JPS5842692A - Zirconium additive for residual fuel oil - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relies on the use of *W zirconium salts in Kfi fuel oil to reduce particulate matter violet formed during combustion.

Grade N114.5 and 6 (AS'1”MD-5
96) and other IJ! 4111 fuel oil is widely used in a variety of industrial heating and steam boiler applications.

- The preferred fuel oil for this purpose is Level 6, which is widely used by gas and electric power companies and others.

US state and federal EP human emissions standards currently restrict the use of residual fuels that produce excessive amounts of particulate emissions during combustion and thus do not meet the standards.

However, this situation has become relatively complex. This is because each state's emission standards tend to be different, and residual fuel oil that meets standards in one state is not necessarily accepted in another state.Furthermore, standards are constantly changing and are currently not consistent. This is because there is a possibility that in the near future, even the fuel oil that is currently used may not be able to be combined in the same region and under the same end-use conditions.

Fuels that tend to have a granular finish of more than 411Ilit typically have one or more of the characteristics associated with them:
That is, the yellow content is greater than FIT%, and the yellow content is greater than about 7%.'771!4WII! Duty (ASTM
1) It has an asphaltene content of -189 or higher. Fuels that produce g2-like emissions in excess of existing standards cannot be used directly, but in some cases fuels that meet existing standards are generally low in sulfur and/or carbon and asphalt. / Can be mixed with fuel with low j content. This situation has resulted in an increased demand for fuel oils that meet emission standards, despite a decrease in their supply and an associated increase in costs.

What is currently desired is a high sulfur content, high Conradoso/f! This is a process that allows it to be used for industrial heating purposes in a manner that still yields acceptable particulate emissions even with high carbon content and/or high asphaltenes.

In the field of related problems, it is known in the art that the use of certain additives in certain cypress hydrocarbon fuels can reduce soot or soot during combustion in some cases. It is also known that 0M salt additives can be used in the fuel to inhibit slag formation in the boiler and reduce the harmful effects of vanadium present in the fuel. It is being

However, the use of selected additives to reduce particulate emissions during combustion of residual fuel oils, especially Hn4 fuel oils, has not yet been demonstrated.

Surprisingly, alcohol/phenol or hasulfo/
Selected oil bathable zirconium salts of acids are added to residual fuel oils, especially M
It has been found that the amount of particulate matter formed during combustion can be significantly reduced by 10-25% or more by adding 6% to the fuel oil.

According to the present invention, in reducing particulate matter violet formed during combustion of residual fuel oil, formula (1) (wherein R is a hydrocarbyl group having 2 to 24 RX atoms) ), or an oil-soluble zirconium salt of alcohol-AI or phenol having the formula (Komata), where R is alkyl, cycloalkyl, aryl,
an oil-soluble zirconium salt of a sulfonic acid having an alkaryl or aralkyl group),
having a molecular weight of about 2.500, burning a residual fuel oil containing an effective amount of an additive selected from fresh, with a molecular weight of about 2.500, in which case said amount reduces the cap of particulate matter formed during combustion. A method for reducing violet granulation is provided which is effective in reducing the amount of granules.

Furthermore, according to the invention, residual fuel oil and an oily zirconium salt of an alcohol or phenol having intermediate (wherein R is a hydrocarbyl group having 2 to 24 envy atoms); 1 formula % formula %) (Here, R is alkyl, cycloalkyl, aryl,
an oil-soluble silconitum salt of a sulfonate having an alcohol or an aralkyl group, and which has a molecular weight of about 100 to
Compositions are also provided that include an effective drug additive selected from the group consisting of: having a molecular weight of about 2.500.

A novel aspect of the invention is that the particulate matter formed during combustion
'4I-reduction lies in the discovery that certain alcohols/phenols or sulfo/@ zirconium salts have a beneficial effect on residual fuel oils. The term "f&[residual fuel oil"] as used herein is a well-known one, as mentioned above, and is also used in AST.
Includes grades NEL4, Grade 5 and Nn6 residual fuel oils that meet MD-594 specifications. Preferred values are m, iG fuel.

It is not clearly understood why these particular zirconium additives exhibit this remarkable effect.

The compound of the present invention promotes the densification of hydrogen ash and ember-containing components in the fuel into oxidized or gaseous compounds during combustion in a specific manner, and also increases viscosity. It seems that it will.

[Zirconium salts or compounds that can be used in the present invention]
(also referred to herein as 1 additive 1) is alcohol/
It consists of phenol or hasulfon 1.1lltl soluble zirconium salt. The zirconium salt of an alcohol or phenol selected is a zirconium salt of an alcohol or phenol having the formula (R is a hydrocarbyl group containing from 2 to 24 carbon atoms). More specifically, SC = for example, R is a branched or unbranched hydrocarbyl group, preferably having from 2 to 134 m carbon atoms. A preferred compound is R
is an aliphatic group having 2 to 8 carbon atoms, preferably 5 to 4 carbon atoms. Most preferred are compounds in which R is a saturated aliphatic group, especially one having 5 to 4 carbon atoms. This woodcutter compound includes alkyl, aryl, alkaryl, aralkyl, and alkenyl compounds. In addition, exemplary alcohols or phenols include ethanol, glopanol, butanol, hexanol, decanol, octadecanol, eicosanol, phenol, benzyl alcohol, xylenol, naphthol, ethylphenol, and crotyl alcohol. There are a lot of people. Other information and documentation on conventional alcohols of this type can be found in Hirk-Olhmer's "Enc.
cyclopediaof ('chemical '['
technology” 2nd edition (194!ri, Vol.
, 1, pp. 561-658.

Zirconium salts of sulfonic acids useful in the present invention include:
Zirconium salts of sulfonic acids having the formula (1) in which R is a hydrocarbyl group having 2 to 200 carbon atoms, preferably 10 to 60 carbon atoms.

More specifically - in one case, the group of the sulfonic acid is alkyl, cycloalkyl, aryl, alkaryl or aralkyl, and the IIA salt is about 100 to about 2.5
00 preferably has a molecular weight of fJ200 to about 700.

Sulho/#! is a sulfo group -80,H (or -5o2o
It is characterized by the presence of tH and can be considered a derivative of sulfuric acid, in which one of the hydroxyl groups is replaced by an organic group. This cypress compound is generally
Obtained by processing petroleum fractions (petroleum sulfonates). Due to variations in the properties of crude oil and the particular oil fraction used,
Since sulfonates generally constitute complex mixtures, it is best to arrange them in a general manner to give the molecular weights as described above. Particularly preferred sulfonates are those having an alkaryl group, such as alkylated benzenes or alkylated benzenes.

Specific examples of sulfo/acids useful in the present invention include dioctylbenzene sulfonic acid, dodecylpenze/sulfo/
C. Didodecylbenzene sulfone, dinonylnaphthalene sulfo/acid, dilaurylpenze/sulfonic acid, laurylcetylbenzene sulfonic acid, polyolefin alkyl, benzene sulfo/acid, etc., such as polybutylene and polypropylene. The details of regret regarding sulfonic acid are 1.
(irk-Qthmer's "Encyclopedi"
a of ('chemical Technology
” dl, 2nd edition (1969), VOl, 1?, No. 5
pp. 11-319 and Manufacturing Ch.
4 of emist (October 1950, xxi, 1o)
On pages 17-422 (Luni, Leslie's “Pet”)
roleeum Sulfonates”.

The above zirconium salt ftl11! Methods of making iron salts are well known in the art, and iron salts are generally available commercially.

The zirconium additive is incorporated into the residual fuel oil by dissolving it therein. This is accomplished by conventional methods such as heating, stirring, and the like.

The amount of zirconium additive to be used is such that the amount of particulate matter formed during sintering of the cod oil is reduced compared to when the residual fuel oil is combusted in the absence of the additive.
The effective trace amount is 1. [Start] "Effective nitrate" means a zirconium nitrifier expressed as metallic zirconium in the fuel oil in a mu weight ratio of about 1 to 1 t, o o o ppm, preferably 10 to 500 ppm%, preferably about 50 to 15%.
means an amount of 0 ppm. However, 1~t,
Amounts lower and higher than the o o o ppm range may also be present, provided that an effective trace amount as defined above is present in the residual fuel oil.

As used herein, the phrase "reducing the amount of particulate matter formed during combustion" refers to reducing the amount of particulate matter formed when the residual fuel oil is combusted in the absence of a zirconium additive. A reduction of about 596 preferably means a reduction of about 10 to 25 g6 and more in particulate matter formed. .

In illegal fuel oils containing such additives, fuel oils containing such additives are generally mixed with #1g (usually in the form of air) to form a fuel/air mixture prior to combustion. Generally, the amount of 9 qi used is in excess of that of a chemist in order to completely burn out the fuel oil, carbon dioxide, and water. The reason for using this excess is that complete mixing does not necessarily occur between fuel oil and air, and that a slight excess of 9 air is desirable (this is due to the fact that soot and S- (helps reduce the tendency for formation). In general,
The excess air used will depend on the actual end-use conditions (which can vary considerably from industrial boiler type to industrial boiler type).
Therefore, it is about 2-55% (based on oxygen) than a chemistry class. One disadvantage of using a large excess of air is that it cannot be used for direct heating purposes. However, in the present invention, the use of specific zirconium additives reduces the KA of soot and soot formation.
It has been found that less air in the 14-gas mixture provides reduced particulate emissions and increases the heating efficiency of the JA distillate fuel oil.

The above process of mixing fuel oil and air is conventional and usually involves producing a fine jet, for example by blowing steam or air, which is then combusted to maintain a flame. will be accomplished. Combustion occurs in a controlled manner at a combustion rate of 1 (which is usually expressed as lb/min of fuel oil combusted).

Combustion of residual fuel oil is generally carried out in conventional industrial boilers, utility boilers.
r), performed ritual rituals in smelting furnaces, etc.

The amount of particulate matter formed during combustion of residual fuel oil varies over a wide range and depends on the type of boiler, boiler dimensions, number and type of burners, the source of residual fuel oil used,
It depends on a number of factors such as the amount of excess air or oxygen, combustion rate, etc. Generally, the amount of particulate material formed will be in the range of about 101 to 10 weight percent of the fuel oil used and more.

1 weight - is formed from the combustion of 100 I of fuel oil 11
of particulate matter. The amount of particulate matter formed (referred to herein as 1 total particulate matter 1) is l! In some cases, 2
Two separate measurements are taken: one is a reservoir of particulate matter deposited on the inside of the boiler, and the other is the particulate matter that forms but escapes the boiler and actually goes up the chimney into the atmosphere. The amount of particulate matter emitted is the sum of the amount of particulate matter that has been filtered and the amount of particulate matter that has been filtered. It only concerns the f'A flue granulation that contributes to the decline.
glands” and increase total operating costs. Historically,
As the tubing collects inside the device, in contrast to the critical effluent, further tubing is then entrained into the flue particulate matter, causing a significant increase in particulate emissions. Thus, in order to fully evaluate the overall operating benefits of a particular jAw fuel oil in boiler operations, the total flue particulate matter as well as the pipe layer particles must be considered to meet the standards. Must be.

#! The amount of smoked granules that are allowed to be contained varies from time to time in the United States, and the amount that is allowed under federal WPA standards also varies. For example, in Florida, the current allowance for existing electricity generation/* is 110 particulate emissions per 100 BTUs.
11), which corresponds to a particulate spontaneous emission* of approximately α1851 amounts per heavy violet of burned fuel oil. If
Because emissions standards vary from jurisdiction to jurisdiction, different amounts of zirconium stock additives are required to produce residual fuel oil compositions that meet these standards.

1 The measurement of the amount of flue granular proboscis 1 is h, P A Met
hod* 55tack Sampling 5yst
em's” Determination of Part
iculate Emissions from 5t
ationary3sources”.

Flue particulate emissions generally consist of particulate flutes, sulfur-containing hydrocarbons, inorganic sulfates, and the like.

The following examples are illustrative of the invention and should not be construed as limiting the scope or spirit of the invention.

Twisting---1- 50 horses 5 forces 1. Combustion experiments were conducted in a BCO (two-pass) water-jacketed IM draft boiler with an air injection nozzle and a nominal combustion rate of 121 b/min of residual fuel oil. This boiler was modified so that the closures at each end could be easily opened for collection of deposits that had accumulated in the boiler. Two other modifications include the provision of a second fuel system so that the boiler can be heated to a comfortable operating temperature and then switched to a separate fuel without changing the operation of the boiler; The burner end of the combustion tube was lined with up to 2 feet of refractory brick, and the Monarch nozzle was replaced with a Cleaver-Pulx nozzle assembly. These deformations result in oil pooling and rapid R1 on the combustion tube wall when residual fuel is burned.
# A adhesion was removed. The diameter of the passage is 49C1l (18
, 575in) x combustion tube length 1781 (5ft 1o
in ), and the second passages each have a diameter of 63 (2
,575in)
It consisted of 52 tubes of n).

Atomization of the fuel was achieved using a low pressure air atomization nozzle. The viscosity of the oil at the nozzle was maintained at 50 centistokes by heating the fuel oil to a temperature of approximately 105°C. Prior to contact with the burner gun, a diffuser plate was placed on the atomized fuel oil. Efficient combustion was ensured by mixing a small amount of secondary air forced into the boiler head. This secondary air was provided by a centrifugal blower attached to the boiler head. The amount of KIi14 was controlled by a KIi14 damper to maintain the oxygen level in the fuel at approximately 1516 excess (above the amount stoichiometrically required for complete combustion of the fuel). .

The experiment began by igniting the boiler using hot oil and heating it to operating temperature for 55 minutes. The feed is then switched to the test fuel and after the F1f trough has had sufficient time for the foreshadowing to stabilize (approximately 25
minute), Castle of Germanmes tared from the flue (215x
2a4cm) Glass 1 [Samples were collected isokinetically for a period of approximately 10 minutes on the filter. The test fuel was Level 6 fuel oil.

The total particulate matter formed is uniformly 6111 constant ()! Sp
AMethod 55tack Samp ng 3y
stem) was determined by adding the amount of flue particulate material deposited on the boiler tubes.

The HPM Method 5 flue sampling scheme was carried out on commercially available equipment for this purpose. This device is 1 B in
Glass prope, cyclone, 125 pieces of glass #*
It consisted of a filter and four inbingers.

The first two inbingers contained water, the third was empty, and the last one contained silica gel. With the exception of inbingers, no flue gas entering the sampling device should be allowed to rise above 504) 11 points.
11. All sampling equipment was heated to approximately 175°C to obtain
maintained.

The deposits deposited on each of the 52 tubes were collected on separate tared glass II & fiber filters.

The deposit was placed in a specially designed filter holder on the 11th section of each tube, a high volume vacuum pump was used to draw air through the tube and filter, and the end of the tube was placed 2.50 in. 1 by hand with a pole wire brush
0 (b) Collected by brushing. The brush was attached to an 88 rod of length a ft and diameter [L2 sin] driven by a demon drill. This method
This resulted in recovery of almost 100- of deposits deposited on one circle. Samples were taken from all palaces. This is because in a given experiment there is a large difference in the bulk electrification of each row of tubes across the boiler and between the upper and lower rows; This is because the weight ratio of deposits is inconsistent.

Analysis of the fuel oil (test fuel) used in each experiment revealed the following components.

Analysis of test fuel sulfur 20 sulfur/residual coal volume 148 electrification ash (bl
α1 heavy weight - vanadium
44? 19m nickel
yoppm iron
The zirconium additive used in the experiment was zirconium propoxide, which is an alcohol salt, and the zirconium metal compound [calculated] It existed at a concentration of 1009?m.

For the test fuel alone, the flue grain quality was IIL for the fuel.
The total tested particulate matter was 154 weight t* compared to the amount of α2Ofi relative to the fuel. When measuring a sample of fuel containing zirconium propoxide, the flue grain quality is α
At a weight of 24, the tubing was approximately 16J to the fuel, and the total particulate matter was 04,040 couls.

The improvement when using zirconium additives is 2! of total particulate matter! &9% decrease.

Example 2 Following the same general procedure as described by NIK (ABCL)
A sample concentration using 100 ppm of a zirconium sulfonate additive, ie, the zirconium salt of dodecylbenzenesulfonic acid, was performed on a 111 to 6 fuel oil using a boiler.

The results for the sample containing silconium sulfonate showed that the flue particulate matter was α29 coulometric with respect to the fuel, the pipe-fitted material was α29 coulometric with respect to the fuel, and the total particulate material was The improvement when using the zirconium additive was due to the IA of the whole particulate material.
It was a decrease of 0%.

Claims (1)

Claims: (11) In reducing the amount of particulate matter formed during combustion of residual fuel oil, (:) where R is a hydrocarpyl group having from 2 to 24 carbon atoms. or an oil-soluble zirconium salt of alcohol or phenol having (-) formula (%) (where R is alkyl, cycloalkyl, aryl,
Addition of an effective amount selected from: an oily di-J/:1 salt of a sulfonic acid having an alkaryl or aralkyl group, and having a molecular weight of about 100 to 100 flzsoo. A method for reducing the amount of particulate matter comprising combusting residual fuel oil containing an agent, said amount being effective to reduce the amount of particulate matter formed during combustion. (2) The method of claim 1, wherein the additive is present in the fuel oil in an amount of from about 1 to 1,000 ppm by weight, expressed as metal zirconium salts. (3) The method according to claim al or 2, wherein the fuel oil is t*6 fuel oil. (4) Fuel oil is 1fJ1]! The method according to any one of claims 1 to S, wherein the method contains more than 1 part of sulfur. (Claims 1 to 4 in which the R group of the 51 alcohol salt is a saturated or unsaturated aliphatic group containing 2 to 8 carbons)
One chess method for either spear. (6J R group of sulfonic acid is alkaryl group,
and the salt has a molecular weight of f) 20 G to about 700. (7) Residual fuel oil and an alcohol having intermediate ROH (where R is a hydrocarbyl group having 2 to 24 vertical atoms), particularly an oil-soluble zirconium salt of phenol, or (i11 formula ( Here, H is alkyl, cycloalkyl, aryl,
an oil-bathable zirconium salt of a sulfonic acid having an alkaryl or aralkyl group, and which has an alkaryl or aralkyl group.
and an effective violet additive selected from the group consisting of: having a molecular violet of ~2.500.