JPS63268796A - Combustion improver for coky hydrocarbon substance - Google Patents

Abstract

PURPOSE:To effectively remove coky hydrocarbon substances, such as soot or hydrocarbon polymers, and obtain a safely handleable and economical combustion improver for fuels, by blending a specific amount of a specified hydrocarbon in a mixture of copper chloride powder with potassium chloride powder at a specific ratio. CONSTITUTION:The aimed combustion improver obtained by blending (B) 5-50wt.% hydrocarbon having >=350 deg.C boiling point (e.g. mineral based hydrocarbon, synthetic lubricating oil, liquid paraffin, crude wax or paraffin wax) in a mixture of (A) mixed powder of (i) copper chloride powder with (ii) potassium chloride powder at 5:95-90:10wt.% ratio (especially preferably 30:70-70:30wt.% ratio). Furthermore, a method for supporting the component (B) on the component (i) and/or component (ii) of the component (A) or impregnating or supporting a porous powder with the component (B) and then blending the resultant porous powder with the component (A), etc., is preferred as the method for blending the components (B) with (A).

Description

[Detailed Description of the Invention] The present invention is directed to the production of soot and coke that are produced when gas, liquid, or solid fuels are burned in a heating furnace or engine or reacted in a chemical reaction device. The present invention relates to a combustion improver for promoting combustion when removing deposits of carbonaceous substances and heavy hydrocarbons adhering to metal walls, etc. by burning them.

Carbonaceous substances adhering to the surface of the piping system and heat exchanger of heat exchange furnaces and exhaust gas boilers, the inside of hydrocarbon heating pipes of heating furnaces, hydrocarbon pyrolysis reactors and kilns, etc. are contaminated with soot, coke, etc. , consisting of deposits or deposits of polymerized hydrocarbons (hereinafter referred to as coke-like hydrocarbon materials).

Conventionally, methods such as normaling, scraping, blasting, or combustion have been employed to remove this coke-like hydrocarbon material, but it is difficult to remove it in practice.

In particular, since it is desirable to remove coke-like hydrocarbons deposited in flues, exhaust systems, and heat exchangers during operation, there is a need for the development of a method that can effectively remove them by using additives.

Under these circumstances, various additives have been proposed to lower the ignition temperature of coke-like hydrocarbons such as soot.
A soot ignition temperature lowering agent is disclosed comprising a combination of 50-70% by weight of C1Os, ~30% by weight of a wooden bar, 1-10% by weight of metal soap, and 12-20% by weight of iron or lead oxide powder. . In other words, the publication states that the above additive increases the ignition temperature of soot from 600-650°C to 260-3°C.
It teaches that as the temperature decreases to 15°C, the combustion of soot is promoted and auxiliary combustion is performed.

Canadian Patent No. 99007 discloses an additive consisting of a mixture of ammonium nitrate and at least one alkali or alkaline earth metal nitrate, sulfur or sulfur compound, and British Patent No. 1249
Publication No. 371 discloses that in order to clean soots, carbon, or thins adhering to the surface of pipes such as boilers, a mixture of alkali metal nitrate and oxidizing substance is conveyed to the target area by a combustion gas flow. A method is disclosed in which the material is deposited and the portion is burned by heating.

However, the method disclosed above uses an agent containing a chloric acid compound or nitrate, which poses a problem in that it is dangerous to handle.

Therefore, there is a need for an additive that is safe to handle and that can burn off coke-like hydrocarbons at relatively low temperatures.

■ The present invention was made in view of the situation on the ridge, and in the combustion and removal of coke-like hydrocarbon substances generated in the above-mentioned combustion equipment and related equipment, the coke-like hydrocarbon substances are Safe in handling, applied by air conveyance, mixing, or direct application to the deposited area of the coke, and effectively removing the coke-like hydrocarbon material by combustion at relatively low temperatures. Our goal is to provide an economically inexpensive combustion aid.

The present invention will be explained in detail below.

The characteristics of the present invention are as follows:
95-90: A combustion aid for coke-like hydrocarbon substances, which is made by mixing 5-50% by weight of a hydrocarbon having a boiling point of 350° C. or more with a mixed powder of 10% by weight.

The term "coke-like hydrocarbon material" as used herein refers to a carbonaceous material consisting of soot, coke, polymerized hydrocarbons, etc. that accumulates and adheres to the various combustion equipment and related equipment described above.

The combustion aid for combustion of coke-like hydrocarbon substances according to the present invention for
Copper chloride powder 5-95% by weight, potassium chloride powder 95-1%
0% by weight of a hydrocarbon having a boiling point of 350° C. or higher in a proportion of 5 to 50% by weight based on the total amount of the mixture.

In the present invention, copper chloride powder and potassium chloride powder are mixed at the above mixing ratio, preferably 20:80 to 80:20 (weight ratio), more preferably 30 + 70 to 70:30 (weight ratio). It is important to use potassium chloride alone; no effect has been observed, and
Copper chloride alone exhibits a catalytic effect, but its combustion promoting effect is low, and only when used in combination with potassium chloride does it exhibit a significant combustion promoting effect, that is, the effect of lowering the ignition temperature of coke-like hydrocarbon substances such as soot.

Note that the copper chloride may be either CuC1 or CuC1, but since CuC1g is hygroscopic and difficult to handle, it is practically preferable to use CuC1.

The steel chloride and potassium chloride are used in powder form or in the form of particles by supporting them on a porous powder carrier so that they can be easily transported by air current.

When supported on porous powder, alumina, silica,
Powder such as silica alumina, zeolite, graphite or carbon black, preferably surface area 30-300r
rr/g, supported on powder particles with a particle size of 20 to 300μ,
Among these porous carriers, which are preferably calcined to a temperature of 200 to 300° C. in the form of particles, carbon black and the like are particularly advantageous since they can themselves be used as a fuel. Note that in the above-mentioned loading, only one of copper chloride and potassium chloride may be supported.

Next, the hydrocarbon to be mixed with the copper chloride and potassium chloride has a boiling point of 350°C or higher, preferably 380°C.
above, particularly preferably 400°C or above, and a melting point of 2
Hydrocarbons that are solid or semi-solid at room temperature below 00°C and have excellent flammability are preferably
Liquid polypropylene used in mineral oil-based lubricating oil fractions (e.g. neutral oil, blystock oil, etc.) with a viscosity of 20 to 150 cSt (30°C), crude wax obtained in the lubricating oil refining process, paraffin wax, synthetic lubricating oil, etc. ,
Examples include higher alcohol ester oils of dibasic acids such as polyisobutylene, polybutene, and adipic acid.

On the other hand, materials with high carbon and asphaltene content such as asphalt, materials that generate toxic gas such as polyvinyl chloride, and hard polyolefins with a high degree of crystallinity are undesirable. ,
Hydrocarbons with a boiling point lower than 350° C., such as light oil or light lubricating base oil, have a low effect of promoting the ignitability of coke-like hydrocarbons and are therefore not practical.

In the present invention, the above-mentioned hydrocarbons are mixed at a blending ratio of 5 to 50% by weight with respect to the total amount of copper chloride and potassium chloride, and if the above-mentioned blending ratio of hydrocarbons is less than 5% by weight, combustion occurs. No promoting effect can be expected, and on the other hand, even if it exceeds 50% by weight, no further improvement in combustion promotion can be expected.

In the Li-like method of mixing hydrocarbons with copper chloride powder and potassium chloride powder, the hydrocarbons are supported on one or both of these powders, or the hydrocarbons are impregnated and supported on a porous powder. and the above-mentioned mixed powder. Furthermore, the hydrocarbon supported on this porous powder may be mixed with a mixed powder of one or both of copper chloride powder and potassium chloride powder supported on the porous powder described above. It is also possible to support the powder, potassium chloride powder and the hydrocarbon on the same porous carrier.

As the porous powder for impregnating and supporting the hydrocarbon, those mentioned above can be used, but powders of wood chips, cotton, rice bran, pulp, rice, etc. can also be mixed and used.

In addition, when the hydrocarbon is supported on the porous powder, the amount of hydrocarbon supported is such that the surface of the powder carrier does not become sticky. Since the porous powder adsorbs hydrocarbons well, the powder may take on a granular shape after being supported.

Incidentally, when a powdered catalyst used for fluid catalytic cracking of heavy oil is used as a porous carrier, and lubricant base oil is adsorbed and supported as a hydrocarbon, the surface becomes smooth and easy to handle. .

In order to burn and remove coke-like hydrocarbons using a combustion improver made of a mixture of copper chloride powder, potassium chloride powder, and hydrocarbons as described above, in the form of powder particles or granules, The coke-like hydrocarbon material is transported by an air current and deposited on the deposited area, or it is suspended in water, alcohol, ketone, or other volatile dispersant to form a slurry, preferably containing a vinyl acetate-based A small amount of adhesive is added, applied directly to the coke-like hydrocarbon deposits, dried, and then heated to ignite the coke-like hydrocarbon material.

When the coke-like hydrocarbon material to which the combustion improver according to the present invention is attached or coated as described above is heated in the presence of an oxygen-containing gas, it ignites at a relatively low temperature of 250 to 350°C, causing combustion. Start. Incidentally, coke-like hydrocarbon substances alone require heating at a temperature of approximately 500 to 650°C for ignition. Therefore, it can be said that the combustion promoting effect of the coke-like hydrocarbon substance of the combustion improver according to the present invention is remarkable.

As mentioned above, since the combustion improver according to the present invention can be transported by airflow, in practice, the combustion improver can be blown into the exhaust gas line of a heating furnace or diesel engine to transport the coke-like hydrocarbon substances by airflow. It can be attached to the deposited area, and combustion can be continued by circulating air.

Furthermore, when hydrocarbons are supported on a porous carrier such as rice bran or sawdust, the ignition starts at a lower temperature.
Moreover, it ensures stable ignition and continued combustion of the coke-like hydrocarbon material.

Furthermore, by using the combustion improver of the present invention, it becomes possible to effectively remove coke-like substances from economizers of large ships equipped with diesel engines during operation, and also to remove coke-like substances that adhere to the inner walls of kilns, etc. For coke-like substances, when a slurry of this combustion improver is applied, dried, and then heated, ignition occurs at a temperature of 250 to 350℃, combustion begins, and coke-like substances are formed in a short time. Burning of substances will now end.

EXAMPLES The present invention and its effects will be specifically explained with reference to Examples below.

Example 1 A coke-like substance attached to the exhaust valve of a large diesel engine (56.2 wt% carbon content, 4.0 wt% hydrogen content, 80-t% total combustible content) was treated with the substances shown in Table 1. A well-mixed mixture of combustion improvers (both adjusted to 200 mesh or less) was placed on the balance of a differential thermal analyzer as a sample, and the measuring section of the analyzer was set at 200 mesh.
The temperature was raised at a rate of .degree. C./min, air was passed through at a rate of 10 tal/min, and the weight of the sample and temperature change were recorded.

The results are shown in Table 1.

(Note) Combustion improvers A, C, D, E, F and G consist of the following composition.

A-...-'CucI powder and KCI powder weight ratio 1:1
Petroleum paraffin wax (melting point 60~
The above wax was heated to 80°C and diluted with heptane.
uCl/KCI mixed powder was added, and after stirring and mixing, the butane was distilled off to support the mixture.

C・---・FCC catalyst (silica alumina type, used one), CuC1, C1 and mineral oil base lubricating oil (
The FCC catalyst powder was added to an aqueous solution of CuC1 and KCI (19:1 weight ratio), stirred to impregnate it, dried, and then calcined at 200°C. The obtained powder is added to lubricating oil to adsorb nuclear oil, and the amount of the tertiary component supported on the FCC catalyst is as follows.

CuC1) 9wt% KCI 1 wt%t% oil
10-t% D-----Flame improver Prepared in the same manner as in C except that liquid polybutene, which is a synthetic lubricating oil, was used instead of mineral oil-based lubricating oil.

E: Combustion improver A prepared in the same manner as A except that CuC1 powder was used instead of CuC1 powder.

F-----Cu in place of CuC1 in the combustion aid C
Prepared by the same procedure as C except for using C1z.

G -...- Light oil (instead of lubricating oil in combustion improver C)
Prepared by the same procedure as C, except using a boiling point range of 230-360°C.

Furthermore, Tis, Tm, and Tf in the table are as follows.

Ti----Temperature at which coke starts to burn as the temperature rises.

Tm - - Temperature when the degree of weight loss of coke reaches 〃.

Tf---Temperature at which coke combustion ends and weight loss stops.

Example 2 The coke-like substance (suit) Ig used in Example 1 was collected in a flat state on a magnetic plate, and 0.5 g of each of the combustion improvers used in Example 1 was sprinkled on it. The magnetic dishes were placed in an electric furnace kept at a constant temperature (300°C, 350°C, 400°C, and 450°C), left for 10 minutes, and then the combustion rate was determined from the change in weight before and after placing them in the electric furnace.

The results are shown in Table 2.

As shown in Table 2, it is recognized that the combustion promoting effect of the suit is high when the combustion improver according to the present invention is used.

Claims (7)

[Claims] (1) Copper chloride powder and potassium chloride powder 5:95-90
A combustion improver for combustion of coke-like hydrocarbon substances, which is made by mixing 10% by weight of a mixed powder with 5 to 50% by weight of a hydrocarbon having a boiling point of 350°C or higher. (2) The combustion improver according to claim (1), comprising a mixture of hydrocarbons supported on one or both of copper chloride powder and potassium chloride powder. (3) The combustion improver according to claim (1), which is formed by mixing a hydrocarbon in the form of a porous powder supported on it. (4) Claim No. 1 consisting of a mixture of copper chloride and potassium chloride or both supported on porous powder and hydrocarbon supported on porous powder.
Combustion aids listed in ). (5) The hydrocarbon is one or more selected from the group consisting of mineral lubricating oil, synthetic lubricating oil, liquid paraffin, crude wax, and paraffin wax. A combustion improver according to any of paragraph (4). (6) The combustion improver according to claim (5), wherein the paraffin wax is a petroleum wax with a melting point of 50 to 150°C. (7) The porous powder is one or more selected from the group consisting of alumina, silica, silica-alumina, zeolite, graphite, and carbon black. Combustion aids listed in section.