DE2410612A1 - METHODS OF CLEANING UP AND HYDROCARBONS - Google Patents

Description

Applicant;

VEB chemical plant construction and assembly combine Leipzig

"Process for the purification of hydrocarbons"

The invention relates to a method for cleaning microbial or enzymatically treated hydrocarbons.

When using petroleum fractions as raw materials for microbial or enzymatic processes in which only a part or certain components of these fractions are used for the process, it was found that in the fraction shares not used, process-specific disturbing ingredients are formed and enriched, which adversely affect the characteristics of the fractions. Should the unused fractions be used again are supplied (e.g. as diesel fuel), these fractions must be subjected to intensive cleaning. Surface-active substances, metabolic and reaction products, Microorganisms and ash formers in the form of "free" inorganic ano the cations and organic metal vex'bindungen on. Me already known, will separate the unused process-specific ingredients obtained through the use of these contaminated oil fractions in a hydraulic refinery. Due to the high proportion of inorganic components, however, strong ash deposits occur on the hydrorafiriation catalysts, which make it necessary to regenerate the catalysts after an unacceptably short period of time.

Also call through the microbiological process in the petroleum fraction enriched substances (e.g. organic acids) cause corrosion in the refining systems. This means that microbial or enzymatic

409882 / 07U

matically treated petroleum fractions without additional treatment for Separation of the ash-forming components and by the microbiological Substances enriched in the process in the petroleum fraction are not suitable for use in large-scale hydraulic refining systems

On the other hand, cleaning can be achieved through a caustic bag or treatment with acidic solvents, especially hydrochloric and sulfuric acid

According to this process, the hydrocarbons to be cleaned with alkaline earth hydroxides or carbonates or with mineral acids, which are able to hydrolyze the surface-active substances, added, stirred for a long time and then a phase separation subject

With the help of these procedures, most of the impurities can be removed will. However, the hydrocarbons treated in this way are not yet suitable for all uses,

The purpose of the invention is to provide a method for cleaning the unused Fractional shares to develop that the quality of the fraction shares so improved that further processing or use of these fractions is made possible

The invention is based on the object of designing the cleaning so that that the process-specific ingredients largely consist of the unused Fractional shares are removed.

According to the invention the object is achieved in that the process-specific emulsion-causing and stabilizing substances from the microbial or enzymatically treated hydrocarbons in contrast to those previously known cleaning methods can be removed by a liquid-liquid extraction with phosphoric acid as the extraction agent. The phosphoric acid loaded with the extract becomes the microbial or enzymatic process as a source of phosphorus fed back or another Subject to treatment or reuse.

This further use can be, for example, the production of phosphate fertilizers or other phosphorus compounds.

Since with the help of the proposed solution, the Ketallverbindungen that are introduced through the IT medium, are removed, the hydrocarbon fractions treated in this way can be removed without further treatment

409882/071 4

Hydro refining are subjected »The serious effect of the invention Procedure consists in the decisive increase in the distribution coefficient for oil-soluble surface-active substances, Metabolism and reaction products in acidic solvents compared to pure water or aqueous alkaline solution as well as in the cleavage organometallic compounds and conversion of the metal components into the extractant. All mineral acids are used as extraction agents both in concentrated and in dilute aqueous solution in question »

So were investigations with sulfuric acid, hydrochloric acid and phosphoric acid carried out at different concentrations · The results showed that phosphoric acid was the best extraction agent Results have been achieved »

Feed hydrocarbon: fermentative

treated raw DK (boiling range: 24o - 36o °) temperature: 25 C

Extractant: 75% 1o% 5o; 5%

H-PO. H-PO. H-SO. H ₀ SO. HCl I 4.? 4 Z 4 ^ 4

Clarification time: 1 min 7 min 3 min 41 min 53 min

Reverse turbidity, clearing time
after shaking the clarified DK with HgO 4 min 11 »in 8 min 18 min 17 min total metabolic and

Reaction products 52 11o 56 122 1o8 mg / l.

Acid number (mg KOH / 100 ml) 3 2 3 3 2

These acids can optionally use organic solvents as solubilizers can be added.

The choice of acids depends primarily on economic considerations ab «So in many cases it is cheap to use phosphoric acid -use as phosphoric acid is used in many microbial processes Phosphorus source is used »This means that the acid coming from the extraction process can be returned to the microbial process as a phosphorus source will. In most cases it is necessary to contact the

409882 / 07U

Acid extraction a lye and water wash to neutralize any acids or acidic metabolic or reaction products that may be entrained to connect.

All types of extractors commonly used in technology can be used as traction apparatus be used, e.g. B. turntable extractors, packed columns, Pulsation extractors, etc.

Determination of special extraction conditions, such as temperature, ratio of extractant to input product, special extraction agent and concentration, residence time, extraction principle, extraction apparatus etc. depend on the specifics of the microbial or enzymatic process and the resulting characteristics of the Feed hydrocarbon as well as the quality requirements placed on the end products and is therefore a problem of technical and economic optimization with respect to predetermined selected target functions.

The choice of the ratio of extraction agent to feed hydrocarbon fraction is largely dependent on the selected extraction principle and the existing extraction equipment.

The tests carried out were in a Drehscheibenextraktor at an extraction temperature between 1o - performed 9o ⁰ C. The weight ratio of the extractant to the hydrocarbon fraction varies between 1: 1 and 1: 3oo. When using 75 # H-PO- as the extracting agent with a »weight ratio of acid to hydrocarbon action equal to 1: 2oo, the extracted hydrocarbons were obtained in sufficient quality»

With recycling of the loaded phosphoric acid, a large part of the in the Bicrobial process stage and the process stage for separating off the hydrocarbon fraction required surface-active substances recovered. This results in significant economic advantages · Since many MÜre · - Bial processes phosphoric acid or phosphates are supplied as a source of phosphorus, are created by the return of the loaded phosphoric acid to the ■ ikrobial process other economic advantages · It is favorable the phosphorus Choose the amount of acid so that the phosphorus requirement in the Permentor is covered can be so that no additional auxiliaries in the form of phosphates or phosphoric acid are necessary. The extraction with phosphoric acid can also be followed by refining with aqueous ammonia solution. Included

A09882 / 07U

is dependent at least added to the fatty acid content of an equivalent Ammonlakmenge in the form of dilute or "concentrated ammonia water, the two phases must be thoroughly mixed · The refining temperature is in the range of 5 - 5o ⁰ C, preferably due to the high vapor pressure of the ammonia at 2o C. the aqueous phase is separated from the refined phase and the thus treated fiaffinat is then freed by washing with Nasser at 5 to 5o ⁰ C, preferably at 2O ⁰ C, or by heating up to 2oo ⁰ C to remove dissolved ammonia. The ammonia-containing refining agent, which is loaded with the extracted acids in the form of their ammonium salts and or * or the ammonia-containing washing water of the raffinate is returned as a nitrogen and carbon source and or "or to regulate the pH value in the microbial or enzymatic process" The following Examples are intended to explain the invention but not to restrict it

example 1

1 liter of a petroleum fraction (crude DK boiling range 24o - 36o ⁰ C), separated by multi-stage separation at corriial temperature from a reaction mixture that was obtained during fermentation with the addition of surface-active substances (e.g. addition products of ethylene oxide on propylene) was obtained with Treated 500 ml of the acidic extractant at 25 ⁰ C for 10 min and then washed neutral with 1 / Sigen ammonia water and a final Was3erwäsohe, the characteristics were determined after the complete settling of the water.

Extractants' 75 # 1o # 5o # 1o # 1o #

H ₃ PO ₄ H ₃ PO ₄ H ₂ SO ₄ H ₂ SO ₄ HCl

Clarification time s a min 21 min 9 min 14 min 21 min

Reversion, clearing time after shaking
of the clarified DK
with HO 7 min 21 min 1o min 13 min 23 min

409882 / 07U

Total metabolism and reaction products mgA 73

114

112

1o9

Acid number

(mg KOH / 100 afl.)

2.5

Example 2

1 liter of a Srdölfraktion (crude DK boiling range 24o - 3ßo C) obtained by separation from the reaction mixture of the fermentation process at 7o - 9o ⁰ C is treated with 1 1 of the acidic extractant. To improve the separation, surface-active substances (e.g. adducts of ethylene oxide with propylene) were added

Extractant: 75% 1o% 5o # ige 1o% 1o% V ° 4 H ₃ PO ₄ H ₂ SO ₄ H ₂ SO ₄ HCl Clearing time: 8 min 14 min 7 min 14 min 18 min Cloudiness time after shaking of the clarified DK with H ₂ O 7 min 15 minutes 7 min 12 min 13 min Total metabolic and reaction pro ducts mgA 51 87 52 93 98 Acid number (rag K0H / 1OO ml) 4th 7th 3 11 15th

409882/0714

Claims (2)

Claims 1. Methods for cleaning up treated microbially or enzymatically Hydrocarbons by treating the hydrocarbons with acidic solvents before washing with alkaline or water be subjected to with or without the addition of solubilizers, characterized in that to remove the one Further use or further processing disruptive process-specific Ingredients, the hydrocarbons subjected to a liquid liquid extraction with phosphoric acid as the extraction agent with the process-specific ingredients loaded phosphoric acid is added back to a microbial or enzymatic process or to another treatment or is supplied for further use. 2. The method according to claim 1, characterized in that according to the Extraction with phosphoric acid a refining with the help of aqueous Ammonia solution is carried out, the raffinate by washing with water at 5 to 5o C or by heating up to 2oo C of dissolved ammonia and that this refining and WSsche with • in recycling than those loaded with fatty acids ammonium salts Amaonia water and / or ammonia OVER Wasohwassers in the microbial or enzymatic process, whereby the ammonia bfew « Fatty acid content as a nitrogen or carbon source known to calibration serve, is combined. 3 · The method according to claim 1, characterized in »that the PhoBphor- Acid used as a 2--100% acid, preferably a 10-80% acid will" 4 · The method according to claim 1 and 3, characterized in that the Extraction in the temperature range of 1o - 9o C is carried out. 5. The method according to claim 1 and 4, characterized in that the Weight ratio of extractant to hydrocarbon fraction varies in the range 1: 1 to 1: 300. 40988 2/0714