EP2938709A1

EP2938709A1 - Fuel composition comprising a heavy fuel oil, and product created from the biomass

Info

Publication number: EP2938709A1
Application number: EP13820842.6A
Authority: EP
Inventors: Bernard Manon; Patrick HAVIL
Original assignee: Total Marketing Services SA
Current assignee: TotalEnergies Marketing Services SA
Priority date: 2012-12-27
Filing date: 2013-12-20
Publication date: 2015-11-04
Anticipated expiration: 2033-12-20
Also published as: PT2938709T; FR3000498A1; EP2938709B1; WO2014102492A1; FR3000498B1; ES2618962T3

Abstract

The invention relates to a method for producing an end fuel composition comprising a soap stock composition and a heavy fuel, comprising steps of mixing the soap stock composition and the heavy fuel in pre-determined proportions, and centrifuging the resulting mixture, in order to obtain the end fuel composition.

Description

COMBUSTIBLE COMPOSITION COMPRISING A HEAVY FUEL AND A PRODUCT FROM THE BIOMASS

The present invention relates to a fuel composition comprising a heavy fuel oil and a product derived from biomass.

Heavy fuel oils are commercial high boiling hydrocarbons, relatively rich in heteroatoms such as sulfur or nitrogen and metals. Heavy fuel oils require, for the most part, to be stored hot so as to avoid any risk of solidification and to facilitate pumping and flow in pipelines. Commercial heavy fuel oils must comply with ASTM D396-98.

Usually, heavy fuel oils are formulated by assembling different bases from petroleum refining. In some cases, where commercial specifications are difficult to achieve with the bases usually used for formulation, heavy fuel oil is blended with lighter cuts such as distillates or desulphurized cuts, for example ARDS effluent ("Atmospheric Residue"). DeSulfurization "), which have a greater added value, which the formulator seeks to avoid. In addition, heavy fuel oils resulting from the assembly of different bases must be sufficiently stable over time. The instability can be materialized for example by an increase in the viscosity or by the sedimentation of certain products. It is therefore necessary to carry out stability tests during any new formulation of heavy fuel oil.

There is therefore a need to obtain heavy fuel oils better adapted to environmental constraints. The applicant is not aware of the marketing of a liquid heavy fuel whose cost per kWh is comparable to that of natural gas. In addition, the systems for post-treatment of fumes to meet environmental constraints have a high cost.

Another requirement related to heavy fuels is their use in installations of type 2910 A and 2910 B according to the ICPE nomenclature.

The refining industry, at least in Western Europe, tends to decrease the production of heavy fuel oil, due to declining demand. This decrease is related to the shift to alternative energy sources by customers, particularly natural gas, as well as environmental constraints that tend to limit the amount of sulfur present in heavy fuels, sulfur is virtually absent from commercial natural gas. Reducing the amount of sulfur in heavy fuels requires refining investments and running costs that make this purification step often economically unsustainable. In addition, the heavy fuel oil generally needs to be stored at a temperature of 50 ° C to make it pumpable. A decrease in storage temperature would improve overall energy efficiency.

There is therefore a need for fuels, liquid or solid, low cost, developed from biomass, which can be incorporated into heavy fuel oil compositions, so that they can be further adapted to environmental constraints.

Among the fuels derived from biomass, the neutralization pastes can advantageously be used, and they essentially comprise base neutralized fatty acids, and come directly from the saponification of a vegetable or animal oil. Among these oils, mention may be made of, but not limited to, rapeseed, soya, sunflower, peanut and olive oil. In addition to the base-neutralized fatty acids, the neutralization pastes may contain, depending on their origin and the quality of the saponification, traces of phospholipids or unreacted mono-, di- or tri-glycerides. Usually, the fatty acids have carbon chains Ci2-C2 _4, preferably C16-C20 or C16-C18 better. Advantages associated with such neutralization pastes reside, on the one hand, in their low cost of implementation, and, on the other hand, in the absence of undesirable toxic substances, such as pesticides, aflatoxins, heavy metals, dioxins, PCBs and nitrites.

However, one of the major difficulties of these neutralization pastes lies in their water content which can be prohibitive as to their use as fuel. Indeed, such pastes may contain significant proportions of water from the saponification reaction, typically, depending on the case, at least 50% by weight. Another difficulty is related to the fact that it is emulsion cases, which should be treated specifically.

The use as a fuel therefore requires the implementation of effective methods of removing this water and other unwanted solids or viscous liquid residues. The invention therefore relates to a process for preparing a final fuel composition comprising a neutralization paste composition and a heavy fuel, comprising the following steps of:

a) mixing the neutralization pulp composition and the heavy fuel in predetermined proportions; and

b) Centrifugation of the resulting mixture, to obtain the final fuel composition. Thus, thanks to this centrifugation operation, it is possible to obtain a final fuel composition, very advantageously having a water content of less than 3%, or even less than 1%, in particular between 0.5% and 0.1%. % in weight.

In addition to removing water, recovered in an aqueous phase, the implementation of the method also allows the effective removal of suspended solid residues, such as sludge, heavy metals and others, frequently present in such fuels.

The centrifugation step has the advantage of simplified implementation, avoiding resorting to complex chemical separation methods, such as distillation, which can be restrictive in terms of unwanted precautions and corrosion, and expensive.

Therefore, the final fuel composition, which represents the oily organic phase, after centrifugation, can advantageously be used as a fuel in installations referred to under items 2910A and 2910B relating to facilities classified for the protection of the environment (Order of 25 / 07/97 on general requirements for classified environmental protection installations subject to declaration under heading No. 2910: Combustion).

Item 2910A is for facilities that use commercial fuels with known characteristics, such as gas, coal and biomass.

Item 2910B refers to fuels not classified as waste and not included in 2910A, which fuels are by-products of the refining or petrochemical industry, such as High Viscosity Fuel (HVC) and oil, with characteristics close to those of commercial fuels, in particular as regards the emissions induced by their combustion. The CHV is a solid fuel at room temperature, liquid at the temperature of use, consisting of a mixture of hydrocarbon molecules, similar to those found in heavy fuel oils. Sulfur and metal contents are essentially related to the nature of the crude oils used in their production.

In the context of the invention, the heavy fuel can be chosen from the group consisting of FCC slurry (of known terminology), High Viscosity Fuel and heavy fuel oils. Alternatively, the heavy fuel may be an oily residue of refining, for example "slops" (recovery products).

The heavy fuel oil in the context of the invention may be heavy fuel oil comprising a mixture of asphaltenes peptized with resins, such as maltenes, in suspension in an oil. These asphaltenes are, in general, one of the main sources of carbon unburned production (asphaltene content of 2 to 8%). Other parameters of heavy fuel oil also include the possible formation of unburnt carbonaceous: a content of Conradson residue of between 6% and 15%, or an imbalance of the ratio between Conradson carbon and metals. Such heavy fuel oils may also be those whose sulfur content is <1% by weight (heavy fuel oil STELs: Very Low Sulfur Content) or comprises a sulfur content <0.55% by weight (heavy fuel oil TTBTS: Very Very Low Sulfur Content), which may further comprise one or a plurality of additives, such as activators or combustion additives. A combustion additive may comprise surfactants. Such compounds are known and commercially available. A combustion additive comprising a mixture of Fe, Ca and / or Ce oxide derivatives in a hydrocarbon solvent, such as apolar hydrocarbon solvents, is the most preferred. Such an additive is preferably present in a content of between 0.020 and 0.030%. An example is the Octapower CA2200 product provided by the Innospec Company.

Other examples of heavy fuel oils are those mentioned above and can be very fluid to reduce NOx and dust emissions.

It may also be conventional household heavy fuel oil, known to those skilled in the art.

A preferred example of heavy fuel oil is that comprising 50% -60% by weight of CHV and 50% -40% of FCC slurry.

Commercial heavy fuel oils must very advantageously comply with ASTM D396-98. The High Viscosity Fuel may be high sulfur content (<3.5% by weight - HTS) or STEL.

The above heavy fuels can be obtained from the Total Refining Marketing Company, and the various physico-chemical properties and the contents of various products of such heavy fuels are readily available, in particular on the said company's website.

In the context of the invention, the heavy fuel may be a solid heavy fuel, such as sloops, dewatered and hydrocarbon polluted soil residues, coke, coal and combustion soot.

The proportion of the neutralization paste composition in the final fuel composition is not limited, and may preferably be between 10% and 80% by weight, advantageously between 30% and 80% by weight, in particular between 50% by weight. and 75% by weight.

The advantage of using such a fuel is particularly related to its PCI (Lower Calorific Value) of 7800 kcal / kg, which can vary according to the proportion of water present in said neutralization paste, and its low production cost and exploitation.

The centrifugation step (step b)) may advantageously be a three-phase centrifugation, which provides the best results in terms of water removal.

However, the centrifugation step may itself be a combination of steps, in particular comprising a first diphasic type centrifugation step, which makes it possible to separate the suspended matter in the form of sludges containing a minimum of hydrocarbons, coupled in a second three-phase centrifugation step, which separates the recyclable hydrocarbon phase, the purified aqueous phase and the residual suspended solids from the first centrifugation. This step can be implemented by any appropriate device known and commercially available. Conventionally, centrifugation can be implemented with speeds of 4000 - 6000 rpm. The duration of the centrifugation depends on the nature of the species to be separated, their partition coefficient, the difference in density between the aqueous phase, the oily phase and the particles, the particle size, the surface tension of the species to separate, from the temperature, the speed of centrifugation. The separation time is therefore adapted to the case by those skilled in the art by conventional means of measurement and control.

The process may comprise, after step a) and before step b), a heating step up to temperatures advantageously of 60 ° C. and 90 ° C. in order to promote the thermodynamic aspects of the centrifugation, in particular by reducing the the viscosity of the mixture, and to decrease the surface tension. According to one embodiment, the temperature may even be between 100 ° C. and 220 ° C. The method may comprise after step b), a filtration step to remove any solid residues in suspension that would not have been removed by the centrifugation step.

Filtration is usually carried out on filters of 400 to 600 μιτι. The method may further advantageously comprise, prior to step a) of mixing, a step of adding an acid to the neutralization paste composition, followed by a stirring step.

Indeed, the applicant has shown that such an addition makes it possible to increase the water separation efficiency during the implementation of step b), since the acid promotes the release of water from the water. neutralization paste composition to an acidic aqueous phase thus generated, and to improve the physico-chemical properties of said composition, in particular by improving the pumpability of the composition and by reducing the adhesion to the walls.

Advantageously, the best results are obtained when the acid is present at a content of between 0.2% and 10%, in particular between 3% and 6% by weight relative to the total weight of the neutralization paste composition.

The acid must be able to ensure its functionality to release water from the organic phase of the neutralization paste. The acid is very advantageously an organic or inorganic acid or their mixture of concentration sufficient to perform this operation. It is thus preferable that the acid is a strong inorganic acid, such as sulfuric acid, hydrochloric acid, phosphoric, of concentration greater than or equal to 25%. Sulfuric acid is preferred.

Once the addition of acid has been carried out, a stirring step is carried out, which can be carried out by any known means, both during a pilot scale and an industrial implementation. The duration of the agitation is variable and generally depends on the nature of the pulp of the neutralization. Stirring is usually carried out for periods of a few minutes, such as 3-10 min, or even longer than 10 min, to reach as needed 10 to 30 min or 30-60 min.

When implementing such a step, in combination with the centrifugation step b), the formation of three phases is generally observed, which are as follows:

- A light oil phase, supernatant, which is clear, comprising from 45 to 55% by weight of oil relative to the total weight neutralization paste and acid. This phase may contain between 1% and 2% by weight of water;

An acidic aqueous phase comprising from 45 to 55% by weight of water originating from the neutralization paste and the added acid, relative to the total weight of neutralization paste and acid. Its pH is usually between 2 and 3.

An intermediate phase between the organic phase and aqueous acid, in the form of a film, capable of comprising residues of the neutralization paste. This intermediate layer may represent between 1% and 10% by weight relative to the total weight.

The sum in weight of all the phases is 100%.

The increase in the volume of acid present in the reaction medium is in favor of a decrease in the intermediate phase, which increases the weight percentage of the oily phase, and a mass gain of a few percent, advantageously of 1%, is observed. at 5%.

Alternatively, the process may comprise an acid addition step, as performed above, very advantageously carried out after step a) and before step b), that is to say on the dough mixture neutralization and heavy fuel. This embodiment is the most preferred because it allows a better release of water to the aqueous phase, and the presence of water in the final fuel composition is therefore advantageously between 1% and 0.1%, or even better, between 0.8 and 0.1%. Such a residual water content promotes the combustion properties of the final composition.

In addition, the Applicant has observed that the residual water content above is even lower than the mixture from step a) contains more heavy fuel. Without wishing to be bound by any theory, this would be explained by the fact that the increasing proportion of the heavy fuel content in the mixture promotes the lipophilic nature of the mixture and the passage of water from the organic phase to the aqueous phase of the mixture. the final fuel composition.

The final fuel compositions may be preferably used in various industrial fields, such as in the cement, sugar, glass, paper and heating industry, without being limiting.

The invention also relates to a fuel composition comprising a mixture of a neutralization paste and a heavy fuel, wherein the water content is less than 3% by weight,

According to advantageous forms, the water content may be less than 1%, in particular between 0.5% and 0.1% by weight.

In addition to the low water content, the fuel composition contains traces of suspended solid residues, such as sludges, asphaltenes, metals, frequently present in such fuels in variable proportions which correspond substantially to the average of their incorporation from of each of the feedstocks used in the present process modulo the sediments separated during the step of separation of water and sediments and losses.

Such a final fuel composition can be obtained by carrying out the above process.

This fuel composition has the advantages as detailed above.

The examples which follow illustrate the invention without limiting its scope. Example 1

Consider 100 liters of a 50/50 (w / w) mixture of heavy fuel TBTS with a neutralization paste composition that was prepared from sunflower oil.

Heavy fuel oil TBTS has a mass content of sulfur <1%. Such heavy fuel oil has been previously described and is available from the Total Refining Marketing Company.

The different characteristics of this heavy fuel oil are given in Table 1.

Table 1

The mixture thus obtained is heated to a temperature of 80 ° C., then subjected to centrifugation for 20 minutes at 5000 rpm and filtration on 500 μιτι filters. An amount of this mixture is taken for analysis (Sample A).

A sample of heavy fuel SIDS (Sample B) and a sample of neutralization paste composition (Sample C) undergo the same analyzes after centrifugation.

The results are given in Table 2.

Table 2

Analytical methods

Water content: ASTMD 95 or NF EN 3733;

Viscosity: NF EN ISO 3104;

Ash content: ASTM D482;

PCI: NFM 07030;

Chlorine content: calcination;

Sulfur content: NF EN ISO 8754 or ASTM D4294; Nitrogen content: ASTM D3228

PCB Content: Gas Chromatography (GC) Heavy Metals: ICP;

Insoluble: NF M 07 063 Example 2

100 liters of a 75/25 (w / w) heavy duty TBTS fuel blend were considered with a neutralization paste composition which was prepared from sunflower oil.

The heavy fuel oil TBTS is that described in Example 1.

A sample is taken (Sample D) and different analyzes are performed to characterize it (Table 3).

Table 3

Combustion tests are performed with sample D on a boiler rated 2910B (ICPE).

Table 4 presents the results in terms of combustion yields and gas emissions, depending on the variation of certain parameters (a, b, c). Table 4

HP = High Pressure.

The fuel is pumped into a charging tank and sent into a loop with a return to the charging tank, and passes into a heater to bring it to the injection temperature in the burner. There is no problem with the combustion. The flame is stable in all cases.

Example 3

The sample C is considered for acidification with an increasing content of concentrated sulfuric acid (50%).

For this, 97 ml of sample C are mixed with 3 ml of sulfuric acid (Sample E) and 95 ml of sample C with 5 ml of sulfuric acid (Sample F). After mixing, three-phase centrifugation is carried out for 10 minutes, and the following is observed. Sample E

Oily phase: 45% by weight and containing 2% of water. The oil is clear and constitutes the final fuel composition.

- Intermediate phase: 5% by weight, mostly consisting of neutralization paste residues.

- Acidic aqueous phase: 50% by weight, having the value of pH = 3.

Sample F

Oily phase: 50% by weight and containing 1% water. The oil is clear and constitutes the final fuel composition.

- Intermediate phase: 2% by weight, mostly consisting of neutralization paste residues.

- Acidic aqueous phase: 48% by weight, having the value of pH = 2.

Example 4

Sample A is considered for acidification with an increasing content of 95% concentrated sulfuric acid.

For this, 97 ml of sample C are mixed with 3 ml of sulfuric acid (Sample G) and 87 ml of sample C with 3 ml of sulfuric acid and 10 ml of water (Sample H). After mixing, three-phase centrifugation is carried out for 10 minutes, and the following is observed.

Sample G

Oily phase: 86% by weight and containing 3% of water. The oil is clear and constitutes the final fuel composition.

- Intermediate phase: no visible presence of this phase;

Acidic aqueous phase: 14% by weight, having the value of pH = 2.

Sample H

- Oily phase containing 2% water. The oil is clear and constitutes the final fuel composition.

- Intermediate phase: less important than that visible for Samples E and F, mostly consisting of neutralization paste residues.

- Acidic aqueous phase has the value of pH = 3.

Claims

1. A process for preparing a final fuel composition comprising a neutralization paste composition and a heavy fuel, comprising the following steps of:

b) Centrifugation of the resulting mixture, to obtain the final fuel composition.

The method of claim 1, wherein the fuel is selected from the group consisting of FCC slurry, High Viscosity Fuel and heavy fuel oils in accordance with ASTM D396-98.

The process according to claim 1 or 2, wherein the proportion of the neutralization paste composition in the final fuel composition is between 10% and 80% by weight, preferably between 30% and 80% by weight, particularly between 50% and 75% by weight.

4. Method according to one of claims 1 to 3, wherein the centrifugation step b) is a three-phase centrifugation.

5. The method of claim 4, wherein step b) comprises a first two-phase centrifugation step coupled to a second triphasic centrifugation step.

6. Method according to one of claims 1 to 5, further comprising, prior to step a) of mixing, a step of adding an acid in the neutralization paste composition, followed by a step of agitation.

7. Method according to one of claims 1 to 5, comprising an acid addition step performed after step a) and before step b).

8. Combustible composition obtainable by the implementation of the method according to one of claims 1 to 7, comprising a mixture of a neutralization paste and a heavy fuel, wherein the water content is lower. at 3% by weight.