JPS6081293A - Liquid-solid dispersed fuel - Google Patents

Abstract

PURPOSE:To obtain the titled fuel of excellent flow properties thus suitable for pipelining, by incorporating specific amount of partially desulfonated lignin sulfonic acid (salt) in a mixture of powdery coal and alcohol. CONSTITUTION:The objective fuel can be obtained by incorporating (A) 0.005- 5wt% of at least one sort of partially desulfonated lignin sulfonic acid (salt) derived from desulfonation of lignin sulfonic acid (salt) in (B) a mixture of powdery coal and alcohol. The counter ion to form salt is pref. of mono-, di-, or tri- valent metal, ammonium or amine. Said desulfonation is to be performed, in the presence of alkali under and initial pH>=9 at 100-300 deg.C, by injecting air or oxygen gas followed by high-temperature oxidation.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a dispersion-solid dispersion fuel that has superior flow characteristics for vibrate feed and combustion.

In recent years, much research has been carried out on the handling of coal as fuel, such as dispersing pulverized coal in fuel oil or water to form a slurry.

This is being transported by pipeline, but
Even when it fell down, the amount of coal was 20 to 40 cars, and the force was low.

There are problems such as a decrease in calorific value during combustion, and it has not yet been possible to solve the problem of low heat generation.

As a way to overcome the above-mentioned deficiencies, mixed fuel with vJ powdered coal alcohol has been attracting attention.

If you simply mix powdered coal and alcohol, the powdered coal will settle and separate due to the difference in specific gravity, condensate, and lose its hydration properties, making it impossible to obtain a satisfactory mixed fuel. I can't do it.

Therefore, developing a nitrifying agent that increases the stability is also one of the military's top priorities, and an example is JP-A-UTQ 57-
An example of this can be seen in No. 14939i, etc., but even when using a removing agent with an amount of 1M or more, the stability of the FM grafted on ships, etc. is poor, and practical application is far away.

No. 55304 of 1982 shows that a combustible pseudo-shock throbbing suspension can be obtained by dispersing simulated pulverized coal in which most of the coal particles are 100 mesh or less in methanol. The suspension can be maintained in a cloudy state during storage (with only mild agitation) and is maintained so that it does not separate when pumped through a pipeline;
Shear thinning rheology is used, and the viscosity is lower than the viscosity of the tank, which is lower than the viscosity of the pump. If the stirring is stopped while stirring, the lower part of the storage container [a part of the charcoal is deposited and becomes a hard coal shield, so-called specific gravity]. In some cases, it is possible to restore fluidity by stirring the compressed duck on its own, but in some cases, it may be difficult to recover the original amount. IiQ with land power 1 and 7 days trading land 1! η Considering shipping and storage @, technical.

This is a huge economic problem and cannot be dismissed as a sacrifice.

If the coal particles are small and the colloidal turbidity is maintained in a vinegar-like state, sedimentation is difficult to occur, the cheapness is good, and the pulverization cost is low. Nice to meet you (
It also has the disadvantage that it exhibits excessive viscosity and is difficult to pump, and it is not possible to obtain a satisfactory powdered coal-alcohol mixture.

In addition, a suspension made by simply mixing powdered coal and alcohol becomes unpalatable and so-called dry when the coal viscosity is increased.

◇Therefore, pipeline transportation and spray combustion are unparalleled, and if you lower the degree of lime by 1. ．． Transmission efficiency 1
It is not practical because the J length is lowered, which poses a big technical and two-way problem.

/4-, Yamei name, etc. is υ-shaped coal, alcohol, and θ)
Overcoming the above-mentioned deficiencies of fuel that uses 7-containing compounds as raw material 1
- By using an abrasive with the same structure as above, it is possible to obtain an excellent effect on the flow resistance of pipeline conveyance and Ic combustion. He discovered this and achieved non-invention.

In other words, the present invention is to add one or more of the following salts to a mixture of powdered coal and alcohol to a mixture of powdered coal and alcohol, a liquid liquid-hedra fractional fuel, and one or more of these salts.
005-5 is a dry song of the 5th Judo attack, and it is characterized by the word M-cho ◇ 7
It is powered by a fractional fuel.

According to the present invention, by using the above-mentioned specific engraving agent, the viscosity is reduced and the fluidity characteristics for pipeline transportation and combustion are excellent. There is a large difference in demineralization, and it is possible to obtain demineralized or recycled fuel [F].

Above mentioned σ) Lignin sulfone ridges, etc. One example of such gates is - wood chips made of ``Kigu wood, Hiroshita'' wood, and their pond glue genin 2. 1 plate of saltwater salt tutc K Yuzoku 7ken and R ζ (steamed) Depending on the base and the platform, β-naphthylamide 7 stone 1a W N, acrifurahin, thio 7 labin.

Before Lime g) Separation of Hekinsu, Pentose Cutting/Ayana's Hyabusu Sugar Excitement, Sugar Yu Chengku, and Mudendai by the Precipitation Method using a precipitating agent, the Hansen Method, the Combination Method, and the extraction method, etc. - Soi 1 ``Gninsulfo/koshiki that settles dust and whether they are σ1 life or injection,
Lignin sulfones and/or their σ) Salt-based products are fine; lignin raw materials, lignin raw materials, and other α) salts are acceptable.
The component 'a '43''nE r cursive processing method has been added by 1 and is not Φ.

Partially desulfonated lignin sulfonate acids and their salts used in the invention include:

The above-mentioned compound σ) has a preferable degree of sulfonation, and is obtained by desulfonating the salts of geninsulfone σ) and σ). 0.25 equivalent of propane unit, below t'l'-+', 1 or 0.2 equivalent or more σ). Sec.
6 compounds obtained by making lignin sulfone ridges and/or by converting them to salt and desulfonization, and the history of them.
jj! Ai 1 - Naru, Isao 1 Narastai are separated and combined 1 and 4
W cup" or cut out.

These partially desulfonated lignin sulfones, katana, and their salts, have a higher tl) and α),
It has a large amount of carboxyl groups and phenolic hydroxyl groups (θ), and a small amount of sulfones and alcohols (= hydroxyl groups),
The father molecule i is comparatively small at about 32,000 J. Partial desulfonation of cholera consists of ni/sulfone compounds and their σ) J benefit, and those with a degree of sulfonation of 51 cm (phenylpropane) or less than 0.25 fi, have an alcohol compatibility of 1 The viscosity of the coal-alcohol slurry is extremely good (haligenin sulfonic acid and its salts exhibit completely different chemical and physical properties).

The agent of the present invention which is used in the preparation of Ld7 body-dividing agent is the above-mentioned partially desulfonated guninsulfone E, S et al.
) Shio de (ha good"EL< is the 11th song, 21th song or 31st group's Kasazanshio.

Ammonium nitride or amine salt. These j
The benefit is that the dazzling is the sword of any of the three groups.--Thou shalt make salt unto the river;
Even if you use 7F of the L-kai base separately, it will not produce a sword or indigo.

salt? Forming and closing gold is lithium. Sodium, Potassium, Magnesium, Calcium & Zinc, Cadmium, Barium, Aluminum, Tuna.

Soot, *IL chromium, mankan, iron, cobalt, nickel, etc. are useful.

Also, examples of amines that form salts include aliphatic amines.

BFJ tM Group amines, aromatic amines, alkanolamines, pyridine and its derivatives, quaternized compounds having πN, etc. Examples include methylamine, ethylamine,
Butylamine, octylamine, laurylamine, stearylamine, oleylamine.

Dimethylamine, N-methyl-laurylamine.

Dilaurylamine, trimethylamine, N,N-dimethyl laurylamine, ethylenediamine.

Hexamethylene diamine. Diethylenetriamine.

Gogetsuji Alkylamine Talohexyldiamine, triethylenediamine.

Morpholine, monoethanolamine, jetanolamine, triethanolamine, monoinfropanolamine, diimpropaturamine, triisopropaturamine, aniline, P-toluidine, m-)7tzidine, nitroanilino, benzylamine, pyridine , phenylenediamine, and benzidine are useful.

The moiety JR sulfonated lignin sulfonic acid Zl'' C)
/． C enemies and their salts. It is a known compound.

It can be manufactured using known methods. The reduced pulp is steamed, ribbed or separated, and geninsulfonic acid and its salts are treated with an alkali such as caustic soda. The first pH is 9 or higher. Temperature 100~300℃ preferably 150~250℃. Inject air or eye drops. Desulfonation is achieved by high temperature oxidation. Depending on the combination, the reaction by-products may be separated and removed, and the reaction by-products may be separated and removed. Samurai J is caused by the β-salt reaction. It is not limited to these. It may also be heat treated at a lower pH to desulfonate it.

A sword for non-invention > 7)) Rudetsu 5 powers L] ilj (1) As a specific example. Synthesis example below. Is there a table item?
These are examples. It is not limited to these.

Partially desulfonated guninsulfonated soda salt (Product name [manufactured by Vaniresox HWJ Yama 1 Yi Sanki Valve (3)] Partially desulfonated guninsulfonated soda salt (product name "Vaniresotasu RN" Yamagata] Prison pulp 1) folds) Gb de-sulfonated/re-converted ninsulfonated soda salt (product name 1Mar
asperse (manufactured by CHjMaratlion) Uninvented Adult - 1 Sea 1 Body Branching Pressure The amount of the special additive used is. It varies depending on the type 8 coal, particle size distribution, etc. In general, 0.0 0 5 for all dispersed fuel
~5% by weight, and the ratio is in the range of 0.01 to 210%. If the amount added is less than 0.005% by weight, it is not suitable because it is difficult to obtain a sufficient fluidity improvement effect.
If it exceeds 5 Jk%, it is not disadvantageous from a social standpoint, but on the contrary, it impairs fluidity and is an uninventive adult-isomer dispersion agent α.
) It is not favorable because the delayed physical properties cannot be determined by f3I.

Also, non-lead additives. Other thinning agents) Single or copolymer salts of unsaturated substances such as acrylic acid.

Force salts such as citric acid. Fufufuhi Aromatic θ Group Combination Rider/Raf. r6 polymer σ) sulfonate. Anionic surfactants such as naphthalene sulfonate, petroleum sulfonic acid, formalin ellipse, and salt. Amine, Δ) 6 units Hanshio,
Ionic compounds such as guate and carbonate are blue.

An example of a stabilizer is a carboxylic acid. alcohol, amine.

An alkylene oxide adduct containing a compound containing at least 11 active hydrogen atoms in the molecule, such as polypropylene glycol, phenol water injection, etc., with an ethylene oxide content in the molecule of 80 twit coefficient or more and a number average molecular weight. or 1,000 to 100,000 compounds $1 = v) Nonionic surfactants, esters of these, phosphorus esters.

N,N,N-distearylψmethylammonium betazine, etc., 1st grade carcinogens, IOA imitation grain silica,
Sword - pump rack, bentonite play θ) May be used in conjunction with the collection of treasures.

In this book, Ming's research results may be used as follows: 1) In order to enhance the effect, pre-preparation of a consortium, such as water, may be used.

Lower alcohols, acetone, toluene, and mixtures thereof, etc. (C and 〃j, and 0 and θ, which are preferred for soft tools) May be added when wet pine 4% or coal λ・J?
? It may be added at the time of mixing, or after the mixing with the pre-pulverized coal.

The powdered coal used in the unidentified liquid-solid dispersion fuel is smelt coal* 'Il'a# coal, sub-iron coal, and lignite.
・Select [F] At least 1 ti of coal + rb
1 Regardless of the extreme size or neck of the coal, or regardless of its chemical composition or water content,
things are also available. Also, regarding the thickness of coal particles, 1 particle θ) Regardless of the size, X invention σ) 1- The viscosity can be lowered by using a loose additive. It is effective in distributing the Qf cut-off characteristics, but one coal particle is 4 meshes or less, and it is unclear that most of these particles are 10 meshes or less for the sword X. It's a good time. This σ) The mixed group of powdered wood-like charcoal is favorable and exceeds 80 Kurumaishi%. When powdered coal is mixed with alcohol, the viscosity becomes 1'<fx and the fluidity deteriorates, which is not good.
) 4tt: Mix 1 In this case, liquid-solid dispersion fuel
) Number body-II! i1-body fuel σ)f is unfavorable because it cannot obtain the desired physical properties.

It usually weighs 30-80 tons, more preferably tl<Li40~
It is in the range of 70 cents.

In addition, the liquid-solid dispersed concretion according to the invention can contain moisture in an amount of 30 weight φ or less with respect to the solid dispersed fuel. If the number exceeds the number, the number of bodies and one solid dispersion is greater than the transportation cost of heating charge, storage cost,
Others - Relatives'θ buried j (Karasu na flea further increases the heat loss due to water emitted by fish R:'l when burning) Zete board: 11! 1
An example is mono and ding [F] and katebi Φ.

The regulations to reduce NOx in the combustion nF residue and return to the bottle are as follows:
5 ~ IO Megumi Q) Moisture 7a' sweetness ρ) Good! L.

The moisture in the coal is usually 1 sword), but the power is 11 things, 1 warping sword, and the visitor can choose 2 loyal and quick ◇.

Unknown σ) Adult - solid content, the alcohol used for 1 medium plate is a small amount of low grade Mt rib alcohol with 1 to 4 ash repertoires. .

Methyl alcohol. Ethyl alcohol, n-propyl alcohol, 1so-7-robil alcohol.

n-methyl alcohol, Left-methyl alcohol.

Melt with ethylene glycol, fluoropylene gelicol, etc. 2
Particularly preferred is methyl alcohol containing molluscs and molluscs, and compounds contained in the alcohol during production, solvents, organic compounds such as water, etc. It is okay to have one's own property.

The liquid-solid dispersion fuel according to the present invention has a low viscosity and excellent flowability, and can be easily transported by pipeline and spray-combusted. The time and department are.

The upper and lower layers of the stationary plate 10' α) Coal and ash working site 25 It is possible to separate the ash from the coal-alcohol furnace, which is used for the dispersed fuel. The ash content in the coal particles causes agglomeration and settles into sieves 1-6. It is considered to be the norm◇.

Next, the invention will be explained in detail with examples and examples.

Synthesis Example 1 Lignin sulfone enemy sodium foam [Product name: "Sun Extract 252" Sanyo-Sakuno Kurupu (this product, daughter 1 m 43 mm
%, the degree of sulfonation of the corresponding gunin sulfonate/basodium (
(per phenylpropane unit) 046 mass, 1232.6
caustic soda 50. (The number of l added? 170~200'
C. After 1.5 hours, the guninsulfone and
v Precipitated and partially desulfonated Kuninsulfone string (
A-1) into a dog. The degree of sulfonation (per unit of phenylfuropane) (JIS K3362-1978 and the enemy barium heavy violet) is 0.06 kankoma.This partially desulfonated guninsulfone yield (A- 1) was neutralized to 1) H7.5 with caustic soda and sulfonated with 92% sulfonation of sodium sulfone (-A-2).

Case 1 Example 2 Sodium lignin sulfone bath solution [Product name: ``Sunextract 252'' Sanyo Gahoe Valve (to) W a6-magnetism 43 Sulfonation of sodium lignin sulfone 1
f(phenylpropane unit +)) 046 unit] to 40
Add 90% sodium chloride solution to pH 12 and Lr, [,150
The air was subjected to inlet oxidation treatment at −1so° C. for 60 minutes. Sulfuric acid was added to the mixture to adjust the pH to 2.5, and the lignin sulfone group (A-3), which was partially desulfonated with the desulfonated lignin sulfone HY1-V, was added. Sulfonation of this #(
Phenylpropane unit <JlsK336.2-
In 1978, 023 silkworms were measured using the barium measurement method. This partially desulfonated Guninsulfonist (A-3) was adjusted to pH 9 with 4 caustic soda,
Then, a desulfonated lignin sulfone (8-4) with a tail of 95% was obtained.

Synthesis Example 3 Lignin sulfonic acid triumra chlorine [Product name 1-''!
7-N Extract 252'' Yama 1 Kabura Kokuan Pulp 19 products.

Once attacked by the 43rd Army B1, the degree of sulfonation of sodium lignin sulfonate (noenylproban base 4i't')
After adding 40% bamboo soda solution to pH 12 to 71C, metal air was press-injected and oxidized for 30 minutes to 150 to 180'C-C.
, 5 and desulfonated guninsulfonic acid￥Shen-M
Partially desulfonated lignin sulfone (A-5)
hurt. The degree of sulfonation (iJ per phenylpropane unit) (measured by JIS K3362-1978 and barium sulfate gravimetric method) is Q, 32 '7
This partial desulfonation 'I kninsulfone i, jkll A-5) ';
8 and added 4 to the partially desulfonated sodium sulfonate (A-6) of 1 trillion 92%. ) 3. o? .

Methyl alcohol 207>', water 30 r Y I O
Put it in a 0m6 beaker, put it in a homomixer and stir it for 10 minutes at 100 Or pm O> under the sweat. , i:%, 200 mesh passing 75.2 quintillion %, 350 mesh passing 53.6 electricity %, Eibetsu, 0 car punch, ash content 14.8 weight %) 3609 begging.

The mixture was stirred for 20 minutes at 11,000 rpm to obtain coal-alcohol slurry 6002.The viscosity (*1) of this slurry was 1,400 CIJ. Next, we determined the deashability (ash content! β *2) and found that the ash content in 1 coal was 9.8 SM:i)i:%
.

The weight of Nakanoso is 11.2, and the lower layer is 20.8% by weight.

The difference in ash content in the coal between the upper and lower samples was striking. This mixed ingredient of coal and alcohol and DingΦ7v
The fuel in the direction of the body is dry or low, and the fluidity lags behind the fluidity, and it is easy to burn the pipeline, and the demineralization property is not good in history. There was 0 (*l) Viscometer two-wheeled cylindrical viscometer (for The Hague, Rotor M vII
) k for a, vi, lA 2'J 'C* rotation H51' pnl -CIll was determined. The viscosity of the dispersed fuel is approximately 1 d higher than the Ule mobility.

(*2) Demineralization (ash content) test Put the above liquid-solid dispersion application into a 500 m cylinder (inner diameter 50 m/m) in an amount of 500 me.

Let it stand for 3 days at the lowest temperature and after aging for 6 degrees, take out the upper part 170 of the fraction in this cylinder and use it as the upper layer sample. Divide the lower 160 kites with the lower layer sample. σ) Ash content in coal in these samples is determined as 61i1 according to JIS M8812. The amount of coal in the coal between layers σ) The large column on the left indicates that the deashing is good. Salt, Sho, S-moon force brother sulfonated guninsulfone IJ Using clay as the main ingredient and Ding/J-squeezed product @, use the same method as Loss 1 ri υ 1 to make coal/ω Daburi 1 Water/
Using alcohol, I prepared a liquid-viscous fuel whose main components were coal and alcohol. Table 1 shows the demineralization properties of these materials. In addition, using Δj sword agent, Jim L inari base, and the combination of Akita with other than the additive of this t9 light is also listed in Table 1 as Higeki j. Same 'J': Processing example and specific soft chestnut tξ river σ) properties from the second u/c
Show me. .

As shown in Table 1. The liquid-solid dispersion heating material of invention Regardless of alcohol. This has the effect of reducing viscosity and improving the flow characteristics of Zevibra 1 transport and combustion. Furthermore, it is clear that the demineralization property is good. The lignin sulfonate shown in the comparative example, which was not partially desulfonated, had a low viscosity, so it was difficult to feed the vibrine. 7 members of the special 1st class of the squad Ouchi Nobi IciI were seriously injured. Furthermore, the demineralization properties were also poor, and it was not possible to use the same method to remove the fine grains.

Table 2 Properties of coal (% indicates weight attack)

Claims (1)

[Claims] (Li) Partially desulfonated lignin sulfonate obtained by desulfonating lignin sulfone modified and their salts in a liquid-solid dispersion fuel mainly composed of a mixture of powdered coal and alcohol. A liquid-solid dispersion fuel characterized by containing reeds or two or more of these fences in a dry range of 0.005 to 5 weight groups. (2) A pair of salts forming two The ion is l″11111m21
11111m21 curved size ammonium or amine'T
: A liquid-solid dispersion fuel according to claim 1 of a patent claim.