Inflame desulfurization and denoxification of high sulfur containing fuels

DESCRIPTION

The present invention relates to a process for preparing liquid fuels and to liquid fuels prepared by said process. More specifically, it refers to a process that makes it possible to convert a fuel with a high content of sulfur and nitrogen into combustion energy, with a notable reduction in the emissions of sulfur oxides and nitrogen oxides.

Low viscosity viscous hydrocarbons found in Canada, the Soviet Union, the United States, China and Venezuela are normally liquids with viscosities between 10,000 and 200,000 CP and API severities less than 12. Currently, these hydrocarbons are produced by pumping mechanic, steam injection or by mining techniques. The widespread use of these materials as fuels is impossible for various reasons, including the difficulty of production, transport and handling of the material and, most importantly, the unfavorable characteristics of combustion, which produces emissions of oxides of Sulfur and unburned solids. To date, power plants make use of two commercial procedures to reduce sulfur oxides emissions. The first procedure is to inject limestone into the furnace, which will react with sulfur oxides to form solid sulfate particles that are separated from combustion gas with conventional particulate control devices. The cost to burn a typical fuel with high sulfur content by applying the limestone injection method ranges between two and three dollars per barrel and the amount of sulfur oxides removed by the method was around 50%. A more efficient procedure to remove sulfur oxides from power plants is to desulfurize the combustion gas by mixing CaO + H2O with the combustion gases of the furnace. In this procedure, 90% of the sulfur oxides are separated; however, the cost to burn a barrel of fuel using this procedure ranges from four to five dollars per barrel. For these reasons, viscous hydrocarbons with high sulfur content have not been able to be used on a commercial scale as fuels, due to the high costs associated with their combustion.

In the prior art it has been described that oil in water emulsions can be made for use as fuels. See, for example, U.S. Patents 4,114,015, 4,378,230 and 4,618,348. In addition, the prior art also indicates that oil-in-water emulsions formed from viscous low gravity hydrocarbons burn satisfactorily. See, for example, the memory of British patent 974,042 and US patent 4,618,348. Applicants of this invention have discovered that sulfur oxides emissions can be controlled when emulsions of viscous hydrocarbons with high sulfur content in water are burned in the presence of sulfur-trapping additives. See US patent applications series numbers 875,450 and 014,871.

Naturally, it would be very desirable to develop a process for preparing liquid fuels and the resulting liquid fuel which, when burning, produced emissions of nitrogen oxides and much lower sulfur oxides.

Accordingly, the main object of the invention is to provide an additive for a hydrocarbon fuel which, when burning the fuel, acts as a sulfur and nitrogen nitrogen capture agent, considerably reducing the formation and emission of sulfur and nitrogen oxides.

A particular object of the present invention is to provide a process, as set forth above, that is useful for hydrocarbons in aqueous emulsions that are burned as fuels.

Other objects and advantages of the present Iraqi invention appearing mine ahead.

The present invention relates to a process for preparing liquid fuels and the resulting liquid fuel and, in particular, refers to a process that allows converting a high sulfur and nitrogenous fuel into energy by a combustion process, whereby the emissions of sulfur oxides and nitrogen oxides are considerably reduced.

It is already known in the art that oil in water emulsions can be formed from natural bitumen or residual oils to facilitate the production and / or transport of these viscous hydrocarbons. Some typical procedures are described in US Patent Nos. 3,380,531, 3,467,195, 3,519,006, 3,943,954, 4,099,537, 4,108,193, 4,239,052 and 4,570,656. In addition, it is known that oil-in-water emulsions formed from natural bitumen and / or residual oils can be used as fuels. See, for example, U.S. Patents 4,144,015, 4,378,230 and 4,618,348.

The present invention relates to a process for preparing a liquid fuel and the resulting fuel which, on burning, exhibits a marked reduction in the emissions of sulfur oxides and

012 163 of nitrogen oxides. As already indicated, the particular process is useful for fuels in the form of hydrocarbon emulsions in water, such as those described in the co-pending serial number application 014.871 and 875.450.

The process of the present invention consists in mixing a hydrocarbon containing sulfur and nitrogen (either a hydrocarbon residue, an emulsion of hydrocarbons in water or other suitable hydrocarbon) with a water soluble additive that acted as a sulfur and nitrogen capture agent during combustion of the hydrocarbon. In accordance with the present invention, the water-soluble additive was essentially composed of Na⁺,Faith⁺⁺ and an element x selected from the group formed by Mg⁺⁺Ba⁺⁺,AC⁺⁺, Li⁺K⁺ and mixtures of them where Na⁺ is present in an amount less than or equal to 40% by weight based on the total weight of the water soluble additive, Fe⁺⁺ It was present in an amount greater than or equal to 0.4% by weight based on the total weight of the water-soluble additive, and the rest is essentially element X, where the ratio of Na⁺ aFe⁺⁺ It ranges between 7.5: 100 and 100: 1.0. It has been observed that the addition of Faith⁺⁺ It acted as a nitrogen capturing agent, thereby reducing nitrogen oxides emissions. Faith⁺⁺ it acted as a powerful sulfur trap, thereby reducing sulfur oxides emissions; however, since the Na⁺ tends to exert a corrosive effect on the boiler, it is necessary to limit the amount of Na⁺ in the additive The remaining element X acted as a sulfur capture agent and is used to supplement the amount of Na⁺ in the formulation of the additive. The additive with the indicated composition is an effective agent for capturing sulfur and nitrogen and does not produce serious corrosive effects in the boiler.

Figure 1 is a graphical representation of bars showing the effect of additives on the reduction of SO2 emissions.

Figure 2 is a graphical representation of bars showing the effect of additives on the reduction of nitrogen oxides emissions.

In accordance with the present invention, the process of the present invention consists in preparing and burning a fuel formed from a residual fuel oil or a natural bereton. One of the fuels to which the procedure can be applied is a bituminous crude oil that has a high sulfur content, as is the case with crude oils that are typically found in the Orinoco area in Venezuela. The betuon or residual oil has the following chemical and phosphoric properties: C: 78.2-85.5% by weight; H: 9.0-10.8% by weight; O: 0.2-1.3% by weight; N: 0.50-0.70% by weight; S: 2-4.5% by weight; Ashes: 0.05-0.33% by weight; Vanadium: 50-1000 ppm; Nickel: 20-500 ppm; Iron: 5-60 ppm; Sodium: 30-200 ppm; Gravity: 1.0-12.0 ° API; Viscosity (cSt) at 50 ° C (122 ° F): 1,000-5,100,000, at 90 ° C (210 ° F): 40-16,000; CLV: 8,250-10,450 Kcal / kg (15,000-19,000 BTU / lb); and Asphaltenes: 9.0-15.0% by weight. According to one aspect of the present invention, a mixture formed by water and an emulsifying additive is mixed with a viscous hydrocarbon or a residual fuel oil to form an oil-in-water emulsion. The characteristics of the oil-in-water emulsion and its formation are described in the aforementioned co-pending applications, which are incorporated herein by reference. In accordance with the present invention, the additive that captures sulfur and nitrogen and prevents the formation and emission of sulfur oxides and nitrogen oxides during the combustion of the hydrocarbon or of the hydrocarbon emulsion in water is added to the fuel before combustion. . The water soluble additive that is used in the process of the present invention consists essentially of Na⁺ ,Faith⁺⁺ and an element X selected from the group consisting of Mg⁺⁺Ba⁺⁺,AC⁺⁺, Li⁺K⁺ and mixtures of them. In accordance with the particular embodiment of the present invention, the Na⁺ It was present in an amount less than or equal to 40% by weight, based on the total weight of the water-soluble additive. Faith⁺⁺ It was present in an amount greater than or equal to 0.4% by weight, based on the total weight of the water-soluble additive. The rest of the water-soluble additive was constituted by element X. The relation of Na⁺ aFe⁺⁺ in the additive it ranges between approximately 7.5: 1.0 and 100: 1.0. The preferred formulation of the additive of the present invention that is used in the process of this invention consists essentially of Na⁺ in an amount that constitutes of the order of 5 to 40% by weight of the total weight of the water soluble additive, Fe⁺⁺ in an amount that constitutes about 0.4 to 2.0% by weight of the total weight of the water-soluble additive, the remainder being element X. To obtain the desired levels of sulfur and nitrogen oxides emission when the fuel Burning in accordance with the present invention, it has been found that the additive must be present in a molar ratio of sulfur additive in the fuel greater than or equal to 0.500 and, preferably, greater than 0.750.

The advantages of the present invention will be apparent from the following example.

Example

10 formulations of additives were prepared to demonstrate the effect of the additive of the present in3

012 163 convention on the combustion characteristics of hydrocarbon fuels containing sulfur and nitrogen. In Table I, the composition of the additive formulations is given.

Table I

Composition (% by weight)

<td>Additive No.</td><td>Mg</td><td>Na</td><td>Faith</td>

<td> 1</td><td> 80,5</td><td> 18,9</td><td> 0,65</td>

<td> 2</td><td> 62,2</td><td> 37,3</td><td> 0,50</td>

<td> 3</td><td> 67,4</td><td> 32,1</td><td> 0,40</td>

<td> 4</td><td> 67,4</td><td> 32,1</td><td> 0,43</td>

<td> 5</td><td> 79,5</td><td> 19,2</td><td> 1,28</td>

<td> 6</td><td> 61,9</td><td> 37,1</td><td> 0,99</td>

<td> 7</td><td> 83,0</td><td> 15,9</td><td> 1,06</td>

<td> 8</td><td> 67,2</td><td> 32,0</td><td> 0,86</td>

<td> 9</td><td> 2,7</td><td> 97,3</td><td> 0,00</td>

<td> 10</td><td> 98,8</td><td> 0,00</td><td> 1,2</td>

Each additive is added to various oil-in-water emulsions to burn them as natural fuels. Tables II-XI indicate the characteristics of the fuels, the operating conditions and the characteristics of combustion of each fuel mixed with each additive.

Tablapasaalapóagina next.

012 163

Table II

Additive No. 1

<td></td><td>Emulsion basal</td><td>Emulsion #one Feature</td><td>Emulsion #two com icas</td><td>Emulsion #3 fuel</td><td>Emulsion #4</td><td>Emulsion #5</td>

<td>1 / S additive</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>(Molar reasoned)</td><td> 0</td><td> 0,25</td><td> 0,38</td><td> 0,50</td><td> 0,75</td><td> 0,91</td>

<td>CLV (Kcal / kg)</td><td> 7.147</td><td> 6.616</td><td> 6.384</td><td> 6167</td><td> 5.766</td><td> 5419</td>

<td>(BTU / lb)</td><td> 12.995</td><td> 12.029</td><td> 11.608</td><td> 11.203</td><td> 10.484</td><td> 9.852</td>

<td>Bitumen,% p.</td><td> 74</td><td> 68,5</td><td> 66,1</td><td> 63,8</td><td> 59,7</td><td> 56,1</td>

<td>Water,% p.</td><td> 26</td><td> 31,5</td><td> 33,9</td><td> 36,2</td><td> 40,3</td><td> 43,9</td>

<td>Sulfur,% p.</td><td> 2,8</td><td> 2,6</td><td> 2,5</td><td> 2,4</td><td> 2,3</td><td> 2,1</td>

Operating conditions

<td colspan="7">Speed ​​of</td>

<td>feed (kg / h)</td><td> 25,3</td><td> 27,4</td><td> 28,4</td><td> 29,4</td><td> 31,4</td><td> 33,4</td>

<td>(lb / h)</td><td> 55,1</td><td> 59,5</td><td> 61,7</td><td> 63,9</td><td> 68,3</td><td> 72,7</td>

<td>Thermal consumption (Gcal / h)</td><td> 189</td><td> 189</td><td> 189</td><td> 189</td><td> 189</td><td> 189</td>

<td>(MMBTU / h)</td><td> 0,75</td><td> 0,75</td><td> 0,75</td><td> 0,75</td><td> 0,75</td><td> 0,75</td>

<td>Temp. of the fuel (^°C)</td><td> 65</td><td> 65,5</td><td> 65</td><td> 66</td><td> 65</td><td> 65,5</td>

<td> (^°F)</td><td> 149</td><td> 150</td><td> 149</td><td> 151</td><td> 149</td><td> 150</td>

<td>Steam ratio / fuel p / p</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>

<td>Steam pressure (bar)</td><td> 2,4</td><td> 2,4</td><td> 2,4</td><td> 2,4</td><td> 2,4</td><td> 2,4</td>

Combustion characteristics

<td>CO (ppm)</td><td> 10</td><td> 16</td><td> 10</td><td> 4</td><td> 15</td><td> 11</td>

<td>CO2 (% v.)</td><td> 14,3</td><td> 14,5</td><td> 14,5</td><td> 15,0</td><td> 15,0</td><td> 14,0</td>

<td>O2 (% v.)</td><td> 3,0</td><td> 3,0</td><td> 2,9</td><td> 2,8</td><td> 2,9</td><td> 2,9</td>

<td>SO2 (ppm)</td><td> 2100</td><td> 1175</td><td> 1000</td><td> 700</td><td> 350</td><td> 200</td>

<td>Reduction of</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>SO2 (%)</td><td> 0</td><td> 44,1</td><td> 52,4</td><td> 66,7</td><td> 83,3</td><td> 90,5</td>

<td>NOx (ppm)</td><td> 550</td><td> 435</td><td> 300</td><td> 240</td><td> 140</td><td> 150</td>

<td>Reduction of</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>NOx (%)</td><td> 0</td><td> 20,9</td><td> 45,5</td><td> 56,4</td><td> 74,6</td><td> 72,7</td>

<td>Performance</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>combustion</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> (%)</td><td> 99,8</td><td> 99,9</td><td> 99,9</td><td> 99,9</td><td> 99,9</td><td> 99,9</td>

012 163

Table III

Additive No. 2

<td></td><td>Emulsion basal Characteristic</td><td>Emulsioin #one com icas</td><td>Emulsioin #two fuel</td><td>Emulsion #3</td><td>Emulsioin #4</td>

<td>2 / S additive</td><td></td><td></td><td></td><td></td><td></td>

<td>(Molar ratio)</td><td> 0</td><td> 0,33</td><td> 0,49</td><td> 0,65</td><td> 0,70</td>

<td>CLV (Kcal / kg)</td><td> 7.147</td><td> 6.616</td><td> 6.384</td><td> 6.167</td><td> 5.766</td>

<td>(BTU / lb)</td><td> 12.995</td><td> 12.029</td><td> 11.608</td><td> 11.203</td><td> 10.484</td>

<td>Bitumen,% p.</td><td> 74</td><td> 68,5</td><td> 66,1</td><td> 63,8</td><td> 59,7</td>

<td>Water,% p.</td><td> 26</td><td> 31,5</td><td> 33,9</td><td> 36,2</td><td> 40,3</td>

<td>Sulfur,% p.</td><td> 2,8</td><td> 2,6</td><td> 2,5</td><td> 2,4</td><td> 2,3</td>

Operating conditions

<td colspan="6">Speed ​​of</td>

<td>feeding (kg / h)</td><td> 25,3</td><td> 27,4</td><td> 28,4</td><td> 29,4</td><td> 31,4</td>

<td>(lb / h)</td><td> 55,1</td><td> 59,5</td><td> 61,7</td><td> 63,9</td><td> 68,3</td>

<td>Thyremic Consumption (Gcal / h)</td><td> 189</td><td> 189</td><td> 189</td><td> 189</td><td> 189</td>

<td>(MMBTU / h)</td><td> 0,75</td><td> 0,75</td><td> 0,75</td><td> 0,75</td><td> 0,75</td>

<td>Temp. of the fuel (^° C)</td><td> 65</td><td> 65,5</td><td> 65</td><td> 66</td><td> 65</td>

<td> (^°F)</td><td> 149</td><td> 150</td><td> 149</td><td> 151</td><td> 149</td>

<td>Steam ratio / fuel p / p</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>

<td>Vapor pressure (bar)</td><td> 2,4</td><td> 2,4</td><td> 2,4</td><td> 2,4</td><td> 2,4</td>

Combustion characteristics

<td>CO (ppm)</td><td> 10</td><td> 5</td><td> 5</td><td> 14</td><td> 7</td>

<td>CO2 (% v.)</td><td> 14,3</td><td> 14,0</td><td> 14,0</td><td> 14,0</td><td> 14,0</td>

<td>O2 (% v.)</td><td> 3,0</td><td> 3,0</td><td> 2,9</td><td> 3,0</td><td> 3,2</td>

<td>SO2 (ppm)</td><td> 2100</td><td> 1150</td><td> 750</td><td> 380</td><td> 280</td>

<td>Reduction of</td><td></td><td></td><td></td><td></td><td></td>

<td>SO2 (%)</td><td> 0</td><td> 45,2</td><td> 64,3</td><td> 81,2</td><td> 86,7</td>

<td>NOx (ppm)</td><td> 550</td><td> 260</td><td> 210</td><td> 180</td><td> 120</td>

<td>Reduction of</td><td></td><td></td><td></td><td></td><td></td>

<td>NOx (%)</td><td> 0</td><td> 52,7</td><td> 62,0</td><td> 67,3</td><td> 78,2</td>

<td>Performance</td><td></td><td></td><td></td><td></td><td></td>

<td>combustion</td><td></td><td></td><td></td><td></td><td></td>

<td> (%)</td><td> 99,8</td><td> 99,9</td><td> 99,9</td><td> 99,9</td><td> 99,9</td>

* Analyzer out of order

012 163

Table IV

Additive No. 3

<td></td><td colspan="2">Emulsion</td><td>Emulsion</td><td>Emulsion</td><td>Emulsion</td><td>Emulsion</td>

<td> 5</td><td>3 / S additive</td><td colspan="3">baseline # 1 # 2 Fuel characteristics</td><td> #3</td><td> #4</td>

<td></td><td>(Molar reasoned)</td><td> 0</td><td> 0,30</td><td> 0,45</td><td> 0,60</td><td> 0,90</td>

<td rowspan="2"> 10</td><td>CLV (Kcal / kg)</td><td> 7.147</td><td> 6.616</td><td> 6.384</td><td> 6.167</td><td> 5.766</td>

<td>(BTU / lb)</td><td> 12.995</td><td> 12.029</td><td> 11.608</td><td> 11.203</td><td> 10.484</td>

<td></td><td>Bitumen,% p.</td><td> 74</td><td> 68,5</td><td> 66,1</td><td> 63,8</td><td> 59,7</td>

<td></td><td>Water,% p.</td><td> 26</td><td> 31,5</td><td> 33,9</td><td> 36,2</td><td> 40,3</td>

<td> 15</td><td>Sulfur,% p. Speed ​​of</td><td colspan="2">2.8 2.6 Operating conditions</td><td> 2,5</td><td> 2,4</td><td> 2,3</td>

<td></td><td>feed (kg / h)</td><td> 25,3</td><td> 27,4</td><td> 28,4</td><td> 29,4</td><td> 31,4</td>

<td></td><td>(lb / h)</td><td> 55,1</td><td> 59,5</td><td> 61,7</td><td> 63,9</td><td> 68,3</td>

<td> 20</td><td>Thermal consumption (Gcal / h)</td><td> 189</td><td> 189</td><td> 189</td><td> 189</td><td> 189</td>

<td></td><td>(MMBTU / h)</td><td> 0,75</td><td> 0,75</td><td> 0,75</td><td> 0,75</td><td> 0,75</td>

<td></td><td>Temp. of the fuel (^°C)</td><td> 65</td><td> 65,5</td><td> 65</td><td> 66</td><td> 65</td>

<td rowspan="2"> 25</td><td> (^°F) Steam / fuel ratio</td><td> 149</td><td> 150</td><td> 149</td><td> 151</td><td> 149</td>

<td>ble (p / p)</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>

<td></td><td>Steam pressure (bar)</td><td> 2,4</td><td> 2,4</td><td> 2,4</td><td> 2,4</td><td> 2,4</td>

Combustion characteristics

<td colspan="2">CO (ppm)</td><td> 10</td><td> 16</td><td> 26</td><td> 6</td><td> 5</td>

<td> 30</td><td>CO2 (% v.)</td><td> 14,3</td><td> 14,0</td><td> 14,5</td><td> 14,0</td><td> 14,0</td>

<td></td><td>O2 (% v.)</td><td> 3,0</td><td> 3,1</td><td> 2,7</td><td> 3,0</td><td> 2,9</td>

<td></td><td>SO2 (ppm)</td><td> 2100</td><td> 1250</td><td> 900</td><td> 600</td><td> 250</td>

<td></td><td>SO2 reduction (%)</td><td> 0</td><td> 40,5</td><td> 57,0</td><td> 71,4</td><td> 88,1</td>

<td> 35</td><td>NOx (ppm)</td><td> 550</td><td> 310</td><td> 210</td><td> 115</td><td> (*)</td>

<td></td><td>NOx reduction (%) Yield of</td><td> 0</td><td> 44,0</td><td> 62,0</td><td> 79,1</td><td> (*)</td>

<td></td><td>combustion (%)</td><td> 99,8</td><td> 99,9</td><td> 99,9</td><td> 99,9</td><td> 99,9</td>

<td> 40</td><td>(*) Analyzer outside</td><td>service</td><td></td><td></td><td></td><td></td>

012 163

Table V Additive No. 4

<td rowspan="2"></td><td rowspan="2">Emulsion basal Feature</td><td colspan="2">Emulsion Emulsion</td><td rowspan="2">Emulsion #3</td>

<td>#one com icas</td><td>#two fuel</td>

<td>4 / S additive</td><td></td><td></td><td></td><td></td>

<td>(molar reason)</td><td> 0</td><td> 0,38</td><td> 0,56</td><td> 0,75</td>

<td>CLV (Kcal / kg)</td><td> 7.147</td><td> 6.616</td><td> 6.384</td><td> 6.167</td>

<td>(BTU / lb)</td><td> 12.995</td><td> 12.029</td><td> 11.608</td><td> 11.203</td>

<td>Bitumen,% p.</td><td> 74</td><td> 68,5</td><td> 66,1</td><td> 63,8</td>

<td>Water,% p.</td><td> 26</td><td> 31,5</td><td> 33,9</td><td> 36,2</td>

<td>Sulfur,% p.</td><td> 2,8</td><td> 2,6</td><td> 2,5</td><td> 2,4</td>

Operating conditions

<td colspan="5">Speed ​​of</td>

<td>feed (kg / h)</td><td> 25,3</td><td> 27,4</td><td> 28,4</td><td> 29,4</td>

<td>(lb / h)</td><td> 55,1</td><td> 59,5</td><td> 61,7</td><td> 63,9</td>

<td>Thermal consumption (Gcal / h)</td><td> 189</td><td> 189</td><td> 189</td><td> 189</td>

<td>(MMBTU / h)</td><td> 0,75</td><td> 0,75</td><td> 0,75</td><td> 0,75</td>

<td>Temp. of the fuel (^°C)</td><td> 65</td><td> 65,5</td><td> 65</td><td> 66</td>

<td> (^°F)</td><td> 149</td><td> 150</td><td> 149</td><td> 151</td>

<td>Steam / fuel ratio</td><td></td><td></td><td></td><td></td>

<td>ble (p / p)</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>

<td>Steam pressure (bar)</td><td> 2,4</td><td> 2,4</td><td> 2,4</td><td> 2,4</td>

Combustion characteristics

<td>CO (ppm)</td><td> 10</td><td> 14</td><td> 14</td><td> 13</td>

<td>CO2 (% v.)</td><td> 14,3</td><td> 14,0</td><td> 14,0</td><td> 10,0</td>

<td>O2 (% v.)</td><td> 3,0</td><td> 2,9</td><td> 2,8</td><td> 3,1</td>

<td>SO2 (ppm)</td><td> 2100</td><td> 1100</td><td> 650</td><td> 200</td>

<td>SO2 reduction (%)</td><td> 0</td><td> 48,0</td><td> 69,1</td><td> 90,5</td>

<td>NOx (ppm)</td><td> 550</td><td> 280</td><td> 240</td><td> 140</td>

<td>NOx reduction (%)</td><td> 0</td><td> 49,0</td><td> 56,4</td><td> 74,6</td>

<td>Performance of the</td><td></td><td></td><td></td><td></td>

<td>combustion (%)</td><td> 99,8</td><td> 99,9</td><td> 99,9</td><td> 99,9</td>

(*) Out of service analyzer

012 163

Table VI

Additive No. 5

<td></td><td colspan="2">Emulsioin</td><td>Emulsioin</td><td>Emulsion</td><td>Emulsioin</td><td>Emulsion</td>

<td> 5</td><td>Additive 5 / S</td><td colspan="3">baseline # 1 # 2 Fuel characteristics</td><td> #3</td><td> #4</td>

<td></td><td>(Molar Reason)</td><td> 0</td><td> 0,15</td><td> 0,38</td><td> 0,50</td><td> 0,75</td>

<td rowspan="2"> 10</td><td>CLV (Kcal / kg)</td><td> 7.147</td><td> 6.616</td><td> 6.384</td><td> 6.167</td><td> 5.766</td>

<td>(BTU / lb)</td><td> 12.995</td><td> 12.029</td><td> 11.608</td><td> 11.203</td><td> 10.484</td>

<td></td><td>Betuín,% p.</td><td> 74</td><td> 68,5</td><td> 66,1</td><td> 63,8</td><td> 59,7</td>

<td></td><td>Water,% p.</td><td> 26</td><td> 31,5</td><td> 33,9</td><td> 36,2</td><td> 40,3</td>

<td> 15</td><td>Sulfur,% p. Speed ​​of</td><td colspan="2">2.8 2.6 Operating conditions</td><td> 2,5</td><td> 2,4</td><td> 2,3</td>

<td></td><td>feeding (kg / h)</td><td> 25,3</td><td> 27,4</td><td> 28,4</td><td> 29,4</td><td> 31,4</td>

<td></td><td>(lb / h)</td><td> 55,1</td><td> 59,5</td><td> 61,7</td><td> 63,9</td><td> 68,3</td>

<td> 20</td><td>Thyremic Consumption (Gcal / h)</td><td> 189</td><td> 189</td><td> 189</td><td> 189</td><td> 189</td>

<td></td><td>(MMBTU / h)</td><td> 0,75</td><td> 0,75</td><td> 0,75</td><td> 0,75</td><td> 0,75</td>

<td></td><td>Temp. of the fuel (^°C)</td><td> 65</td><td> 65,5</td><td> 65</td><td> 66</td><td> 65</td>

<td rowspan="2"> 25</td><td> (^°F) Steam / fuel ratio</td><td> 149</td><td> 150</td><td> 149</td><td> 151</td><td> 149</td>

<td>ble (p / p)</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>

<td></td><td>Vapor pressure (bar)</td><td> 2,4</td><td> 2,4</td><td> 2,4</td><td> 2,4</td><td> 2,4</td>

Combustion characteristics

<td colspan="2">CO (ppm)</td><td> 10</td><td> 3</td><td> 3</td><td> 4</td><td> 6</td>

<td> 30</td><td>CO2 (% v.)</td><td> 14,3</td><td> 14,0</td><td> 14,0</td><td> 14,5</td><td> 14,5</td>

<td></td><td>O2 (% v.)</td><td> 3,0</td><td> 3,0</td><td> 3,0</td><td> 3,0</td><td> 3,0</td>

<td></td><td>SO2 (ppm)</td><td> 2100</td><td> 1100</td><td> 725</td><td> 680</td><td> 350</td>

<td></td><td>SO2 reduction (%)</td><td> 0</td><td> 47,6</td><td> 65,5</td><td> 67,6</td><td> 83,3</td>

<td> 35</td><td>NOx (ppm)</td><td> 550</td><td> 350</td><td> 350</td><td> 200</td><td> (*)</td>

<td></td><td>NOx reduction (%) Yield of</td><td> 0</td><td> 36,4</td><td> 36,4</td><td> 63,6</td><td> (*)</td>

<td></td><td>combustion (%)</td><td> 99,8</td><td> 99,9</td><td> 99,9</td><td> 99,9</td><td> 99,9</td>

<td> 40</td><td colspan="2">(*) Out of service analyzer</td><td></td><td></td><td></td><td></td>

012 163

Table VII

Additive No. 6

<td rowspan="2"></td><td colspan="3">Emulsion Emulsion Emulsion</td><td rowspan="2">Emulsion #3</td>

<td>basal Feature</td><td>#one com icas</td><td>#two fuel</td>

<td>6 / S additive (molar ratio)</td><td> 0</td><td> 0,49</td><td> 0,65</td><td> 0,70</td>

<td>CLV (Kcal / kg)</td><td> 7.147</td><td> 6.384</td><td> 6.167</td><td> 5.766</td>

<td>(BTU / lb)</td><td> 12.995</td><td> 11.608</td><td> 11.203</td><td> 10.484</td>

<td>Bitumen,% p.</td><td> 74</td><td> 66,1</td><td> 63,8</td><td> 59,7</td>

<td>Water,% p.</td><td> 26</td><td> 33,9</td><td> 36,2</td><td> 40,3</td>

<td>Sulfur,% p.</td><td> 2,8</td><td> 2,5</td><td> 2,4</td><td> 2,3</td>

Operating conditions

<td colspan="5">Speed ​​of</td>

<td>feed (kg / h)</td><td> 25,3</td><td> 28,4</td><td> 29,4</td><td> 31,4</td>

<td>(lb / h)</td><td> 55,1</td><td> 61,7</td><td> 63,9</td><td> 68,3</td>

<td>Thermal consumption (Gcal / h)</td><td> 189</td><td> 189</td><td> 189</td><td> 189</td>

<td>(MMBTU / h)</td><td> 0,75</td><td> 0,75</td><td> 0,75</td><td> 0,75</td>

<td>Temp. of the fuel (^° C)</td><td> 65</td><td> 65,5</td><td> 65</td><td> 66</td>

<td> (^°F)</td><td> 149</td><td> 150</td><td> 149</td><td> 151</td>

<td>Steam / fuel ratio</td><td></td><td></td><td></td><td></td>

<td>ble (p / p)</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>

<td>Steam pressure (bar)</td><td> 2,4</td><td> 2,4</td><td> 2,4</td><td> 2,4</td>

Combustion characteristics

<td>CO (ppm)</td><td> 10</td><td> 4</td><td> 10</td><td> 15</td>

<td>CO2 (% v.)</td><td> 14,3</td><td> 15,0</td><td> 15,0</td><td> 15,0</td>

<td>O2 (% v.)</td><td> 3,0</td><td> 2,7</td><td> 3,0</td><td> 3,0</td>

<td>SO2 (ppm)</td><td> 2.100</td><td> 650</td><td> 350</td><td> 250</td>

<td>SO2 reduction (%)</td><td> 0</td><td> 69,0</td><td> 83,3</td><td> 88,1</td>

<td>NOx (ppm)</td><td> 550</td><td> 320</td><td> 140</td><td> 140</td>

<td>NOx reduction (%)</td><td> 0</td><td> 41,8</td><td> 74,5</td><td> 74,5</td>

<td>Performance of the</td><td></td><td></td><td></td><td></td>

<td>combustion (%)</td><td> 99,8</td><td> 99,9</td><td> 99,9</td><td> 99,9</td>

012 163

Table VIII Additive No. 7

<td></td><td>Emulsion basal Feature</td><td>Emulsion #one icas of the c</td><td>Emulsion #two mbustioon</td><td>Emulsion #3</td>

<td>7 / S additive (molar reason)</td><td> 0</td><td> 0,45</td><td> 0,60</td><td> 0,90</td>

<td>CLV (Kcal / kg)</td><td> 7.147</td><td> 6.784</td><td> 6.167</td><td> 5.766</td>

<td>(BTU / lb)</td><td> 12.995</td><td> 11.608</td><td> 11.203</td><td> 10.484</td>

<td>Bitumen,% p.</td><td> 74</td><td> 66,1</td><td> 63,8</td><td> 59,7</td>

<td>Water,% p.</td><td> 26</td><td> 33,9</td><td> 36,2</td><td> 40,3</td>

<td>Sulfur,% p.</td><td> 2,8</td><td> 2,5</td><td> 2,4</td><td> 2,3</td>

Operating conditions

<td colspan="5">Speed ​​of</td>

<td>feed (kg / h)</td><td> 25,3</td><td> 28,4</td><td> 28,4</td><td> 31,4</td>

<td>(lb / h)</td><td> 55,1</td><td> 61,7</td><td> 63,9</td><td> 68,3</td>

<td>Thermal consumption (Gcal / h)</td><td> 189</td><td> 189</td><td> 189</td><td> 189</td>

<td>(MMBTU / h)</td><td> 0,75</td><td> 0,75</td><td> 0,75</td><td> 0,75</td>

<td>Temp. of the fuel (^°C)</td><td> 65</td><td> 65,5</td><td> 65</td><td> 66</td>

<td> (^°F)</td><td> 149</td><td> 150</td><td> 149</td><td> 151</td>

<td>Steam / fuel ratio</td><td></td><td></td><td></td><td></td>

<td>ble (p / p)</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>

<td>Steam pressure (bar)</td><td> 2,4</td><td> 2,4</td><td> 2,4</td><td> 2,4</td>

Combustion characteristics

<td>CO (ppm)</td><td> 10</td><td> 10</td><td> 6</td><td> 8</td>

<td>CO2 (% v.)</td><td> 14,3</td><td> 15,0</td><td> 15,0</td><td> 14,5</td>

<td>O2 (% v.)</td><td> 3,0</td><td> 3,0</td><td> 2,9</td><td> 2,8</td>

<td>SO2 (ppm)</td><td> 2.100</td><td> 800</td><td> 550</td><td> 200</td>

<td>SO2 reduction (%)</td><td> 0</td><td> 61,9</td><td> 73,8</td><td> 90,5</td>

<td>NOx (ppm)</td><td> 550</td><td> 260</td><td> 150</td><td> 62</td>

<td>NOx reduction (%)</td><td> 0</td><td> 52,7</td><td> 72,7</td><td> 88,7</td>

<td>Efficiency of the</td><td></td><td></td><td></td><td></td>

<td>combustion (%)</td><td> 99,8</td><td> 99,9</td><td> 99,9</td><td> 99,9</td>

012 163

Table IX Additive No. 8

<td></td><td>Emulsion basal Feature</td><td>Emulsion #one icas of the c</td><td>Emulsion #two mbustióon</td><td>Emulsion #3</td>

<td>Additive 8 / S (molar reason)</td><td> 0</td><td> 0,56</td><td> 0,75</td><td> 0,93</td>

<td>CLV (Kcal / kg)</td><td> 7.147</td><td> 6.384</td><td> 6.167</td><td> 5.766</td>

<td>(BTU / lb)</td><td> 12.995</td><td> 11.608</td><td> 11.203</td><td> 10.484</td>

<td>Bitumen,% p.</td><td> 74</td><td> 66,1</td><td> 63,8</td><td> 59,7</td>

<td>Water,% p.</td><td> 26</td><td> 33,9</td><td> 36,2</td><td> 40,3</td>

<td>Sulfur,% p.</td><td> 2,8</td><td> 2,5</td><td> 2,4</td><td> 2,3</td>

Operating conditions

<td colspan="5">Speed ​​of</td>

<td>feed (kg / h)</td><td> 25,3</td><td> 28,4</td><td> 29,4</td><td> 31,4</td>

<td>(lb / h)</td><td> 55,1</td><td> 61,7</td><td> 63,9</td><td> 68,3</td>

<td>Thermal consumption (Gcal / h)</td><td> 189</td><td> 189</td><td> 189</td><td> 189</td>

<td>(MMBTU / h)</td><td> 0,75</td><td> 0,75</td><td> 0,75</td><td> 0,75</td>

<td>Temp. of the fuel (^° C)</td><td> 65</td><td> 65,5</td><td> 65</td><td> 66</td>

<td> (^°F)</td><td> 149</td><td> 150</td><td> 149</td><td> 151</td>

<td>Steam / fuel ratio</td><td></td><td></td><td></td><td></td>

<td>ble (p / p)</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>

<td>Steam pressure (bar)</td><td> 2,4</td><td> 2,4</td><td> 2,4</td><td> 2,4</td>

Combustion characteristics

<td>CO (ppm)</td><td> 10</td><td> 30</td><td> 7</td><td> 10</td>

<td>CO2 (% v.)</td><td> 14,3</td><td> 14,0</td><td> 14,0</td><td> 14,0</td>

<td>O2 (% v.)</td><td> 3,0</td><td> 3,0</td><td> 2,9</td><td> 3,0</td>

<td>SO2 (ppm)</td><td> 2.100</td><td> 550</td><td> 180</td><td> 75</td>

<td>SO2 reduction (%)</td><td> 0</td><td> 73,8</td><td> 91,4</td><td> 96,4</td>

<td>NOx (ppm)</td><td> 550</td><td> 230</td><td> 150</td><td> 100</td>

<td>NOx reduction (%)</td><td> 0</td><td> 58,2</td><td> 67,3</td><td> 81,8</td>

<td>Performance of the</td><td></td><td></td><td></td><td></td>

<td>combustion (%)</td><td> 99,8</td><td> 99,9</td><td> 99,9</td><td> 99,9</td>

012 163

Table X

Additive N ° 9

<td></td><td>Emulsion basal Feature</td><td>Emulsion #one icas of the c</td><td>Emulsion #two mbustióon</td>

<td>Additive 9 / S (molar ratio)</td><td> 0</td><td> 0,011</td><td> 0,097</td>

<td>CLV (Kcal / kg)</td><td> 7.335</td><td> 7.302</td><td> 7.095</td>

<td>(BTU / lb)</td><td> 13.337</td><td> 13.277</td><td> 12.900</td>

<td>Bitumen,% p.</td><td> 78</td><td> 78</td><td> 70</td>

<td>Water,% p.</td><td> 22</td><td> 22</td><td> 30</td>

<td>Sulfur,% p.</td><td> 3,0</td><td> 3,0</td><td> 2,7</td>

Operating conditions

<td colspan="4">Speed ​​of</td>

<td>feed (kg / h)</td><td> 27,6</td><td> 27,6</td><td> 30,7</td>

<td>(lb / h)</td><td> 60,0</td><td> 60,0</td><td> 66,7</td>

<td>Thermal consumption (Gcal / h)</td><td> 206,6</td><td> 206,6</td><td> 206,6</td>

<td>(MMBTU / h)</td><td> 0,82</td><td> 0,82</td><td> 0,82</td>

<td>Temp. of the fuel (^° C)</td><td> 68</td><td> 68</td><td> 68</td>

<td> (^°F)</td><td> 154</td><td> 154</td><td> 154</td>

<td>Steam / fuel ratio</td><td></td><td></td><td></td>

<td>ble (p / p)</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>

<td>Steam pressure (bar)</td><td> 2,4</td><td> 2,4</td><td> 2,4</td>

Combustion characteristics

<td>CO (ppm)</td><td> 36</td><td> 27</td><td> 20</td>

<td>CO2 (% v.)</td><td> 13,0</td><td> 12,9</td><td> 12,9</td>

<td>O2 (% v.)</td><td> 3,0</td><td> 2,9</td><td> 3,0</td>

<td>SO2 (ppm)</td><td> 2.347</td><td> 1.775</td><td> 165</td>

<td>SO2 reduction (%)</td><td> 0</td><td> 24,4</td><td> 93,1</td>

<td>NOx (ppm)</td><td> 450</td><td> 498</td><td> 434</td>

<td>NOx reduction (%)</td><td> 0</td><td> 9,7</td><td> 3,5</td>

<td>Performance of the</td><td></td><td></td><td></td>

<td>combustion (%)</td><td> 99,8</td><td> 99,8</td><td> 99,9</td>

012 163

Table XI Additive No. 10

Additive 10 / S (molar ratio)

CLV (Kcal / kg) (BTU / lb)

Bitumen,% p.

Water,% p.

Sulfur,% p.

Feed rate (kg / h) (lb / h)

Toxic consumption (Gcal / h) (MMBTU / h)

Temp. of the fuel (^°C) (^°F)

Steam / fuel ratio (p / p)

Steam pressure (bar)

CO (ppm)

CO2 (% v.)

O2 (% v.)

SO2 (ppm)

SO2 reduction (%)

NOx (ppm)

NOx reduction (%) Combustion efficiency (%)

<td>Emulsion</td><td>Emulsion</td><td>Emulsion</td>

<td>basal</td><td> #1</td><td> #2</td>

Fuel characteristics

<td> 0</td><td> 0,30</td><td> 0,78</td>

<td> 7.197</td><td> 7.008</td><td> 5.965</td>

<td> 13.086</td><td> 12.742</td><td> 10.845</td>

<td> 76</td><td> 74</td><td> 63</td>

<td> 24</td><td> 26</td><td> 37</td>

<td> 2,9</td><td> 2,8</td><td> 2,4</td>

Operating conditions

<td> 25,3</td><td> 25,8</td><td> 30,4</td>

<td> 55,1</td><td> 56,2</td><td> 66,0</td>

<td> 182</td><td> 182</td><td> 182</td>

<td> 0,72</td><td> 0,72</td><td> 0,72</td>

<td> 50</td><td> 50</td><td> 50</td>

<td> 149</td><td> 149</td><td> 149</td>

<td> 0,30</td><td> 0,30</td><td> 0,30</td>

<td> 2,4</td><td> 2,4</td><td> 2,4</td>

Combustion characteristics

<td> 21</td><td> 30</td><td> 10</td>

<td> 13,5</td><td> 14,0</td><td> 13,2</td>

<td> 3,0</td><td> 2,9</td><td> 3,0</td>

<td> 2357</td><td> 1250</td><td> 167</td>

<td> 0</td><td> 47,0</td><td> 92,9</td>

<td> 500</td><td> 430</td><td> 218</td>

<td> 0</td><td> 14,0</td><td> 56,4</td>

<td> 99,8</td><td> 99,9</td><td> 99,8</td>

012 163

As you can see in the previous Tables, the addition of Faith⁺⁺ The additive has a marked effect on reducing the emissions of nitrogen oxides when the fuel burns. A comparison of the effect of Fe is made in Figure 2⁺⁺ on the emissions of nitrogenous oxide with the effect obtained by adding Na + and element X (in this case magnesium). In Tables II-XI it can also be seen that Na⁺ it has a marked effect on the reduction of sulfur oxides emissions, compared to Fe⁺⁺ and element X. See Figure 1.

In addition to this, the combustion data indicate that the molar ratio of sulfur additive in the hydrocarbon fuel has an effect on the reduction of SO2 and nitrogen oxide, resulting in SO2 reductions greater than 80% at molar ratios of sulfur additive greater than 0.500 and preferably greater than 0.750.

The characteristics of the combustion ashes for emulsion 5 of Table II and for emulsion 2 of Table IX have also been analyzed. The results are given in Table XII below.

Table XII

<td colspan="5">Ashes characteristics</td>

<td>Additive</td><td>Compound</td><td>pf ^°</td><td>C, (^°F)</td><td>Observations</td>

<td></td><td>3Na2O.V2O5</td><td> 850,</td><td> (1562)</td><td></td>

<td></td><td>2Na2O.V2O5</td><td> 640,</td><td> (1184)</td><td></td>

<td>Table X</td><td>Na2O.V2O5</td><td> 590,</td><td> (1166)</td><td>potentially</td>

<td>Additive 9</td><td>Na2SO4</td><td> 880,</td><td> (1616)</td><td>corrosive</td>

<td></td><td>Na₂Ov₂OR₄.5V₂OR₅</td><td> 625,</td><td> (1157)</td><td></td>

<td>MgSO4</td><td> 1124, (2055)</td>

<td>3MgSO₄ . V₂OR₅</td><td> 1190, (2174)</td>

<td>Table II</td><td>non corrosive</td>

<td>NiSO4</td><td> 840, (1544)</td>

<td>Additive 1</td><td></td>

<td>MgO</td><td> 1450, (2642)</td>

<td>Na2SO4</td><td> 880, (1616)</td>

The ash composition when the additive 9 (a high sodium additive composition) is used indicates that the ashes are potentially corrosive and therefore undesirable. Therefore, the ideal composition of the additive to minimize emissions of sulfur oxides and nitrogen oxides and reduce the corrosion potential was constituted by about 5 to 40% by weight of Na⁺, 0.4% to 2.0% in weight⁺⁺, the rest being essentially element X.

012 163