Method of synthetic oil production out of greenhouse gases

FIELD: oil and gas industry.

SUBSTANCE: group of inventions is related to method of synthetic oil production out of greenhouse gases. The invention suggests the method of synthetic oil production out of gas containing CO2; synthetic oil produced by the above method, usage of synthetic oil as well as use of gas containing CO2 are specified in the suggested method. The method includes the following stages: gas delivery to the reactor containing culture of at least one species of microalgae capable of photosynthesis; photosynthesis using CO2; anaerobic fermentation of the received biomass; thermochemical decomposition of fermented biomass to receive synthetic oil mixed up with water and gas and separation of the produced synthetic oil. Upon photosynthesis stage from 5 up to 100% of the culture is removed from the reactor and divided into solid and liquid fraction. Solid fraction is subject to anaerobic fermentation stage. Carbonates and/or bicarbonates are separated from liquid fraction. Then liquid fraction less carbonates and bicarbonates is returned at least partially to the reactor.

EFFECT: inventions ensure large capture of CO2.

29 cl, 5 dwg, 11 tbl, 3 ex

 

The technical field TO WHICH the INVENTION RELATES

The present invention relates to a method for producing synthetic oil from greenhouse gases, and the method is effective on an industrial scale and is carried out continuously. Through this method you can effectively capture, convert and re-evaluate WITH2and other greenhouse gases (NOx, CH4,...) and thus to achieve a negative net balance, or, in other words, this method allows you to capture more CO2than to produce, and what beneficial and environmentally safe for the environment.

Thus, high-energy artificial oil that is suitable for use in any internal combustion engine, turbine or boiler. This synthetic oil is distinguished mainly by its analogy with the currently used fuel (a mixture of chemical components, hydrocarbons, of which after purification receive different types of clean fuels such as gasoline, diesel fuel, kerosene, etc.).

Moreover, the present invention relates to the use of synthetic oil in internal combustion engines.

The LEVEL of TECHNOLOGY

Under understand global warming increase average temperature earth's atmosphere and oceans, resulting from�teniu climate. This increase accelerated in the last decades of the 20th century and early 21st century as a result of human activity, as a consequence of industrial emissions (greenhouse gases, such as NOxWITH2, CH4etc.), along with deforestation, which to some extent broke the existing balance in nature. This phenomenon is known as the greenhouse effect.

Greenhouse gases absorb photons in the infrared region of the spectrum emitted by the earth, warmed by the sun. The energy of these photons is not enough to start the chemical reactions with rupture of covalent bonds, rather they just raise the energy of rotation and vibration of molecules involved. Due to the collision of molecules of the excess energy is then transferred to other molecules in the form of kinetic energy, i.e. is heated by increasing the temperature of the air. In the same way, the atmosphere cools by emitting infrared energy, along with appropriate transitions from vibrating and rotating state in molecules lead to lower levels of energy. All these transitions require a change of the dipole moment of the molecules (i.e., modifications in the distribution of electric charges on their polar relations) that does not affect the two main gases that make up air, namely nitrogen (N2) and oxygen molecules which, because they are formed by two �same atoms, there is no dipole moment.

"Anthropogenic theory" predicts that global warming will continue if greenhouse gases continue to stand out. The human race is one of the most significant climatic agents. His influence began with deforestation for cultivation of crops or pasture, however, at the present time, the human influence has greatly increased due to the production of a copious emission of gases that cause the greenhouse effect, i.e. CO2from factories and vehicles and methane from intensive livestock and rice fields.

To date, and emissions of gases and deforestation has increased to such an extent that the reduction would have been difficult in the immediate and delayed future due to technical and economic consequences for the involved industries.

By the end of the 17th century people began to use fossil fuels accumulated in the bowels of the Earth during geological history. Kerosene, coal, and natural gas has led to increased CO2in the atmosphere, which recently reached 1.4 ppm per year and creates the resulting temperature rise. I believe that since man started to measure the temperature about 150 years ago (in the industrial era), it has increased by 0.5°C, and suggests that there will be 1°C higher by 2020 and by 2°C by 2050.

There are several possible effects of global warming according to theories of global warming would hypothetically affect the environment and human life. The main effect is the progressive increase in average temperatures. This in turn leads to a large number of changes, such as rising sea levels, changes in agricultural ecosystems, the spread of tropical diseases and the increasing intensity of natural phenomena. Some of these phenomena actually occur in the present time, however, it is difficult to accurately and uniquely associate with global warming.

In this regard, the Kyoto Protocol I supported the reduction of polluting emissions, such as greenhouse gases (mainly CO2).

Also due to the fact that one of the main sources of emissions of CO2is the burning of oil and its derivatives, we developed a large number of systems and methods for minimizing this problem.

One of these is the development of synthetic oil (biodiesel) based on the cultivation of high quality crops, however, today they showed their low efficiency; furthermore, the possibility of obtaining significant quantities of synthetic oil requires vast areas of the soil; often the cultivation of these crops requires advanced�th deforestation of existing forests and in many cases they also burn, which entails associated emissions.

Subsequently, groups of researchers have developed new systems and ways in which as capture agents WITH a2used microscopic algae, to then convert them to synthetic oil (biodiesel) through reactors that are open to the external environment, which had a significant drawback due to the environmental pollution caused by methods of cultivation (also, they are harder to control, they can't pump out About2that have less production per hectare, etc.).

Due to this significant problem has created a closed system that worked horizontally and, thus, to eliminate possible external contamination. However, the main problem with them was that because the systems are horizontal and are working with vast fields of grain, their removal or treatment requires a significant inclusion in the system of energy that briefly created an extensive pollutant emissions and unfavorable energy balance.

In the future, to the present time developed ways to address all of these challenges and producing synthetic oil (biodiesel). However, they still allowed junk cleaner balance because, at the end of�nom account, they continue to emit huge quantities of CO2.

The described systems are systems that their limitations can actually create an artificial oil (in this case, biodiesel) based on seizure2. However, due to low yield per hectare, production per m3(and therefore unsatisfactory coefficients capture WITH2), the complexity of the procedure and ability of the production of only one fuel (since it is done only biodiesel, it does not solve the shortage of oil in the future) there are many reasons for finding a new way to solve all these issues and specifically the way that will capture large amounts of CO2than the number of CO2that are subsequently released, or, in other words, a need for new sustainable ways that achieved a negative net balance of CO2for a long day.

Description of the INVENTION

The present invention relates to a method for producing synthetic oil from greenhouse gases, which is advantageous in industrial relation and is continuous. Through this method it is possible to capture, convert and re-evaluate WITH2among other greenhouse gases (NOx, CH4,...) effective way�m, to achieve a negative net balance, or, in other words, through this method captured more CO2than is formed, and a positive and sustainable manner for the environment.

Thus, high-energy artificial oil that is suitable for use directly in any internal combustion engine, turbine or boiler, which operate using a liquid fuel. This synthetic oil is distinguished mainly by its analogy with the currently used oil (a mixture of chemical components, hydrocarbons, of which the refining process receive different types of fuel, gasoline, diesel fuel, kerosene, etc.).

Therefore, the first aspect of the invention relates to a method for producing synthetic oil from gas, which contains CO2, wherein the method comprises the steps:

and. Receipts gas containing CO2in a reactor containing a culture that includes at least one species of micro-algae capable of photosynthesis;

b. The process of photosynthesis carried out by the form of microalgae-based CO2received for production of biomass;

C. Anaerobic fermentation of biomass obtained;

d. Thermochemical decomposition of fermented biomass at a pressure of IU�do 0 and 20 MPa and at a temperature between 200 and 420°C for synthetic oil, mixed with water and gases, and

E. Department of the obtained synthetic oil,

characterized in that after the implementation phase of photosynthesis between 5% and 100% culture is released from the reactor and subsequently separated into a solid fraction containing biomass that will be subjected to further stages of anaerobic fermentation, and a liquid fraction containing carbonates and/or bicarbonates, which are separated from the liquid part, then to at least partially recover the liquid fraction in the reactor, and essentially free from carbonates and/or bicarbonates.

In General, the method of the invention includes stages:

- biological treatment of greenhouse gases;

- mechanical treatment of the culture medium;

- mechanical-chemical treatment of aqueous phases and

- mechanical-chemical treatment of biomass.

Stage biological treatment of greenhouse gases

According to a preferred first embodiment of the implementation stage of the biological treatment of greenhouse gases includes the following podpisy:

- the flow of gas that includes CO2in the reactor, which contains a culture containing at least one kind of microalgae, which can perform photosynthesis; and

- fixation and the biological conversion of CO2by photosynthesis carried out by the form of microalgae, for the production of biomass�.

According to another preferred embodiment of the sub-phase to gas containing CO2such as , for example, greenhouse gases, contains endogenous and/or exogenous flow of greenhouse gases into the reactor photosynthetic type, in which there is at least one species of micro-algae capable of photosynthesis.

In this respect, throughout this descriptive messages under "greenhouse gases" should be understood as any gas that includes CO2and potentially other components, such as NOx, CH4or other, in any combination. The only in fact a precondition of the method of the invention is the inclusion in the gas at least WITH2. Thus, these gases, which are so harmful to the environment, become part of the nutrients added to the reactor for "feeding" are there microalgae.

Moreover, greenhouse gases, added exogenously, usually comes from the atmosphere or from any industry, and endogenous supplements come from gases created in the method according to the present invention.

Based on the composition of these gases, there is an opportunity to expose them to pre-treatment prior to the introduction.

According to another preferred embodiment of the of neobythites�Naya pretreatment of greenhouse gases can be accomplished by eliminating the SO x, NOxand humidity and adjusting the temperature to about 30-40°C. By the pre-processing phase (if necessary), these gases are introduced into the culture.

According to another preferred embodiment of the sub-phase commit and biological transformation of CO2contains the process of photosynthesis by the microalgae. Moreover, in the most preferred embodiments of the invention, the reactor containing them is subjected to continuous exposure to light, whether natural or artificial, and added into culture medium as nutrients and not necessarily of antibiotics and antifungal agents.

Thus, microalgae, being in the reactor due to the flow of gas, which includes at least CO2fix carbon from carbon dioxide and other nutrients and assimilate it and turn in for biological molecules such as carbohydrates, fats and proteins.

Moreover, microalgae recorded greenhouse gases at the previous stage, the culture medium in the reactor is mainly subjected to turbulent regime. Thus is achieved that the entire culture of microalgae are able to capture these gases and to receive the light required for the implementation of photosyn�ESA. Also, creating a turbulent environment gives the advantage of preventing the formation of deposits, that is, the undesirable accumulation of microorganisms on the surface of the photobioreactors. Obtaining turbulence to achieve this goal may be accomplished by any method, although in preferred embodiments of the invention is carried out by injection to the reactor of any of the following gases: air, N2WITH2, CO, NOxand gases obtained by combustion, or any combination thereof.

In addition, microalgae present in the reactor, selected from the group formed by: Chlorophyceae, Bacillariophyceae, Dinophyceae, Cryptophyceae, Chrysophyceae, Haptophyceae, Prasinophyceae, Raphidophyceae, Eustigmatophyceae, or any combination thereof.

Stage of machining the culture medium

According to another preferred embodiment of the stage of mechanical treatment of the culture medium contains podpisy:

- at least partial emptying or removing culture from the reactor;

- separation of the extracted culture on a solid fraction containing biomass and a liquid fraction containing carbonates and/or bicarbonates.

According to another preferred embodiment of the in podpisu emptying is extracted at least from 5 to 100% culture medium, preferably from 5 to 50% and preferably even pain�e, i.e. 10% of the culture medium, so that the remaining part is retained in the reactor and continues to capture and convert WITH2continuously using microalgae as a biological medium for this purpose. It is important to note the fact that this % extraction preferably replace quickly with water, which is essentially lacking in the algae and in the absence of carbonates or at very low concentrations, on the basis of stages of separation that will be described in detail below; the amount of algae present in water, which re-add will depend on the efficiency of separation of each specific method.

According to another preferred embodiment of the sub-phase of separation of the extracted culture on solid fraction, which contains biomass and a liquid fraction, which contains carbonates and/or bicarbonates, represents at least one stage of mechanical extraction, selected from filtration, centrifugation, education floc, electrocautery, ultrasonic, evaporation, decantation, or any combinations thereof. Thus it is possible to separate the liquid phase from the biomass.

According to another optional preferred embodiment of the stage after emptying must be carried out stage podci�ing the culture medium, extracted or extracted from the reactor. This optional sub extracted or extracted culture medium is accumulated in a storage tank in which add at least one acidifying agent until a pH value between 3.5 and 8, preferably between 6 and 8. The acidifying agent is selected from the group formed by CO2(this CO2can be butilirovannyh or industrial), the mixture WITH2and air, strong or weak acids, or any combination thereof. Preferably, the acidifying agent was a mixture of CO2with air. This way you can ensure that the environment from the reactor, which is enriched in CO2and bicarbonate, not precipitable (due to the impossibility of formation of carbonates) and, thus, prevents phenomena such as adhesion and deposition.

Mechanical-chemical treatment of the water phase

According to another preferred embodiment of the chemical treatment of the aqueous phase includes the following podpisy:

- chemical conversion of CO2that is present in the liquid fraction obtained by at least partially removing the culture from the reactor, in the form of carbonates and/or bicarbonates dissolved in the corresponding carbonized forms, precipitated PU�eat adding alkali, and

- at least partial return of the liquid phase, is already essentially devoid of carbonates and/or bicarbonates in solution, to the reactor.

Therefore, according to another preferred embodiment of the sub-phase chemical transformations WITH2includes transport water produced from the separation of biomass from water podpisy, in a container for cleaning, which accumulate the aqueous phase containing water, dissolved nutrients, WITH2, carbonate and bicarbonate, all of them are in a dissolved state. When reaching the water phase vessel for cleaning there is added at least one basic environment for deposition in the form of carbonates species that are in equilibrium (CO2bicarbonate and carbonate). So this way you can eliminate even more CO2because it is converted to carbonate salts that can be used in a large number of industries, and it is no longer a pollutant.

After the liberation of water from the CO2precipitated in the form of carbonate and bicarbonate is carried out podpisu return water to the reactor, where the culture medium.

Thus, at this point of the method was carried out double elimination or conversion of CO2; capture or biological fixation, carried out by the microalgae present in cultural�th environment and chemical conversion or transformation as a result of this deposition. In the implementation of this process in water culture medium is less CO2, bicarbonate and carbonate, and it can capture additional CO2up to the limit of solubility. During the next cycle, the procedure is repeated and ends during the deposition of the greatest number of WITH this2that was entered. In the absence of this rapid deposition of a large part WITH2will remain dissolved in the aqueous phase which is returned to the culture. Therefore, repeated administration WITH2in culture the ability of dissolution will be less because it already contains dissolved CO2.

Stage mechanical-chemical treatment of biomass

According to another preferred embodiment of the stage of the mechanical-chemical treatment includes the following podpisy:

anaerobic fermentation of biomass obtained by the photosynthesis performed by algae;

- branch of the fermented biomass from the water culture medium;

- thermo-chemical transformation of the fermented biomass by thermo-chemical decomposition at a temperature of between 200 and 420°C and a pressure of between 0 and 20 MPa to obtain a synthetic oil mixed with water and gases; and

- the Department received artificial�internal oil.

According to another preferred embodiment of the biomass with podpisy separation from biomass to aqueous phase is subjected ptpase anaerobic fermentation, which is carried out in the fermenter. During the fermentation process at a temperature between 10 and 165°C and preferably between 30 and 75°C the biomass is injected at a concentration of solids of between 1 and 50% solids, and preferably between 5 and 12%.

In the process of anaerobic fermentation, the biomass is transformed by different microbial communities present in the fermenter (anaerobic bacteria), About losing and N in the form of H2O, CO2and NH3and enriched with N and C. the Product obtained after this stage, similar to kerogen (the predecessor of gasoline). Along with anaerobic fermentation is the process of methanogenesis, leading to the formation of methane due to the fragmentation of the chains, this methane will be used as an energy source heating.

According to another preferred optional embodiment of the prior podpath anaerobic fermentation of biomass is carried out through a stage of homogenization or cavitation, in which the algae are subjected to pressure between 1 bar and 2500 bar and preferably between 250-1200 bar for the purpose of fragmentation. According to a preferred embodiment of the phase homogenization or cavitation is repeated 1-5 times involving�plant once. Then after podpisy anaerobic fermentation of the resulting product is carried out through podpisu branch of the fermented biomass from the water using a method selected from filtration, centrifugation, education floc, electrocautery, ultrasonic, evaporation, decantation, or any combinations thereof. In accordance with this processing gain biomass with a concentration of solids between 14-40% solids, preferably between 20-25%.

After phase separation of the fermented biomass from the water is necessary to carry out phase thermochemical transformation, in which the biomass is subjected to high pressures and temperatures, which leads to the formation of hydrocarbons.

This stage consists of chemical decomposition of organic material, due to moderate heating at high pressure or atmospheric pressure, although preferably at high pressures. The main advantage of working at high temperatures (of the order of 10-20 MPa or atmospheric pressure) and moderate temperatures (between 200 and 420°C, preferably between 240 and 340°C) is that the main raw material is not necessarily dry, so you can enter the raw materials in a thermochemical reactor with humidity up to 95%, preferably between 80-60%, which gives an obvious advantage of getting rid of not�bademosi drying (energy saving heating). In this phase synthetic oil.

In conclusion, is preferably carried out podpisu, which eliminate water related synthetic oil, using at least one way selected from the group formed by decantation, the formation of floc, adhesion, centrifugation, evaporation, drying, or any combination, and thus synthetic oil that can be used in internal combustion engines, boilers or turbines operating on liquid fuel, which is not necessarily clear.

Not necessarily according to a preferred embodiment of the after podpisy eliminate water artificial oil obtained is subjected ptpase homogenization or cavitation, wherein the seaweed is subjected to pressure between 1 bar and 2500 bar, preferably between 250-1200 bar for the purpose of fragmentation. According to a preferred embodiment of the phase homogenization or cavitation is repeated 1 to 5 times, preferably once. Thus, the following occurs:

- Break long chains of hydrocarbons with the formation of light hydrocarbons, increasing the number of alkenes, the increased production of ketones, lower crystallization temperature and a decrease in harmful emissions;

- Mixing of the two fluids, which �peculiar mix (synthetic oil and water).

Not necessarily according to another preferred embodiment of the after podpisy the removal of water or after the phase of homogenization will be performed sub-phase purification of synthetic oil. Purification step must be equivalent to the existing adopted cleaning at the refinery, except that the content of sulfur and heavy metals below, or they are missing.

Based on the specified target that is based on its components, it is desirable to obtain (gasoline, diesel fuel, kerosene, plastics, etc.), the structure of the refining industry may be different. Therefore, based on this, the installation must also include at least one of the following phases:

- atmospheric distillation (or topping),

- vacuum distillation

- gas generator installation,

- processing the water-oil

catalytic reforming.

- hydrocracking

catalytic cracking FCC fluid,

- easy cracking

- isomerization,

- alkylation,

- steam cracking,

- oxidation of bitumen

- installation for coking.

In conclusion, by the method described in the present invention, it is carried out on the concentration of C in a molecule of CO2(27% C) to final product (65-95% C, preferably between 75-90%).

The second aspect of the present invention relates to an artificial oil�, obtained by the previously described method, the characteristics of which are listed below:

Flash point (°C)35-200
The content of non-combustible matter in coal (% m/m)0-3
PCI (MJ/kg)29-45
Aluminum (mg/kg)<1
Silicon (mg/kg)<1
Vanadium (mg/kg)<1
Sodium (mg/kg)<1
Calcium (mg/kg)<1
Magnesium (mg/kg)<1
Phosphorus (mg/kg)<1

The third aspect of the present invention relates to the direct application of the obtained synthetic oil in internal combustion engines, turbines or boilers running on liquid fuel.

A fourth aspect of the invention relates to the use of gas that includes CO2such as gas emitted cement �promyshlennosti, for producing synthetic oil, using the method according to the present invention.

Throughout the description and claims the word "include" and its variants are not intended to exclude other technical characteristics, additives, components or steps. Specialists in this field other objectives, advantages and features of the invention should be clear part from the description and partly from the invention. The following examples and figures are provided to illustrate and are not intended to limit the scope of the invention.

BRIEF DESCRIPTION of FIGURES

Figure 1 shows the block diagram of the method according to the present invention. It illustrates each of the stages of the method.

Figure 2 shows a diagram representing the transformation of energy WITH2in accordance with a negative net balance.

Figure 3 presents the balance of emissions of CO2example 2 in the method of transformation of energy WITH2in accordance with a negative net balance.

Figure 4 shows the balance of emissions of CO2example 3 in the method of transformation of energy WITH2in accordance with a negative net balance.

Figure 5 presents the artificial separation of oil at various grades.

EXAMPLES of embodiment of

Below are a series of examples that at any given moment illustrate sintezatory specific components of the present invention and provide examples of basic ways. In accordance with the above the following examples are not intended in any way to limit the scope of the invention described in this descriptive message.

In this description, the symbols and conventions used in these procedures, diagrams and examples are consistent with the international system and contemporary scientific literature, for example, Journal of Medicinal Chemistry. Unless otherwise stated, all main materials received from suppliers and used without any further purification. Specifically, you can use the following abbreviations throughout this description: g (grams); mg (milligrams); kg (kilograms); µg (micrograms); l (liters); ml (milliliters); µl (microliters); mmol (millimoles); mol (moles); °C (degrees Celsius); Hz (Hertz); MHz (megahertz); δ (chemical permutation); s (singlet); d (doublet); t (triplet); q (quadruplet); m (multiplet); NMR (nuclear magnetic resonance); M (molarity); Et3N (triethylamine); DMF (dimethylformamide); DMSO (dimethyl sulfoxide); ACN (acetonitrile); PBS (phosphate buffered saline); NCV (net calorific value of fuel).

Example No. 1: energy Conversion2, obtaining a negative net balance

The starting point in this procedure is the emission of gases obtained by combustion with cement plants, and optional gases, �must register during the combustion actually received the product (synthetic oil).

Table 2 below shows an example of the gases emitted by cement plants:

Table 2
Temperature420°C
Pressure1Bar
Density0,79kg/m3
The mass flux2000kg/h
Specific heat0,25Kcal/kg
Volumetric flow2531,64m3/h
CO212vol. %
N261vol. %
O21,9vol. %
H2OA 20.7vol. %
CH42500 Hours/million
NOx90Hours/million
SO250Hours/million
WITHThe 1.65Hours/million

In accordance with the composition of the gas from cement plants is assumed that only one process will eliminate SOxand reduce the temperature. With this purpose, the adsorption column was installed in countercurrent with NaOH (aqueous solution with NaOH concentration of 10%). It is important to note that in the method of the invention in addition to the reduction of the net balance of CO2also achieve reduction in the end-product concentrations of NOx(95% of NOand the rest of NO2) dissolved in water NOand NO2(especially the latter). After this treatment, injected gas of the following composition (table 3).

Table 3
Temperature40°C
Pressure1,98Bar
Density2,22kg/m3
The mass flux1760kg/h
Specific heat0,24Kcal/kg
Volumetric flow792,79m3/h
CO213,5vol. %
N263vol. %
O22,1vol. %
H2O3,2vol. %
CH42300Hours/million
NOx62Hours/million
SO22Hours/million
WITH0Hours/million

In addition to the gases obtained in the emissions from the cement plant, again as stated previously, the gases emitted during the combustion of artificial oil, the floor�internal in this way, re-introduced into the culture; below presents the composition of this gas at the outlet of the processing system (using the absorber gas for heat treatment, in this case, there is no SOxand why not impose NaOH):

Table 4
Temperature40°C
Pressure1,98Bar
The mass flow CO278kg/h
CO214,9vol. %
N258vol. %
O22,7vol. %
H2O1,1vol. %
CH41100Hours/million
NOx120Hours/million
SO20/td> Hours/million
WITH0Hours/million

General chart presented in figure 2. The gases are mixed in a receptacle designed for that specific purpose and system. In this capacity for mixing in addition to mixing these two streams are mixed, the third air flow to bring the final mixture to the desired concentration of CO2; in this particular case, the average content of CO2is 13.5%. To create the mixture, measure the concentration of CO2the first two threads and activate the solenoid valve for the passage of larger or smaller amount of air, thus adjusting the final concentration. Thus, this mixture is a mixture that is introduced into the reactor (continuously shake photosynthetic reactors, light transmissive, and for this purpose made of transparent material), they contain monospecifičeskoj culture of microalgae (Nannochloris sp).

To study the absorption system WITH a2composition WITH2for a long time measured at the inlet and outlet. According to this data, you can determine the amount of CO2captured by the system (biological fixation + chemical fixation); along with a dry weight of culture and you can determine how many CO2was biologically recorded�Vano algae depending on its photosynthetic characteristics) and how much was recorded by the system. In the table 5 below presents the results of monitoring2:

In accordance with this table to install a total volume of 735 m3production of synthetic oil should be 681,11 kg/day. To obtain this product, based on the performance capture WITH269%, calculated on the basis of the preceding table, you will need to Supplement the photobioreactors 342,49 kg/h2; 264,44 kg CO2/h obtained from cement plants, and other 78 kg CO2/h obtained by applying emission combustion actually put synthetic oil.

For implementing the method of obtaining the biomass is first extracted with 367,64 m3per day (50% culture). Before carrying out the next phase of centrifugation (first stage extraction) it must pass through a stage of acidification, which is carried out in tanks of 500 m3. General characteristics of this stage of acidification is as follows:

Culture, extracted as a result of the continuous formation of bubbles of exhaust gas contains CO2bicarbonate and carbonate in solution at high concentrations. When hit WITH this2in the vial, the pH value in solution tends to increase, disrupting the balance towards formation of carbonates. When a large amount of carbonate will be PR�of Visina point of solubility, and he will begin to precipitate. This precipitation may cause the problem of pollution, and in turn pollution can lead to contamination, and additional complications when decanting water. So as to method mechanical separation (first stage separation), the entire amount extracted at one time, during this phase the storage you need to add acid. Specifically, in this case, a solution of H2SO4(1 M) to maintain pH value constantly below 7.5.

When emptying 367,64 m3culture effective mechanical separation of water from biomass. For this purpose, centrifugation, and thus get the volume of 1.89 m3/day at a concentration of solids of 15%.

In addition to the concentrated fraction (15% solids) is prepared aqueous fraction (saturated), amounting to a total volume of 3657 m3/a day. This water is due to the fact that it forms part of the culture, saturated WITH2, bicarbonate and carbonate. To release water from the load it made basic with NaOH to achieve pH 9 to shift the balance towards the formation of carbonate, and thus exceeded the solubility limit of the carbonate, which causes its precipitation. Thus chemically capture WITH2when getting water, WITH depleted2, bicarbonate� and carbonate. This water, which is depleted in these elements, re-injected into the system (in bioreactors) with updated capture ability in relation WITH2. With the introduction of this water in the absence of the implementation of the previous stage of the chemical capture of the water's capacity to assimilate WITH2would be minimal, since it would be close to saturation.

Concentrate with 15% solids, obtained by centrifugation, is conducted through a stage of anaerobic fermentation at 38°C. In the process of anaerobic fermentation, the biomass is transformed with the participation of a large number of microbial communities present (anaerobic bacteria), About losing and N in the form N2Oh, WITH2and NH3and enriched with N and P In the continuation of the fermentation process is celebrated as the content of N and O drops, the concentration of N and grows. At the same time, methane is generated as a consequence of the fragmentation of these molecules, providing the energy that is used as a source of thermal energy for subsequent thermochemical stage. Because of the fragmentation of 54,57 kg/h of dry biomass, which can potentially miss out on the second stage, only 45,48 kg/day is passed to the next stage as a result of fragmentation and destruction.

Then after the stage of anaerobic fermentation, the resulting product is again subjected to centrifugation, get up to 2% of solids; this product is obtained with a production speed of 967 kg/day, in spite of its pasty consistency, however, can be pumped, and it is passed to the next stage of thermochemical transformation. More purified water obtained in the process (1.6 m3/day), saturated with ammonia, and return again in the photobioreactors, and ammonium serves as an additional source of nutrients for microorganisms.

Thermochemical transformation takes place in the reactor at 270°C and 22 MPa in a continuous process carried out at a speed 40,32 kg/h, with the production of synthetic oil (with transformation 62,20% relative to the major dry biomass) 28,38 kg/h artificial oil with 3% water after phase decantation, held at the end of the phase in the reactor. In addition to producing synthetic oil in thermochemical process and fractionated gas (mainly CH4WITH2and CO) that is burned for the purpose of generating heat energy for this particular stage.

The end product has a PCI of approximately 9300 kcal/kg, which gives the possibility of obtaining electric power 138 kW after combustion in an internal combustion engine with the efficiency of transformation of heat energy into electrical energy 45%. CO2obtained by the combustion, once again injected into the system.

N� figure 3 shows the balance of emissions of CO 2.

In accordance with the balance upon receipt of electrical energy after the introduction 264,44 kg/h2thrown only 112.98 kg/HR CO2that implies a negative net balance -150,47 kg CO2/C. the result in this process WITH2not only ejected, but more CO2is captured than is emitted according to the following balance sheet:

Table 6
Introduced264,44kg CO2/h
Thrown113,98kg CO2/h
Balance-150,47kg CO2/h

Example No. 2. Assessment of energy WITH2

The starting point is a gases emission, obtained by the combustion in cement plants, the emissions contained in the following table:

Table 7
Temperature150°C
Pressure1Bar
Density0,77kg/m3
The mass flux43914kg/h
Specific heat0,25Kcal/kg
Volumetric flow57377m3/h
CO26vol. %
N267,6vol. %
O22,1vol. %
H2OA 20.7vol. %
CH49 000Hours/million
NOx50Hours/million
SOx50Hours/million
WITH2,69Hours/million

Given the characteristics of the gas ejected for cement�odes, believed that the elimination of SOxand reduce the temperature required for processing. To this end absorption column was installed in countercurrent with NaOH. It is important to note that in this method of the invention in addition to the reduction of the net balance of CO2also get a lower final concentration of NOx(95% of NOand the rest of NO2) dissolved in water NOand NO2(especially the latter).

In accordance with the next processing gas is introduced into photosynthetic reactors (photosynthetic reactor, which continuously shaken and the creating of a transparent material to permit light) and containing polyspecific culture of microalgae (Nannochloris sp, Tetraselmis chuii and Isocrisis Galbana).

Table 8
Temperature40°C
Pressure1,98Bar
Density2,22kg/m3
The mass flux38716kg/h
Specific heat 0,24Kcal/kg
Volumetric flow17473m3/h
CO2Value of 7, 37vol. %
N285,95vol. %
O22,95vol. %
H2OOf 3.69vol. %
CH410502Hours/million
NOx23,2Hours/million
SO21Hours/million
WITH0Hours/million

In accordance with the composition of these gases and the efficiency of the system to capture CO2achieved production of biomass 4017 kg/day, the transformation which allows to obtain bio-oil 1607,13 kg/day of synthetic oil in the plant with 230 photosynthetic reactors for a total capacity 4020 m3.

To obtain this �of iomasa first extracted with daily 1005 m 3(25% culture). This culture, passed to the next stage of centrifugation (first stage extraction), is required for carrying out the stage of acidification, which occurs in the vessel, which amounts to 1500 m3. The basis of this stage of acidification is the following:

Due to the continuous formation of bubbles of the exhaust gas is extracted culture contains a CO2bicarbonate and carbonate at high dilution. When leaving this TO2to form vesicles, the pH value of the solution tends to increase, thus shifting the balance towards the formation of carbonates. In the formation of significant amounts of carbonate, it exceeds the point of solubility and begins to precipitate. This deposition can lead to problems of clogging, and in turn specified the blockage may cause pollution along with problems when decanting water. Therefore, since the mechanical separation (first stage separation) is not able to skip the whole extracted volume at a time, during this period of storage must be added acid. Specifically, was added a solution of HCl (1 M) to ensure that the pH was always below 7.

Thus, when the release of 1005 m3culture water is mechanically separated from the biomass. This is carried out by centrifugation, thus, p�of time volume 36 m 3concentrated culture, however, it is still liquid; the concentration reaches 10% solids.

In addition to the concentrated fraction 10% solids receiving water fraction (saturated), the number of which is 9680 m3/a day. This water, due to the fact that it is part of a culture that is saturated WITH2, bicarbonate and carbonate. To release water from the load it made basic with NaOH to achieve a pH of 9.5 to shift the balance towards the formation of carbonate, thus exceeding the solubility of carbonate and causing its precipitation. Thus, WITH2chemically captured, yielding water WITH depleted2, bicarbonate and carbonate. Water, depleted in these elements, is introduced into the system again (in bioreactors) with the renewed ability of capturing CO2. With the introduction of this water in the absence of a preliminary stage of chemical capture ability of assimilation WITH2water would be minimal, since it would be close to saturation.

The concentrate at a concentration of solids of 10% (36 m3/diameter), obtained by centrifugation, performed on the stage of cavitation, which consists of two stages, each of which is carried out at a pressure of 750 bar; and, thus, the cells become fragmented, which facilitates �next phase of anaerobic fermentation. This anaerobic fermentation is carried out at 40°C and, thus, biomass is transformed with the participation of a large number of microbial communities present (anaerobic bacteria), About losing and N in the form N2Oh, WITH2and NH3and enriched with N and P as the success of the fermentation celebrated as the content of N and O begins to decrease, and the concentration of N and C is increased. At the same time, methane is generated as a consequence of the fragmentation of these molecules, the energy of which is used as a source of thermal energy for subsequent thermochemical stage. As a result of this fragmentation from 4017 kg of dry biomass that can potentially skip to the next stage, the next stage is passed only 2800 kg/day as a result of the fragmentation and destruction.

Then after the stage of anaerobic fermentation, the resulting product is centrifuged again, and the solids concentration therein reaches 23%; this product with the products of 10.7 m3/on a day that already is a product of pasty consistency, although it can be pumped, carried out through the next stage of thermochemical transformation. The water obtained by this division (19,8 m3per day), saturated ammonium, re-returned to the bioreactors, wherein the ammonium serves as an additional source of nutrients �La microorganisms.

Thermochemical transformation takes place in the reactor at 300°C and 15 MPa in a continuous delivery process is carried out at a speed 485,24 kg/h of concentrate with 23%, with the production of synthetic oil (in accordance with the transformation of 60% relative to the original dry biomass) at a rate of 1607,13 kg/day in artificial oil with 7% of water after phase decantation, implemented after the phase in the reactor.

The final product with approximately 8 PCI 100 kcal/kg is burned in the turbine, thus gaining 284 kW of installed capacity with an efficiency of conversion of thermal energy into electricity 45%.

In accordance with all of the above balance WITH2presented on figure 4.

In accordance with this diagram is administered 24724,98 kg/day CO2and ejected 441,96+8653,74+4419,61=13515,31 kg/day. Therefore, the net balance is: -11209,67 kg CO2on the day, and at2more is captured than is thrown.

Example No. 3: Synthetic oil-based CO2with cement plants

The starting point is the emission of gases obtained by the combustion in cement plants, the emissions shown in the table below:

Pressure Hours/million
Table 9
Temperature170°C
1bar
Density0,81kg/m3
The mass flux22000kg/h
Specific heat0,25kcal/kg
Volumetric flow27160,49m3/h
CO27vol. %
N266,8vol. %
O21,9vol. %
H2OThe 17.3vol. %
CH48000Hours/million
NOx40Hours/million
SO270Hours/million
WITHOf 3.69

Given the characteristics of the gases believed that the elimination of SOxand reduce the temperature required for processing. To this end absorption column was installed in countercurrent with NaOH.

After this processing in photosynthetic speakers introduced the following gases:

Table 10
Temperature40°C
Pressure1,98Bar
Density2,22kg/m3
The mass flux19360kg/h
Specific heat0,24kcal/kg
Volumetric flow8720,72m3/h
CO27,5vol. %
N287vol. %
O2vol. %
H2O3,32vol. %
CH49600Hours/million
NOx45Hours/million
SO21Hours/million
WITH0Hours/million

Gases listed in the table above, obtained in the processing, is introduced into a reactor (photosynthetic reactors, which are constantly shaken and the creating of a transparent material to permit light) and that contain monospecifičeskoj culture of microalgae (Isocrisis Galbana). As a result of this procedure receive products 170 kg/h of biomass to install volume 2041 m3.

To obtain this biomass first, the extraction is carried out at a speed of 714 m3per day (35% of culture). This extracted culture is passed into the container for decanting, with a maximum capacity of 1000 m3where it is subjected to a stage at which it separated from the seaweed (the first phase of extraction) by the method of coagulation is the formation of flakes. It coagulates with al�Minija, neutralizing in this way the load of microalgae, and it forms flakes using polyelectrolyte polymer (ZETAG). Thus, after 10 minutes, decanting the biomass remains at the bottom of the tank, giving a product with a solids concentration of 15%, which is sent to the next phase of fermentation.

In addition to the concentrated fraction (15% solids) is prepared aqueous fraction (the residue in the vessel for decanting), which reaches a total volume 7026 m3/a day. This water, because it was part of a culture that is saturated WITH2, bicarbonate and carbonate. To release water from the load it made basic with KOH to achieve pH 9 for shifting the balance towards the formation of carbonate and, thus, exceed the solubility limit of the carbonate, causing its precipitation. Thus, WITH2is captured chemically, yielding water WITH depleted2, bicarbonate and carbonate. Water that is depleted in these elements, is introduced into the system again (in the photoreactors) with the ability to re-capture WITH2. With the introduction of this water in the absence of a preceding phase chemical capture of the water's capacity to assimilate WITH2would be minimal, since it would be close to saturation.

The concentrate, which is a solid substance at a concentration of 15% (11,56 m 3/day), obtained by centrifugation, passed through a phase of anaerobic fermentation at 33°C. In the process of anaerobic fermentation, the biomass is transformed present different microbial communities (anaerobic bacteria), About losing and N in the form of H2O, CO2and NH3and enriched with N and S. In further fermentation is possible to notice how the content of N and O is used, while N and C is increased. At the same time, methane is generated as a result of fragmentation of these molecules, which is used as a source of thermal energy for subsequent thermochemical stage. In accordance with this fragmentation of 2040,65 kg of dry biomass per day, which can potentially miss out on the next stage, as a result of the fragmentation and decay at next phase is passed only 1360 kg per day.

Table 9 below shows the variation of C, N, O, and N in accordance with the fermentation process:

Table 11
Prior to fermentation (%)After fermentation (%)
50,360
N7,32
O26,8217,7
HA 7.5812,3

Then after stage anaerobic fermentation of the resulting product is subjected to the method of filtration under pressure to increase the content of solids. The material obtained in this phase, is a moist product with a 30% concentrate of solids. This product when products 4534,77 kg per day has the consistency of paste, however, it is to be pumped, and it is passed to the next stage of thermochemical transformation. Received more than purified water (11,47 m3per day) saturated with ammonia, and return again in the photoreactors, and ammonium serves as an additional source of nutrients for microorganisms.

Thermochemical transformation takes place in the reactor at 320°C and 20 MPa in a continuous process carried out at a speed of 189 kg/h, with the production of biofuel (in accordance with the transformation of 52% relative to the major dry biomass) 29,47 kg/h with 5% water after phase decantation, implemented after the phase in the reactor.

The end product has a PCI of approximately 8400 kcal/kg, and after the step of removing water by evaporation under vacuum, it is purified to obtain the different fractions, as shown in the following�following figure, with the method described as follows: artificial oil is preheated, and then carried through a furnace where the artificial oil is partially vaporized. Then it is passed through the column for distillation or rectification, and separated into various fractions based on boiling point. The percentages are as follows:

Of 5.6% → gases

- 11% → light naphtha

For 23.8% → heavy naphtha

- 18% → kerosene

Is 29.6% → diesel fuel

- 12% → heavy gasoil

1. Method for producing synthetic oil from gas containing CO2and which includes stages:
(a) a feed gas that contains CO2in a reactor containing a culture that contains at least one species of microalgae that are capable of photosynthesis;
b) photosynthesis carried out by the form of microalgae, using CO2filed to obtain biomass;
c) anaerobic fermentation of biomass obtained;
(d) thermochemical decomposition of fermented biomass at a pressure of between 0 and 20 MPa and a temperature between 200 and 420°C for producing synthetic oil mixed with water and gases, and
(e) separating the obtained synthetic oil,
characterized in that after the stage of photosynthesis from 5 to 100% of the culture is removed from the reactor, then it is separated into a solid fraction, which contains biomass, the solid fraction is then subjected to humiliating�Laut stage of anaerobic fermentation, and a liquid fraction containing carbonates and/or bicarbonates, carbonates and/or bicarbonates separated from the liquid fraction and the liquid fraction, essentially devoid of carbonates and bicarbonates, return, at least partially, into the reactor.

2. A method according to claim 1, in which at the stage of at least partial removal from the reactor is recovered from 5% to 50% of the culture.

3. A method according to claim 2, in which at the stage of at least partial removal from the reactor is recovered approximately 10% of culture.

4. A method according to any one of the preceding claims, in which to stage feed gas containing CO2in the specified reactor gas is pre-treated by at least one of the following ways: a substantial elimination of SOx, NOx, humidity and adaptation of the gas temperature to 30-40°C.

5. A method according to any one of claims. 1-3, in which stage of photosynthesis is carried out in the turbulent regime and exposed to natural and/or artificial lighting.

6. A method according to any one of claims. 1-3, in which, after the stage of at least partial extraction of culture extracted from the reactor culture was acidified with to pH-value between 3.5 and 8.

7. A method according to claim 6, wherein the extracted culture acidified to pH between 6 and 8.

8. A method according to claim 6, wherein the acidification is carried out by adding to the culture at measures� one acidifying agent, selected from the group consisting of CO2mixtures of CO2and air, strong or weak acids or any combinations thereof.

9. A method according to claim 8, in which the acidification is carried out by adding to the culture a mixture of CO2and air.

10. A method according to any one of claims. 1-3 and 7-9, in which, after the stage of at least partial extraction of the culture from the reactor is carried out the separation of the solid fraction, which contains biomass, and liquid fraction, which contains carbonates and/or bicarbonates, by at least one method selected from the group consisting of filtration, centrifugation, flocculation, electrocoagulation, ultrasonic, evaporation, decantation, or any combination thereof.

11. A method according to any one of claims. 1-3 and 7-9, in which the separation of carbonates and/or bicarbonates from the liquid fraction obtained by at least partially removing the culture from the reactor, is carried out by precipitation of the corresponding carbonate salts obtained by addition of at least one alkali.

12. A method according to any one of claims. 1-3 and 7-9, in which stage of anaerobic fermentation contains anaerobic fermentation of biomass, in which the concentration of solids is from 1 to 50%, and this stage is carried out at a temperature between 10 and 165°C.

13. A method according to claim 12, in which the biomass has a concentration of solids from do 12% and anaerobic fermentation is carried out at a temperature between 30 and 75°C.

14. A method according to claim 13, in which anaerobic fermentation is carried out at a temperature of approximately 38°C.

15. A method according to any one of claims. 1-3, 7-9, 13 and 14, in which before or after the stage of anaerobic fermentation, realize miss homogenization or cavitation of biomass, in which process it is subjected to pressure between 1 bar and 2500 bar.

16. A method according to claim 15, in which the biomass is subjected to pressure between 250 and 1200 bar.

17. A method according to claim 15, which is repeated 1 to 5 times.

18. A method according to any one of claims. 1-3, 7-9, 13, 14, 16 and 17, in which stage thermochemical decomposition of fermented biomass is carried out by heating the mass to a temperature between 240 and 340°C and a pressure from 10 to 20 MPa.

19. A method according to any one of claims. 1-3, 7-9, 13, 14, 16 and 17, in which, after stage anaerobic fermentation and before stage thermochemical decomposition of water fraction containing ammonium salts is separated from the biomass obtained by anaerobic fermentation, and the aqueous fraction is then recycled to the reactor again.

20. A method according to any one of claims. 1-3, 7-9, 13, 14, 16 and 17, in which species of algae that carry out photosynthesis, selected from the group consisting of Chlorophyceae, Bacillariophyceae, Dinophyceae, Cryptophyceae, Chrysophyceae, Haptophyceae, Prasinophyceae, Raphidophyceae, Eustigmatophyceae, or any combination thereof.

21. A method according to any one of claims. 1-3, 7-9, 13, 14, 16 and 17, in which a gas which contains CO2and served� into the reactor, supplied exogenously from the atmosphere or from any production and/or from endogenous gases generated in a real way, in any combination.

22. A method according to claim 21, in which the exogenous component gas containing CO2comes with cement plants or similar proceedings.

23. A method according to any one of claims. 1-3, 7-9, 13, 14, 16, 17 and 22, in which a gas containing CO2additionally contains other greenhouse gases, such as NOxand CH4.

24. A method according to any one of claims. 1-3, 7-9, 13, 14, 16, 17 and 22, which includes the final stage of purification of the obtained synthetic oil.

25. Artificial oil obtained by the method according to any one of claims. 1-24, characterized in that it comprises from 65 to 95% carbon and has the following features:
the density of 800-1200 kg/m3;
kinematic viscosity at 50°C 2-100 mm2/s;
flash point 35-200°C;
the content of non-combustible matter in coal 0-3% m/m;
PCI 29-45 MJ/kg;
the aluminum content is less than 1 mg/kg;
the silicon content is less than 1 mg/kg;
the content of vanadium is less than 1 mg/kg;
the sodium content is less than 1 mg/kg;
the calcium content is less than 1 mg/kg;
magnesium content of less than 1 mg/kg;
the phosphorus content is less than 1 mg/kg.

26. Artificial oil according to claim 25, which contains from 75 to 90% of carbon.

27. The use of synthetic oil according to claims. 25 or 26 for combustion engines and internal Shor�tion, turbines or boilers running on liquid fuel.

28. The use of gas containing CO2for producing synthetic oil, using the method described in any one of claims.1-24 above.

29. The use according to claim 28, in which the gas flows from production, such as cement plants.



 

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