Process for the production of gaseous and liquid hydrocarbons and products obtained by this process.
Here is the full text of the only patent issued by Doctor Laigret concerning his work on obtaining gas and oil from bacteriological fermentation. You can download the text in its original form in .pdf here.
The present invention relates to a method of producing gaseous and liquid hydrocarbons hydrocarbons, especially crude oils, from organic substances by fermentation.
The applicant has in fact found that, under particular environmental conditions, certain microorganisms were capable of causing fermentations leading to the formation of hydrocarbons from organic substances with quantitative or almost quantitative yields. He further found that these microorganisms were able to perform their destructive action of organic substances with production of hydrocarbons almost indefinitely without appreciable consumption of nutrients and without degradation of the catalysts employed.
The microorganisms specific to the production of hydrocarbons by the process forming the subject of the invention belong to the category of anaerobic microbes and more, particularly to the class of the bacillus perfringens. Preference is given to the strain of bacillus perfringens identified by Professor Weinberg and cataloged under number 5.029 in the collection of the Institut Pasteur in Paris.
So that the fermentation is oriented towards the production of hydrocarbons, the applicant has found that the presence of iodine and silica, in the medium in which the bacillus works, was essential; for convenience and without having to link a theory to this choice of term, iodine and silica will be referred to globally as catalysts.
The most convenient and favorable medium is an aqueous medium in which iodine is present in a very small amount, the optimum iodine content being about 0,02 to 0,01 percent and the silica present in the form of. a fully flooded bed. In order to obtain rapid and active fermentation, it is advantageous for the height of this bed to represent at least one sixth of that of the bath above the bottom of the container which contains it.
The silica, in order to have a large surface action, is preferably in the very divided state (grains or powder for example). All kinds of sands consisting essentially of silica can be used, but Kieselgühr is particularly recommended.
As for the iodine, it can, for example, be introduced into the medium in the form of an iodine-iodide liquor such as Lugol's liquor.
Among the organic substances capable of supplying hydrocarbons under the action of anaerobic bacilli, the soluble salts of aliphatic acids, more particularly the alkali salts, including ammonium salts, as well as the lower aliphatic acids themselves and alcohols lower aliphatics, have proved to be particularly advantageous and easy to use because of their solubility in water. The substances in question can be used either individually or in the form of mixtures, in particular industrial mixtures or industrial solutions. Salts of higher fatty acids can in particular be used in the form of soaps, such as commercial soaps, prepared from vegetable or animal fats.
Thus, in the form which is preferably adopted in practice, in particular for reasons of economy, the process which is the subject of the invention consists mainly in maintaining, in the presence of silica, in the conditions for carrying out a fermentation anaerobic, an aqueous and neutral solution of one or more substances of the category consisting of lower aliphatic acids, water-soluble salts of aliphatic acids and lower aliphatic alcohols, solution which also contains iodine , microbes of the Bacillus perfringens class and nutrients for these bacilli. However. the invention resides, more generally, in the application of these microbes from organic substances in the presence of silica and traces of iodine.
The execution of a fermentation and the conduct of this fermentation under the conditions required for anaerobiosis obviously means that the environment in which the process takes place must be at a temperature of the order of 37 ° C and that the presence of air is harmful. Regarding the temperature. The applicant has found that it is possible to operate at temperatures a little lower than 37 ° C without causing serious damage to the production of hydrocarbons; this is how this production is still good at 30 ° C but slower. In order to exclude air as far as possible, it is convenient to operate in tanks closed by a cover provided with a gas release tube with valve and to fill these tanks with liquid up to the cover.
In normal operation, the fermentation balances itself to neutrality (ph 7) but if, accidentally, the medium becomes acidic, it is necessary to restore neutrality, for example by adding soda or sodium carbonate.
For the implementation of the process it is advantageous to first prepare an aqueous solution of nutrients, to add a pure culture of bacilli as well as iodine, to place the whole in the container or containers lined with 'a sterile silica bed, filling them completely. then to add the fermentable substances which one renews as and when they are consumed.
Fermentation, once started, is thus continued continuously without the need to renew the nutrients and catalysts, provided, at least, that one can conclude from a test of ten consecutive months of fermentation.
To maintain the strain of bacillus chosen, the procedure is carried out in the manner well known to bacteriologists, for example according to the method of subculturing in Veillon agar or in Y tubes. Lobby. When you want to inoculate a medium intended for fermentation, you can start by transplanting the strain in glucose broth at 2 per thousand, put in an oven at 37 ° C for 48 hours, check the purity of the culture - adjust the pH to 7 and take 20 cubic centimeters of this seed for a liter of the medium you want to ferment.
Nitrogenous substances from various sources can be used as nutrients: maceration of meat or fish, sterile decoctions of animal waste, manure, etc. A particularly advantageous medium is peptone water at 10 per thousand. It is recommended not to exceed the corresponding nitrogen content otherwise the activity of the ferment will drop.
When lower aliphatic acids or their alkali salts are subjected to fermentation, the hydrocarbon which begins to form after a certain period of time and which is then produced continuously is methane or mainly methane. For the proper functioning of the fermentation, it is advantageous to initially use an alkaline salt of lower aliphatic acid as a fermentable material, which leads to the formation, in the reaction medium, of alkaline carbonate subsequently playing the role of buffer. and the operation can be continued with the acid itself as soon as the methane fermentation has started.
When it comes to subjecting lower aliphatic alcohols or salts of higher aliphatic acids (the latter leading to the production of oils), it is advantageous to initiate a methane fermentation beforehand, for example by means of a alkali formate, and then proceed to the addition of alcohols or salts of higher acids, optionally with concomitant continuation of the addition of acid or salt of lower aliphatic acid.
The invention comprises, as new industrial products, mixtures of gaseous hydrocarbons and liquid hydrocarbons which can be prepared by the process defined above. Due to their similarity in appearance, constitution and properties to natural oils, mixtures of liquid hydrocarbons are referred to herein, for convenience, as oils.
In order to illustrate the manner of carrying out the method forming the subject of the invention, a few examples will be given below which, of course, are in no way limiting.
In a nutrient and iodized medium, prepared as described above, sodium formate is introduced at a rate of 4 to 8 parts by weight per 1000 parts by volume of this medium, it is inoculated and brought to 37 ° C
During the first three days, carbon dioxide and hydrogen are released.
The volume of this release is variable: it is, on average, 500 parts by volume for 1000 parts by volume of cuvée. Its composition also varies in fairly large proportions, the hydrogen being able to constitute from 30 to 80 percent of the mixture.
From the fourth day, a negative period is observed during which nothing emerges. It lasts 8 days. Toward the tenth or twelfth day, a new release appears: it consists of carbon dioxide (average 50%) and methane (average 50%). Were collected, and for this gaseous fuel mixture, on average 1000 parts by volume per batch of 1000.
The methane fermentation is then installed. It can be maintained indefinitely by adding new formate or, more simply, formic acid, because the medium is spontaneously buffered with the carbonate resulting from the decomposition of the formate. From this moment, 2 to 4 parts by volume of formic acid are introduced per day and per 1000 parts by volume of cuvée; there is a bubbling of carbon dioxide which is allowed to leave freely then the fermentation is allowed to continue. Continuous walking is, by this means, assured. Its flow rate, very regular, is 800 parts by volume of gas per day and per 1000 parts by volume of cuvée. However, the practical yield is poor reduced to the unit of weight of raw material, it does not exceed 200 parts by volume of gas per part by weight of formic acid and the gas, although a good fuel, contains only 50% e of methane.
Fermentation of formates alone is of little interest for the continued maintenance of methane production, but it is useful for initiating the latter and, in general, for preparing the medium for other types of fermentation. Consequently, in practice, it is recommended to always start with the formate alone and then to move on either to the additions of alcohol if one wishes to continue producing gas, or to the additions of soaps if one wishes to obtain liquid carbides. , as emerges from the following examples.
In a medium where the methane fermentation has been initiated beforehand by one or more successive charges of formate, methanol or ethanol is added at a rate of one part by volume per day and per 1000 parts by volume of cuvée. This volume of one part is understood for pure alcohols, but it is equally possible to use the same volume of mixtures of alcohols or the corresponding volumes of various alcoholic solutions.
The results are the same whether methyl alcohol or ethyl alcohol is used. A gas is obtained containing 60 to 82 percent of methane; the rest is carbon dioxide, never carbon monoxide. This gas is therefore not toxic and it is easy to remove carbon dioxide from it if desired.
The following guidelines highlight the values yields:
at. A cuvée with a capacity of 1000 parts by volume was maintained from April 25 to May 4, 1947, i.e. for 10 days, by adding ethyl alcohol. A total of 6 parts by weight of alcohol was used. The vessel provided 5430 parts by volume of gas.
Average flow per day per 1000 parts vintage volume: 543 parts by volume of gas.
Production per parts by weight of alcohol: 905 parts by volume.
b. A cuvée with a capacity of 1000 parts by volume was maintained from March 31 to May 9, 1947, i.e. for 40 days, alternately with methyl alcohol and ethyl alcohol. A total of 41 parts by weight of alcohols were used. The vessel provided 29445 parts by volume of gas.
Average flow per day per 1.000 parts vintage volunre: 736 volume parts.
Production per part by weight of alcohol: 718 parts by volume.
vs. A cuvée with a capacity of 1000 parts by volume was maintained from March 31 to August 7, 1947, ie for 130 days, by additions of methanol and ethanol representing a total of 71 parts by weight of alcohols. It released 81425 parts by volume of gas.
Average flow per day per 1000 parts vintage volume: 626 volume parts.
Production per part by weight of alcohol: 1146 parts by volume.
In an environment where the methane fermentation has been initiated beforehand with formate. formate is continued to be added at a rate of 2 to 3 parts by weight per day and per 1000 parts by volume of the batch, and in addition an equal weight of sodium or potassium oleate is added each day. To facilitate the addition of the soap, a certain quantity of the medium is withdrawn from the tank, the soap is dissolved therein hot, boiled for a few minutes and returned to the tank.
The release of methane stops; for a few days, only carbon dioxide is released and then nothing is finally released. At the same time we see forming on the surface of the medium a zone of reddish appearance, with a lower limit at first indecisive; then this zone condenses to make a layer clearly separated from the underlying aqueous liquid, it takes a mahogany hue which darkens more and more and tends towards black.
This layer consists of crude oil which is easily collected by suction or simple decantation.
Thus, from June 5 to August 24, 1947, a tank received, for 80 days, 224 parts by weight of formic acid and 208 parts by weight of ordinary commercial soap prepared with olive oil. and potash. 197 parts by volume of crude are formed, which are subjected to fractional distillation.
Is obtained percent:
- 1 part by volume at 100 degrees (water);
- 4 parts by volume from 100 to 200 degrees;
- 5 parts by volume from 200 to 300 degrees;
- 20 parts by volume of fractions passing between 300 and 320 degrees;
- 30 parts by volume of fractions passing fwre 320 and 340 degrees
- finally 5 parts by volume of fractions between 340 and 350 degrees.
At 350 degrees, 35 parts by volume of a black pitch remain which is not distilled but which burns leaving a thin coating of residual coke.
It is convenient to operate at atmospheric pressure but one does not depart from the scope of the invention by working at a different pressure.
The proportions of raw materials indicated in the examples are the optimum proportions, of course, the invention is not limited to the adoption of such proportions but if one deviates from them notably, in particular if the 'we clearly exceed the double or if we reduce them, the yields decrease.
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- The project Laigret