TW524848B - Fuel additive for bituminous heavy oil-water emulsion fuel and method of combustion - Google Patents

Abstract

A fuel additive for adding to bituminous heavy O/W emulsion fuel includes particles of magnesium hydroxide, polycarboxylic acid and/or a salt or salts thereof, a dispersion deflocculant that is a salt of phosphoric acid, polyphosphoric acid, silicic acid, carbonic acid, sulfuric acid, boric acid, or hydrochloric acid, and a saturated or unsaturated fatty acid, with the remainder being water.

Description

524848 V. Description of the invention (1) The present invention relates to an additive for asphalt heavy oil / water emulsion fuel and a combustion method thereof. More specifically, the present invention relates to a fuel additive for use in water and emulsified fuels such as Orinook ⑺㈠⑽ ⑶) "Qingzhi" asphalt heavy oil with high vanadium, sulfur and nitrogen content, & A large amount of addition will not have an adverse effect on the dispersion stability of the fuel emulsifier. I can help it with stability, and it can also prevent the high and low temperature corrosion of the boiler when the fuel burns, and prevent the unburned carbon. The damage caused by sulfur trioxide, nitrogen oxides, and boilers can be operated stably for a long time by improving the absorption rate of the heating surface. The present invention also relates to a method for burning the fuel. Asphalt heavy oils such as Orino Gram asphalt and Athabasca asphalt are super heavy oils, which are sugar-like or semi-solid at a temperature of 400 t or higher, and contain 60% to 70% or more of heavy parts. Straightening in this state will not flow. "... Because? It is so heavy that it cannot be used as easily as petroleum. And because it contains high amounts of heavy metals and sulfur and nitrogen, the boilers used when they are used as fuel must be well maintained to prevent corrosion and slagging. In addition, the exhaust gas generated by the combustion process must meet much stricter environmental tests than before: due to these problems and disadvantages, the commercial application of the heavy oil has been delayed. However, in recent years, technology has progressed to form an oil / water emulsion fuel by adding water and a surfactant to Orinook asphalt. This allows the oil to be used and transported by Gu Yi. The recoverable deposits of this type of oil are quite large, exceeding the recoverable deposits of all oils throughout the Middle East. Therefore, for reasons including the availability of a stable supply under the Organization of Petroleum Exporting Countries (OPEC), and the fact that the oil is so cheap that it is possible to convert it to a thermal power plant,

C: \ 2D-CODE \ 90-07 \ 90111814.ptd Page 4 524848 V. Description of the invention (2) This oil has been used in Canada, the United Kingdom, and φ new fuel, not to mention Japanese. Min /, Heguo, etc. are used as a high-temperature guide f: using the bituminous emulsion to burn and reheat m, etc .: a consideration of the rapid erosion caused by the super heater and raw ash U: 5 f boiler High temperature corrosion caused by internal combustion of vanadium. Environmental measurement due to such a high amount of A dagger 3 oil: quilt :: material :: high amount of sulfur and nitrogen, high ash content. Special ;: ί ': Another consideration is that the involved will reduce the absorption of the smelting furnace, leading to the possibility of two ash content in the dazzling furnace, reducing the time during which the boiler can be continuously operated. In addition, there are two ways to increase the temperature of the dish. There are two ways to prevent the rotten maggots and petrified worms in the south temperature from turning into α, the daily rate, and inhibiting the harmful substances caused by combustion. 1 pass ^ high; burning efficiency t, magnesium acetate, magnesium nitrate, thorium hydroxide, calcium carbonate, stone η: other alkaline earth metal compounds or iron sulfate and * mFe〇 stone (or the number of or above)) iron Wherein: η is 0 mixed ^ = added to the fuel or discharged into the fuel, the fuel additives of the prior art described in Γ Club, Institute, France / 隹 are used for such as A, B and shell oil and tar kerosene, Asphalt, light oil, second-grade heavy oil " " L-fuel phase on the second stage of the present invention ... The quality will be described below, if it is not modified, it will be because of its use for budou. Strong adverse effects make it impossible to use the prior art? Chemical material is strong water-emulsified fuel. First… T ’s fuel additives are oil / different from oil-based fuels, bitumen heavy oil / water-emulsified fuels have a small amount of \\ 312 \ 2d-code \ 90-〇7 \ 9〇ing14 ptd page 5 524848

524848 V. Dimensions of the description of the invention (4). Another object of the present invention is to provide a fuel additive with a low monk and an ancient t of .n as low as 1 lb, which has a particle diameter of 0.1 to 1 0 // m, more preferably 0 $ > Lab ... The most magical agricultural degree of, is _ by weight ratio. ~ 5, Oxygenation of lice: to achieve the above purpose. The present invention provides a kind of tar for heavy oil / water tar… As an additive, it contains (1) a particle size of 30 to 60% by weight. 0.1 mg of magnesium hydroxide; (2) 1% by weight of polycarboxylic acid and / or its salt; (3) 0 ~ U by weight containing one or more lithium, sodium, unloading and Ammonium acid and more. Disperse deflocculating agent of acid breaking, oxalic acid, carbonic acid, sulfuric acid, lithopenic acid and hydrochloric acid salts; (4) 0 to 5% by weight of saturated or unsaturated fatty acids with 8 to "carbon atoms ; And (5) Residual water ^. :: In addition to the above ingredients, the fuel additive of the present invention still contains 10% denier, and the particle size of the iron compound is between 0 and 1; (7) 0 · 01 ~ 1% weight :: thickener; and ⑻〇 · Η0% weight ratio of hydrocarbon oil. The method and the purpose are also achieved by a method of burning and degrading heavy oil / water emulsified ingredients, which Contains the addition of the fuel additive ... ^ mM ^% The fuel is burned or the 3 combustion additives are directly added to the combustion atmosphere. 1 * 1 A ,,, & ¾ elbow particles formed by combining the ingredients specified above The high-concentration magnesium hydroxide adjuvant with a size of 0 · 1 ～ 1 0 // m makes it possible for it to be easily combined with asphalt heavy oil / water and water. Among them, the pot can be η ~~ Eight private s make a mixture of ritualized fuel and water, and it is easy to disperse and even helps — this can prevent high levels of boilers and the like. Warm corrosion, in order to improve the heat absorption rate of the heating surface due to the problems: ::, burning gas, operating the boiler. The recovery rate and long-term stability

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524848 V. Description of the invention (5) The fuel additives in this article X Ming will be described as follows. Press these questions. And the iron compound ^ 2 is to protect the various problems of the steel furnace or in 010. The particle size of the lice emulsified magnesium and iron compounds (water has: f) such as < magnesium acid or acetic acid can be added to the combustion atmosphere with a homogeneous liquid component, and the combustion reaction (g0) of ultrafine particles (diameter 10 ~ 50A). ", The disadvantage is that the particles produced: the initial adhesion (yield) of soil to vanadium pentoxide on the surface of the guide is not

<Another ^ day of soil small particles SA Gan &gt;, / V heart &gt; / 1U asks for the effect of soot removal as a soot blower (the uniformity of the second-class flowability) The slurry in which the component particles are dispersed is supplied to the combustion atmosphere. If the diameter of the rough particles used is 10 mm or more, the specific surface area of the particles will become too small, which will make the components Vanadium sulphur monoxide) becomes less reactive, and in addition the stability of the mud becomes worse. For these reasons, the particles of magnesium hydroxide (1) and iron compounds (6) which are preferred for the fuel additive of the invention are preferred. The size is within a range of 〇 · 丨 ~ 丨 〇 # m, and more preferably within a range of 0.5 to 5 // m. Polycarboxylic acids and / or their salts (2), dispersing flocculants (3) and saturated or unsaturated fatty acids (4) are used to make magnesium hydroxide (1) and iron compounds (6); , Copolymer or copolymer with other copolymerizable monomers, or (meta) acrylate, itaconic acid (anhydride), maleic acid (anhydride), etc. dispersed. Sodium, potassium, lithium and ammonium are suitable salts. 300-50,000 is its preferred molecular weight.实施 Examples used include (a) acrylic polymer, (b) meta-acrylic polymer, (c) maleic anhydride, itaconic anhydride, maleic acid, and itaconic acid.

524848 V. Description of the invention (6) At least one copolymer, and at least one acrylic acid, meta-acrylic acid, fluorenyl vinyl ether and other copolymerizable monomers (vinyl compounds), (d) acrylic acid and fluorene Copolymer of alkyl acrylates' (e) maleic acid compounds of meta-acrylic acid and polybutadiene, (f) maleic acid compounds of meta-acrylic acid and styrene / butadiene copolymer Polymer acids and their salts. Acid The dispersant deflocculant (3) contains one or more salts of bellows, sodium, potassium and ammonium, polydonic acid, oxalic acid, carbonic acid, sulphuric acid, acid and hydrochloric acid. Common examples that can be used include special scale salts such as sodium sulphate, metascale salts such as (κ P 〇 3) n, pyrolites (diphosphates) such as Na 4 P 2 07, polydoterate (Triphosphate) such as N ^ P3〇1 (), hexametaphosphate such as (NaP03) 6, lithium oxalate, sodium oxalate (water glass No. 1, 2, 3), carbonate, sulfate , Metaborate salts such as NaB〇2, tetraborate salts such as N ~ B407, sodium chloride, ammonium chloride and hydrates thereof. The component (4) of the fuel additive is a saturated or unsaturated fatty acid having 8 to "carbon atoms. Examples that can be used include branched fatty acids such as 2-ethylhexanoic acid (8 carbon atoms) and isostearic acid ( 1 8 ^ Porcupine 秘 Mi Guang 10 乂 门 山 〆, 炅 刀 曰 0 夂 石石安 原子); Saturated fatty acids (antiatoms), stearic acid (18 carbon atoms), and mountain polyacids (2 2 Stone anatomic atom); unsaturated fatty acids 刖 ^ ^ 々0 such as oleic acid (18 carbons® early), linseed linseed oil (18 carbon atoms) and erucic acid (22, added when needed— Qunhuaren & Jingzi), and its compounds. Damage to the formula, or suppression of these helps to protect the various uses of the boiler, the particle size is 0.;! ~ 丨 0 with m '/ line compounds with Oxides in particle form), Fe2O3.M (per &quot; oxygen &quot; V: examples of use include red iron nose, goethite, pyrite oxide) and ml $ 9 pages W312 \ 2d-code \ 9.〇7 \ 90111814.ptd ^ 24848 V. Description of the invention (7)

Fe304 (ferric iron tetroxide, magnetite). When needed, a second group of employees added to improve the dispersion stability of the fuel additive: the viscosity of the material is maintained at ⑺ ^ (20. 〇 In the special, it is used to include inorganic thickeners such as sepiolite The conventional examples of the use of sodium methylcellulose (CMC) and methylcellulose include only f thickeners such as di'M 03. (called (called) 4 · 8M hydrous magnesium. 22) : For a long time, it has been used to increase viscosity and prevent sedimentation and dripping. Saponite is different from sepiolite but has similar properties., And other liquid components. Methyl cellulose is composed of cellulose II :: to = methyl Cellulose can be referred to as a methyl ester. It is widely used, mainly as an adhesive. 第三 The third group of compounds added when needed, hydrocarbons promote the viscosity of the fuel additive itself, and good flow. And the contact between Γίΐ Γ and other ingredients and dicyanine particles. Examples include kerosene, light oil, A, B, and heavy oils and other such mineral oils. Ii. Add fuel with the above components. ; 'Used to prevent or suppress the knowledge of the boiler. The particle composition includes (丨Magnesium hydroxide, which is obtained by (2 acids and / or salts thereof, (3) dispersing flocculants and (4) saturated or saturated fatty acids; and if necessary, (6) iron compounds (powder ingredients) ), (?) Thickening (8) hydrocarbon oil dispersion. Among them, the ratio of magnesium hydroxide (1) and iron compounds (2) should be added, and the amount should be added, depending on the operating conditions, boiler form and other factors. It is different, so it should be decided according to the purpose. The proportion of dispersant (2), (3) and (4) is in accordance with \\ 312 \ 2d-code \ 90-07 \ 901118l4.ptd page 10 524848 Description of the invention (8 ) The concentrations of granules (1) and (6) are different. Generally speaking, higher concentration of granules requires larger amounts of dispersants (2), (3), and (4), especially it must be increased ( 2) or (3), or the amount of both. Similarly, the appropriate ratio of the thickener (7) varies depending on the particle composition (1) and (6), the degree and distribution. Generally, In other words, a lower concentration of granular ingredients requires a larger amount of thickener (7). However, it is also related to the amount of dispersant (2) and (3). Lower viscosity requires a larger amount of thickener (7). The specified particle composition (丨) and the ratio range are appropriate ranges for solving combustion-related problems. The range is set according to factors such as operating conditions and boilers. It prevents the occurrence of unburned carbon, = Sulfur oxide and oxygen: problems caused by compounds' and improved heat absorption on heated surfaces. Erguang. Problems related to combustion will not be resolved if these proportions fall outside the Capricorn Circle of the Moon. Part II 3) and ⑷, the range is selected to ensure good particle disintegration () and (6) in water (5). This range is also the fuel additive is added to the asphalt heavy oil / water emulsification d ~ Shadow t, even when added in large quantities. The facts shake it? = Addition of the agent, its stability can be * ^, the wrong reason is to add a homogeneous mixture of separation, so that 哕 =;: = to produce a particle-free composition range, then do + bucket = etc. to achieve greater results. If it falls in this selection, only the stability of the J / Ran additive is important. The addition of heavy oil / water emulsified fuel may be low and green. Especially when a large amount of γ is added, it has an adverse effect.

524848. Description of the invention (9) The compound is separated into semi-solid heavy oil and water. Examples of the present invention will be described below. It must be understood that the present invention is not limited to the following examples. Example 1: Corresponding to the composition ratios shown in Table 1, calculate (1) magnesium hydroxide, (6) iron compounds, (2) polycarboxylic acids and / or salts thereof, (3) dispersing deflocculants (4) selected amounts of (4) saturated or unsaturated fatty acids, (7) thickener and (8) hydrocarbon oil and (5) water so that the total amount is 300 §. The mixture was taught for 30 minutes at 3000 rpm to obtain a fuel additive in a stable water-slurry state. In Comparative Examples 1 and 2, the composition was prepared without adding (2) a polycarboxylic acid and / or a salt thereof, (3) a dispersion deflocculant, (4) a saturated or unsaturated fatty acid, and (7) a thickener. Agent and (8) hydrocarbon oil.

Fuel 2 additive properties, standing stability and mixture stability: * Measure the specific gravity and ratio of the fuel additive mixtures 1 to 10 and Comparative Examples 1 and 2 and verify the stability and mixture stability. The results are shown in Schedule 7. The stability of the fuel additives is based on the following rules: The selection of fuel additives * ^ ^ ^, the son-in-law's properties are measured after standing for one month. η. / Bu is t 疋; there are only a few clarified fractions of separation • about 10% of the upper layer of the fence, double 4 &quot;

〇 Δ X Approximately 10% of the clarified material separated from the upper layer 'Approximately 20 ~ 30% of the upper layer mixed with a clarified product that increases the separation of the knife 0 &lt;

50% or more points

524848 V. Description of the invention (ίο)-Stability of mixture; stability of additives and asphalt heavy oil / water. The results shown in Table 2 are based on the following rules. ", 20g of mixed heavy green oil / water emulsified fuel (its properties are shown in Table 3 and 2g of dry additives are mixed and stirred with a glass rod on a petri dish) ^ ... and fuel a. No change in the mixture. Knife, 'li.' Some small agglomerates of heavy oil were observed. — Emulsion completely collapsed; Large agglomerates of heavy oil were observed. Example 2: Oral. The fuel mixtures 3, 5 and 7 are forcibly injected into a boiler, and the fuel additive and the green heavy oil / water emulsifier are mixed into the line. The mixing example is 1 part of the additive to 500 parts of the fuel. = Nitrogen oxides produced by measuring the ratio of these 5 substances, = Sulfur oxide and coal;: Heating is measured at the exhaust gas preheater outlet. For the measurement =.-A rolled stone melon 〇-〇31〇1

G34 62 STBA-24) was hung in the super plus wailing _ J. Formula sheet (JIS as a control. The results are shown in the attached table 4. ..., °° Additive-free fuel The present invention is not limited to the above examples and can be modified within. Define the scope of the fuel additives of the present invention, As mentioned earlier, bitumen heavy oil / water emulsified fuel will not be added to the compound, and it can also improve its stability. Therefore, it will make the quality of the knife more detrimental and detrimental. The quality oil / water emulsified fuel makes 3you / inventive additives hinder the combustion reaction, 2 ^ low temperature rotten money and Ihui I furnace can be stable for a long time. Page 13 C: \ 2D-CODE \ 90-07 \ 90111814.ptd 524848

C: \ 2D-CODE \ 90-07 \ 90111814.ptd Page 14 524848 V. Description of the invention (12) Table 1

Composition Example Comparative Example Composition (W t,%) 1 2 3 4 5 6 7 8 9 10 1 2 (1) Magnesium hydroxide particle diameter 5-1 0 μm 6 0 5 5 Particle diameter 2-7 μm 4 5 5 0 3 5 Particle diameter 0.5-5 μ m 5 0 4 5 4 5 5 0 3 0 Particle diameter 0 · 1-3 μ m 4 0 3 0 (6) Dioxide particle diameter 3 8 μ m 2 Iron Particle diameter 0 · 5-5 μ m 5 5 Particle diameter 0. 1-3 μ η 10 Iron peroxide particle diameter 0.5-5 μ m 2 4 Particle diameter 0. 1-4 μ m 1 (2). Molecular weight A 〇Λ 〇 Polyacrylic acid sodium salt 10000) U. 1 U. 5 0.5 ("27000) 0.2 .3 Polyacrylic acid / metaacrylic acid sodium salt (&quot; 3000) 0.3" ("45000) 0.1 0.45 Polymethylethylene® ether / ("20000) Maleic acid 0.3 2 (" 50000) 0.2 Polymethylethylene S ether / (41 1 5 0 0 0) 0.4 Anhydrous maleic acid 0.8 ("25000) (3) Sodium special phosphate] 2 Hydrate 0.3 0.2 Sodium triphosphate 0.04 0.2 Sodium hexametaphosphate 0.5 0.2 Lithium silicate 0.02 Potassium tetraborate 4 hydrate 0.3 Sodium chloride 0.01 0.05 (4 ) Isostearic acid 0.2 oleic acid 0.5 linoleic acid 0.1 erucic acid 0.2 (7) sepiolite 0.2 0.2 saponite 0.3 0.3 0.3 0.3 carboxymethyl cellulose 0.2 methyl Element 0.2 (8) Kerosene 7 (5) Water 5 3.9 3 8.3 4 8.5 5 4.15 5 8.78 4 7.4 5 3.3 4 2.0 4 3.5 4 9.7 6 5 6 5 Total 10 0 10 0 10 0 10 0 10 0 10 0 10 0 10 0 10 0 10 0 10 0 10 0 Page 15 C: \ 2D-CODE \ 90-07 \ 90111814.ptd 524848 V. Description of the invention (13) Table 2

Composition Example Comparative Example 1 2 3 4 5 6 7 8 9 1 0 1 -2 Specific gravity (20 ° C) 1.36 1.53 1.43 1.40 1.35 1.45 1.37 1.48 1.38 1.44 1.26 1.28 Viscosity (m P a · s) 5 8 0 14 2 0 12 10 8 0 0 9 7 0 7 5 0 6 8 0 9 15 3 10 7 3 0 9 6 0 10 5 0 Master / ^ CTO / -j ~ r 円 尹 置 女性 性 〇〇 ◎ 〇 ◎ ◎ ◎ ◎ ○ △ △ Mixture stability 〇〇〇 ◎ ◎ ◎ ◎ ◎ 〇〇XX Table 3 Composition Moisture content Ash content Other (organic matter) 2 9.4% 0.1% 7 0.5% Elemental analysis 6 1.5% 7.5% 0.5% 2.8% 2 7.7% Properties d Density (1 5 ° C) Viscosity (20 ° c) Flash point Residual carbon 1.01 1 0 5 m P a · S 9.2% ___ Metal analysis .. Vanadium magnesium iron 3 5 0 ppm 2 ρ pm 2 ppm Off page 16 C: \ 2D-CODE \ 90-07 \ 90111814.ptd 524848 V. Description of the invention (14) Table 4 Nitrogen oxide sulfur dioxide sulfur trioxide coal ash

Test strip corrosion S / H

Test strips 饨 A / H m pp suppression (%) measured ppm suppression (%) m pp suppression (%) l pp suppression (%) measured by TL 値

値 量 ly \ ly nnr * = 7 ° / ¢-φ / V Inhibition (%) Composition Example 230 15 790 35 28 38 96 27 7 65 12 52

Composition Example Composition Example No Additive The unit of test strip corrosion is mdd (mg / dm / day) 9 C: \ 2D-CODE \ 90-07 \ 90111814.ptd page 17 524848 Schematic illustration

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Claims (1)

Report No. 90118814 is amended; reimbursement I 9L 7. 219 ^ M $ β \ 1. A fuel additive for green heavy oil / water emulsion fuel, the fuel additive contains: (1) 3 0 ~ 60 0% A weight ratio of magnesium hydroxide having a particle size of 0. 1 to 1 0 // m; (2) 0.1 to 1% by weight of a polycarboxylic acid and / or a salt thereof, wherein the polycarboxylic acid and / or a salt thereof The salt is one or more copolymers selected from the group consisting of polymers, copolymers and other copolymerizable monomers of meta-acrylates, itaconic acid (anhydride), maleic acid (anhydride), and has a molecular weight of 30. 0 0 ~ 5 0 0 0 0; and lithium, sodium, potassium and ammonium as their salts; (3) 0 ~ 1% by weight of carbamic acid, polyphosphoric acid containing one or more kinds of sodium, sodium, potassium and ammonium , Silicic acid, carbonic acid, sulfuric acid, boric acid, and hydrochloric acid salts; deflocculating agents; (4) 0 to 0.5% by weight of saturated or unsaturated fatty acids with 8 to 22 carbon atoms; (5) residual Moisture. 2. For example, the fuel additive in the scope of patent application No. 1 further contains 1 to 10% by weight iron compound (6) with a particle size of 0.1 to 10 // m. 3. The fuel additive according to item 2 of the patent application, wherein the iron compound is one or more selected from the group consisting of ferric oxide, iron peroxide and ferric oxide. 4. For example, the fuel additive of the scope of patent application No. 1, which further contains 0.01 to 1% by weight of the thickener (7). 5. The fuel additive according to item 4 of the application, wherein the thickener is one or more selected from sepiolite, saponite, carboxymethyl cellulose and methyl cellulose. 90111814.ptc Page 19 524848 _Case No. 90118814_ Year Month Amendment _ 6. Application for patent scope 6. If the fuel additive of the scope of application for item 1 of the patent, it still contains 0.1 to 10% by weight of hydrocarbons Compound oil (8). 7. The fuel additive according to item 6 of the application, wherein the hydrocarbon oil is one or more selected from the group consisting of kerosene, light oil, A heavy oil and B heavy oil. 8. A method for burning bitumen heavy oil / water emulsified fuel, comprising adding a fuel additive such as any one of claims 1, 2, 4 and 6 to the fuel and burning or directly adding the fuel additive to the burning In the atmosphere. 90111814.ptc Page 20