of the recovered aqueous phase can be recycled. For example, it is arched possible, about 96% by weight of the aqueous in the product Separate phase, of which (on the same basis) about 20 wt .-> o are discarded. The circulatory current will be complementary Quantities of the necessary nutrients are supplied, whereupon it is returned to the fermenter. If necessary, can the supplementary nutrients are fed to the fermenter as a separate stream.

When applied to the cultivation of yeast, the method can comprise the following product separation steps. In certain In addition to yeast, other microorganisms can also be separated in this way.

By centrifuging the product from the fermenter, three fractions are obtained, in increasing order Density:

I) an oil phase containing yeast cells,

II) an aqueous phase containing traces of oil and yeast, and

III) a "yeast cream" made from yeast, on whose cells a certain Amount of oil is bound, exists together with the aqueous phase.

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After fraction II has been obtained, fraction III or a mixture of fractions I and III with an aqueous one Surfactant solution mixed. The purpose of this treatment is to get the oil through, obviously Adsorption on the cells is held to separate from the yeast cells.

It can be beneficial to have an edible surfactant Means to be used, e.g. a sugar ester, which makes it possible to the effort for the subsequent washing, which is necessary to remove an inedible surface-active from the yeast To remove funds, to decrease.

The emulsion thus formed is centrifuged broken, obtaining three fractions:

IV) an oil phase

V) an aqueous one containing the surfactant Phase which is circulated for the treatment of fractions l) and III), and

VI) a "yeast cream" that consists of yeast that is still with oil is contaminated along with an aqueous phase of the surfactant.

In order to keep the consumption of surface-active agent as low as possible, the aqueous washing solution containing the agent is circulated.

Fraction VI can be washed alternately with surfactants Medium and centrifugation are worked up until the oil content of the yeast is a desired low Has reached value. The. now from yeast and aqueous surface-active agent bestefiae yeast cream can go ¥ with Water washed and centrifuged again. If necessary, this yeast cream can be washed twice or more will. If desired, one or more of these can be washed with water (but preferably not for the last) salt water (e.g. sea water) can be used. The final wash is preferably done with soft water.

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In order to keep the demand for soft water, which is necessary for the process, as low as possible, the entire Utilized water from the last wash: Part of it serves as top-up water for the nutrient medium in which the Fermentation takes place, some - if necessary - as make-up water for the solution of the surface-active agent, and the rest is added to the salt water used for washing, to reduce its salt concentration. Finally, the yeast can be dried under conditions that are suitable for later use as food and feed.

The hydrocarbon obtained, which is not broken down, is with or without inserted refining stage of the leugen wash subject. Aqueous or alcoholic sodium hydroxide is preferred for carrying out the lye wash and aqueous or alcoholic potassium hydroxide. The eyewash can with a 30-50% by weight aqueous alkali solution at a ratio of hydrocarbon to treatment medium in the range from 1: 1 to 1: 5 (based on Volume). If necessary, lye washing can be done with a 15-25% alcoholic alkali hydroxide solution carried out at a volume ratio of hydrocarbon to treatment medium in the range of 2: 1 to 1: 2 will. The process is preferably carried out with stirring. The temperature used is usually in the range from 60-100 ° C.

Measures that can be taken to prevent a> cleaned Microorganism or a product derived therefrom or the process with regard to the manufacture of the not To improve the split hydrocarbon fraction, are in the patents and patent applications mentioned below described. These measures can be taken as part of the Invention applied with the method described here will.

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_ ₁₂ _ 15A5239

Preferred processes which are used in the cultivation of the microorganisms and in the production of products are described in the following patents or patent applications;
British Patent 914 567

German patents (patent application B 74851

IVa / 6a), (patent application B 79521 IVa / 6b) and

(Patent application B 79522 IVa / 6b).

British patent applications

44606/62 49069/62 45005/65

46906/62 II68 / 65 45OO6 / 65

49051/62 2254/65 45007/65

49055/62 21255/65 45008/65

49054/62 21668/65 45OIO / 65

49058/62 25210/65 45OII / 65

49059/62 44998/65 45012/65

49060/62 45OOI / 65 45015/65

49065/65 45002/65 45014/65

49068/62 45005/65

In the following examples, the cell density is expressed as the dry weight of the yeast per liter of culture medium.

example 1

4o 1 of an aqueous mineral nutrient medium of the following composition are filled into a fermenter made of stainless steel, which has a capacity of 60 °. In order to keep the temperature in the fermenter constant at 50 ^° C., water was circulated in an annular space which was formed by the space between two concentric cylinders, the smaller of which represented the fermenter itself. The aqueous nutrient medium had the following composition:

Diammonium phosphate 2 g Potassium chlorate 1 * 15 g

Magnesium sulfate heptahydrate 0.65 g

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Zinc sulfate 0.17 g

Manganese sulfate monohydrate 0.0 ^ 5 g

Egg (II) sulfate heptahydrate 0.068 g

Yeast extract 0.025 g

Tap water 200 g

Distilled water (to make up to 1000 ml)

20 1 of an inoculum from a 24-hour culture hk of Candida lipolytlcy on a mixture of Cq-C, - iToruialparaffinen were then added so that the cell density was about 1 g / l. Then 1.03 l of weight were put into the fermenter Gnsöl (15 g / l) introduced, this amount was enough to keep the Bring cell density to 2 g / l. The temperature of the culture was kept at 30 ί 1 ° C, the pH value at 4. the Ventilation and agitation were made to be 3 millimoles Oxygen / l medium / min. ·

By an automatic pH control system, aqueous 10η-Aramonia introduced. After the addition of ammonia reached 20 ml, gas oil became according to the theoretical Needs of the culture assuming a yield of

100 χ dry weight of the yeast formed _ _{1 (} w required gas oil -7 °

added to a gross cell division time of 3 hours. These It was added every hour until the total amount of gas oil added was 17 l, i.e. 250 g / l.

Starting from a cell density of 2 g / l it was after 25 hours reaches a cell density of 18 g / l (at the end of the exponential growth phase).

Key figures of the gas oil used:

Density 15 ⁰ CA ⁰ C 0.876

Flash point, Afnor above 120 ⁰ C

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Cloud point + 20 ° C

Flow point + lo ° C

Noriiialparaffine 10 wt .- ^ u

Saybolt distillation

Siedeanfang 221 ^Ü C

5 # ■ 22o ° C

4C2 ° C end of boiling above 40 ^ ° C

Residue 1 vol

Loss 0 vol .- ^

A part of the culture was removed from the Perr.ionter after 25 hours. For this part 3 ^ 0 ml not delaminated gas oil were obtained by centrifugation at +50 ⁰ C. The remaining gas oil had the following key figures:

Density 15 ° C / 4 ° C 0.0939

Flash point according to Afnor over 120 C

Cloud point 0 ⁰ C

Flow point -16 ° C

n-paraffins $ 1.8 wt

Saybolt distillation ⁰ C

Initial boiling point 245

5 $ 296

50 # 365

95 # ^ 02

End of boiling - over 405 ° C

Residue 1 vol .- ^

Loss 0 vol .- #

ml of the non-split gas oil and 300 ml of 20 # strength alcoholic potassium hydroxide were placed in a 100 ml round bottom flask fitted with a reflux condenser and refluxed for 2 hours. The treated gas oil was decanted. 909831/1158

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Its cloud point was lowered from 0 to -16 ° C. Example 2

The experiment described in Example 1 was carried out with gas oil from a continuous culture of Candida lipolytica. repeated.

5 1 of a continuous culture in a 5 1 fermenter were with 500 rnl / h. an emulsion containing $ 10 gas oil in $ 90 of a mineral medium the composition mentioned in Example 1 was emulsified, supplied. The gas oil used had the following key figures:

Density at 15 ° A ° C 0.8? 5

Pour point + 17 ° C

Cloud point + 20 ⁰ C

Sulfur $ 1.6 wt

n-paraffins 12 wt .- $

Flash point according to Afnor 155 ° C

Saybolt distillation: ⁰ ° C

Beginning of boiling 159

5% 504

50 $ 562

95 * 598

Winning over

Residue 1 vol .- $

Loss' 0 vol. $

The pH was kept at 4-0.1 by the automatic addition of 10n ammonia using a suitable apparatus. The temperature was maintained at 50 ⁰ C. The movement and aeration were carried out in such a way that 5 millimoles of oxygen / l medium / min were supplied »

The cell density became constant after a few days with a value of 10-1 g dry matter / l. Then it became one

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Amount of culture withdrawn that by centrifugation at 5 C 500 ml of non-split gas oil was obtained. The rest Gas oil had the following key figures:

density
Pour point cloud point total sulfur n-paraffins flash point acc

Afnor

0.891 - 8 ⁰ C +20 ⁰ C 1.86 wt.

1.6 wt -.% 147 ⁰ C.

Saybolt distillation: Start of boiling

5% 50%

End of boiling residue
loss

^U C 260 506 564 398 over 1 vol. # 0 vol. %

This non-split gas oil was worked up in the manner described in Example / l. Its cloud point was lowered from +20 to -6 ⁰ C.

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Claims (6)

Claims ίΐ / Process for removing straight-chain hydrocarbons from their mixtures with other hydrocarbons compounds through cultivation of microorganisms in the presence of an aqueous culture medium on the mixture of hydrocarbon compounds in Presence of a gas containing free oxygen, characterized in that after the separation of the Microorganisms the remaining hydrocarbon fraction a Laugenv; üsche will be subjected- 2. The method according to claim 1, characterized in that subject a waxy petroleum gas oil fraction to the process becomes and the treated 3asöl with lye to one Frccukt is washed with a reduced cloud point. 3. The method according to claims 1 and 2, characterized in that lye washing with aqueous or alcoholic solutions of alkali metal hydroxides. especially Katriurnc-Ser Kaliumhydrc-xyd is carried out, with expediently 30 to 50% aqueous alkali metal hydroxyl solutions are used and the ratio of hydrocarbon to treatment agent in the range of 1: 1 to 1: 5 parts by volume. 4. The method according to claims 1 and 2, characterized in that that the lye wash Mt a 15 to £ 5 Ciew .- ^ igen alcoholic alkali metal hydroxide solution and a ratio from hydrocarbon to treatment agent carried out in the range from J: 1 to 1: £ VcI, parts will. 5. The method according to claims 1 to h, characterized in that the caustic washing in the temperature range from βθ to ICO Q is carried out. 909831/1158 6. The method according to claims 1 to 5 * characterized that yeast fczw 'bacteria used as microorganisms willηο 909831/1158 Β »OBKMNAL