JPS6099197A - Petroleum coke-water slurry composition - Google Patents

Abstract

PURPOSE:To provide the titled stable composition having high solid concentration and low viscosity, and capable of keeping the solid fuel powder from coagulation and precipitation, by using a dispersing agent comprising a compound containing tricyclodecane or tricyclodecene skeleton and a sulfonic acid group as essential constituents. CONSTITUTION:The objective petroleum coke-water slurry composition can be produced by adding preferably 0.05-1wt% compound containing tricyclodecane or tricyclodecene skeleton and a sulfonic acid groups as essential constituents [e.g. a compound obtained by sulfonating a polymer of the cyclopentadiene (derivative) of formula I or formula II, sulfonating the reaction product mixture of said cyclopentadiene (derivative) and the compound of formula III, or condensing the sulfonated cyclopentadiene derivative of formula IV, etc.].

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to petroleum coke water slurry compositions containing specific dispersants. For more details.

The present invention relates to a petroleum coke-water slurry composition using a compound essentially containing a drinkloacane or tricyclodecene skeleton and a sulfonic acid group as a dispersant.

A method of gasifying solid fuel such as coal to produce water gas is well known. As one method.

There is a method of pulverizing solid fuel into a fine powder and supplying it to a water gas generator as a dispersion in a gaseous medium such as water vapor or nitrogen-permeated gas. However, with this method, it is difficult to control the amount and rate of solid fuel supplied to the water gas generator. For this reason, in recent years, a method has been proposed in which powdered solid fuel is dispersed in water to form a slurry and this is supplied to a water gas generator, but this method has various problems.

The solid fuel-water slurry for water gas generation preferably has the following properties.

■High solid content (a).

■ Low viscosity.

■ Solid fuel paddy rice should be stable without agglomeration or sedimentation.

Especially when the solid fuel is petroleum coke.

Due to the high water dispersion properties of the surface, systems containing only petroleum coke powder and water often aggregate and remain in a lump-like shape even after strong stirring, but the mixture can be dispersed uniformly by stirring the two components. Even if this occurs, agglomeration will occur soon and a hard sedimentary layer will be formed.

This petroleum coke is the residual coke obtained by further thermally decomposing the silkworm residues such as asphalt and pitch during the distillation of petroleum oil at pan temperature, and its powder is extremely terrible compared to coal powder containing inorganic substances. It is difficult to get wet with water.

In order to obtain a petroleum coke-water slurry that satisfies the above-mentioned conditions ① to ②, they conducted extensive research and found that the slurry contains a tricyclodecane or tricyclodecene skeleton and a sulfonic acid group. The present invention has been achieved by discovering that a petroleum coke-water slurry composition using a compound essentially containing as a dispersant satisfies the conditions (1) to (2) above.

That is, the present invention provides a petroleum coke-water slurry composition characterized by containing a compound essentially containing a tricyclodecane or tricyclodecene skeleton and a sulfonic acid group in the molecule, petroleum coke, and water. be.

Next, the present invention will be explained in detail.

The dispersant used in the present invention is a compound containing a tricyclodecane or tricyclodecene skeleton and a sulfonic acid group in the molecule, and at least one type selected from the following fil to (6) is used. Ru.

In the present invention, the tricyclodecane skeleton or tricyclodecene skeleton is shown as follows. ((stomach),
(B)) (-'! That is, tricyclo(5,2,1,0) akan or decene) (1) Cyclo expressed by the general formula (al or general formula (bl) as shown in Japanese Patent Application No. 57-35148) A sulfonated product obtained by sulfonating a polymer obtained by polymerizing pentadiene or a cyclopentadiene derivative.

(In the formula, 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) (In the formula, 1 and 1% are the same or different, and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) (2) cyclopentadiene or cyclopentadiene derivatives represented by the general formula (at or general formula (bl) and the general formula (c, l) as shown in Japanese Patent Application No. 57-35149.
A sulfonated product obtained by sulfonating a reaction product mixture obtained by reacting a compound represented by the above with L6, or a condensate of the sulfonated product.

(In the formula, 1 (4 and YL are the same or different and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

A condensate obtained by condensing sulfonated cyclopentadiene derivatives represented by the general formula (mountain).

(In the formula, R6, l(, and It are the same or different.

represents a hydrogen atom or an alkyl group having 1-6 carbon atoms,
It, and i(,, o are the same or different.

Represents a hydrogen atom or alkyl having 1 to 3 carbon atoms, n
represents 1 or 2, and M represents hydrogen, an alkali metal, an alkaline earth metal, ammonium, or ammonium selected from amines. ) (4) Dicyclopentadiene represented by the general formula (cl) as shown in Japanese Patent Application No. 57-175666 (where d and M are the same as the formula (di), ) ( 5
) General formula (
A polymer or copolymer of a sulfonated product of hydroxodicyclopentadiene represented by f).

(In the formula, n and M are the same as the formula (di.) condensate.

(In the formula, 几, l, 1 mo, and 2 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and 9M and n are the same as in formula ((I)). (1) Specific compounds that can be represented by the general formula (a'l or general formula (bl) include 9, for example, cyclopentadiene,
Preferred examples include argylcyclopentadiene, such as methylcyclopentadiene, ethylcyclopentadiene, and furobylcyclobenotadine, and dimers formed by arbitrary combinations of these, such as dicyclopentadiene. Examples include cyclopentadiene and dicyclopentadiene.

Alternatively, a mixture of both may be used.

In the above (2), specific compounds that can be represented by the general formula (c, l) include 2, for example, benzene.

Toluene, xylene (o −+ l11-, l) −'
), ethylbenzene, +1-phyllobylbenzene, 1
so-globylbenzene, methylethylbenzene (0,
Ill, l”)+ +1-butylbenzene,' 5
ec-butylbenzene, tert-butylbenzene.

1so-propyl'toluene (o-,...-,,p-).

amylbenzene, hexylbenzene, amyltoluene (
Examples include benzene derivatives such as mono- or dialkyl-substituted benzenes such as o-1m-2p-), particularly preferred are benzene, toluene, xylene, probylbenzene.

Butylbenzene can be opened.

Next, a method for manufacturing the dispersant used in the invention will be explained.

However, regarding the production of dispersants in fil to (6) above, each is disclosed in Japanese Patent Application No. 57-'35148. Special application 1987,
-:35149. %Gan Sho 57-351117゜Special application Sho 5
7-175666', % Application No. 58-43729, and Japanese Patent Application No. 58-42205.

An example of the production of dispersant (11) will be explained.

Cyclopentadiene or 7 Lopentadiene derivatives (general formula (al or (1)l) are combined with coordination compound catalysts (for example, sulfuric acid, phosphoric acid, hydrogen fluoride, boron trifluoride and its complexes, aluminum chloride). .

Examples include aluminum bromide, tin tetrachloride, zinc chloride, titanium trichloride, and the like. ) and, if necessary, a solvent such as a hydrocarbon or a halogenated hydrocarbon, and the polymerization reaction is carried out at a reaction temperature of -20 to 150'C over several hours to obtain a polymer.

The polymer is preferably treated with an inorganic oxidizing agent (e.g. nitrates,
nitrites, etc.) and solvents (e.g., water.

Methyl alcohol, ethyl alcohol, etc.) (1) Usually at a reaction temperature of 50 to 200°C and under normal pressure or increased pressure.

A sulfonation reaction is carried out using a metasulfite or a sulfonated compound such as a sulfite alone or as a mixture, and the sulfonated product is turned blue. From the viewpoint of ease of progress of sulfonation of the polymer, the preferred number average molecular weight is 1 (J(10
0μ or less, particularly preferably: 300 to 5000. The sulfonated compound is usually one in which 20 to 100% of the remaining double bonds in the above-mentioned type combination are sulfonated, and the degree of sulfonation is determined by converting the obtained sulfonated compound into an acid form by an ion exchange method. Convert to .

This can be determined by total alkali titration.

In addition, the sulfonated product can be mutually converted into an acid form or a salt of an alkali metal, an alkaline earth metal, ammonium, or ammonium derived from amines by a method or a neutralization reaction.

An example of manufacturing the dispersant (2) will be explained.

/Rylopentadiene or Hanklopentadiene 1 transparent conductor (
The compound of the general formula (a'l or (11+)) and the compound of the general formula (c-1) are reacted in the presence of the above-mentioned one-layer compound river lubricant and a heating medium, usually at -20 to 150°C. 4. The reaction product mixture is a reaction product in which one molecule of a synchlopentadiene compound is added with one molecule of a compound represented by the general formula (c, l).

Synchropentadiene 4A2 molecules are given the general formula ((,)
In addition to several compounds such as anti-1,6 products obtained by adding one molecule of the compound represented by
Alternatively, the synclopentadiene head polymer and its polymer may be combined with the above-mentioned -1-pronged formula (cl).
It is a mixture of various compounds such as J11 reaction products. (The number average molecular number of the reaction product mixture is preferably 10,000 or less from the viewpoint of ease of cleaning the sulfonation reaction described later. 3.) The reaction product mixture is mixed with the dispersant (
Sulfonation is performed in the same manner as the sulfonation method of the polymer described in the production method 1) to obtain a sulfonated product of a physical combination produced by two reactions. The sulfonated product is heated with an acid catalyst (for example, sulfuric acid, etc.) using a condensation monomer such as benzene, toluene, xylene, or phenol as necessary. ) to the total number of moles of skewered bodies for condensation, and 1
Usually, the condensate is rIJed by using an aldehyde (1!; formaldehyde, acetaltehyde, gropionaltehyde, etc.) using 0.00t11 to 10 times the molar number.

The number average weight of the condensate is preferably 500 to 30,000 in terms of the dispersed seedlings of stone i[11 coke.

An example of the infarction of the dispersant (3) will be explained below.

Compounds represented by the general formula 1 (1) are benzene, toluene, and quintinfurobylbenzene.

butylbenzene, etc.) and a compound represented by the general formula fit (for example, a dimer of cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, etc.) as a catalyst (
Friedel-Crafts reaction is carried out in the presence of (for example, sulfuric acid, phosphoric acid, hydrogen fluoride, boron trifluoride and its complexes, aluminum chloride A, aluminum chloride, etc.), preferably at 0 to 100°C for 1 to 5 hours. 1. A compound represented by the general formula (jl) is obtained.

(H, 6, I also, +-1?, 8 is the previous 7.I2 General (
Same as in the mountain) (I's, LL+o is 1) General formula 11 (il in di) 1l-) (H, 6,, + and 7, 1, , horse, It,, i, as above) General formula (same as in di) A compound represented by general formula (jl) is sulfonated in the same manner as the polymer sulfonation method explained in the manufacturing method of 9 dispersant (1), and then an alkali is added as necessary. A sulfonated product of a 7-clopenic acid derivative represented by the general formula (di) can be obtained by using a metal, an alkaline earth metal, ammonia, etc. to form a sulfonate. A condensate is obtained by subjecting the compound to a combination reaction in the same manner as the method for producing the condensate described in the method for producing the dispersant (2).

611-) In the general formula ((1), when M is hydrogen, alkaline earth metal/ammonyl, n = 1, and when M is an alkali metal, 1l-J:1 to -2 .

-Thorium, potassium, etc. can be mentioned as the 11-carbon alkali metal, and examples of the amine include methylamine, ethylamine, and propylamine.

Alkylamines such as dimethylamine, diethylamine, triphthylamine, tributylamine:
71 such as ethylenediamine and triethylenetetramine? Riami/;
Morpholine, piperine, etc. can be used in total, and calcium is an alkaline earth metal.

Magnesium/Um, +111 lead, etc. can be mentioned.

In addition, these N1 are mutually intersected with the N1 of Φ by the ion exchange reaction or the intermediate reaction.

[Production of dispersant -+=++] A row for blue will be explained.

//R a pentanene is sulfonated using the same method as the sulfonation method of the polymer explained in the production method of Jl, and then converted into a sulfonate as needed to form -I functional formula ((・) is obtained.This compound is subjected to a 4f polymerization reaction in the same manner as the method for producing the polymer described in the !!method for dispersant (1).

Add the polymer. In addition, in the polymerization reaction, olefin co-i
Jf storage is available.

The number average molecular weight of the polymer or copolymer is preferably above 500 U, most preferably from 1.500 to 5'000'0, from the viewpoint of the 5+ dispersion effect of petroleum coke.

The details regarding the production of the dispersant (5) will be explained in detail.

Preparation of Dispersant (4)] The procedure was the same as that for Preparation of Dispersant (4), except that hydroxycinclopentazene was used in place of dinoclopentadiene, the blue starting line A'.

The number average sap weight of the polymer or copolymer is preferably 500μ or more in terms of the %N λ power of petroleum coke. (+ O1 mouth)
It is.

An example of the production of dispersant (61) will be fully explained.

7/Clopentadiene a and benzene or habenze 7i
The reaction product reacted with the M+ form overnight by the Freethyl-Craft reaction in the presence of a catalyst is subjected to an addition reaction with, for example, 1lli Mt M sterium hydrogen, and if necessary, Sulfone 1421. By eliminating C to complete the general formula (10), we obtain the proboscis.

(I(,,, lt2. to 1 is the same as in the above general formula Fgl.

0] is l or 2. ) General formula (using a compound in f of ki, using an organic solvent if necessary, sulfuric acid such as sulfuric acid, sulfuric anhydride, @fuming sulfuric acid, etc.) (preferably 0.1 to 5 times the number of moles) preferably 50 to 150°
When reacted with C, a disulfonated compound of general fg+ is obtained. The disulfonated product is condensed in the same manner as explained in the preparation of the dispersant (2) to give a condensate.

The dispersant in the previous 11 cases is used in at least one building, and if necessary, the surfactants, additives, etc. described later, and the petroleum coke (not limited to Ll'<j') Since the viscosity decreases, the amount added can be selected depending on the desired viscosity, and is usually 0.01 to 10% of the total slurry.
It may be a weight control, but from the viewpoint of workability and economy, it is 0.
05 to 1 weight ratio is preferable.

Surfactants that may be used as needed in the slurry composition of the present invention include t-thread nonionic threads, anionic surfactants, and the like.

Nonionic surfactants include, for example, alkyl polyether alcohol-alkyl allyl polyether alcohol, polyoxyethylene fatty 1"J2 ester, polyoxy/ethylene sorbitan fatty wrinkle ester, polyalkylated/oxygenated bro, polycopolymers, etc. Commercially available products containing these, such as ethylene oxide yarn, jetanolamino yarn, anhydrosorbitol yarn, glucoside yarn, gluconamide yarn, glycerin yarn, and glycidol yarn, are used as a dispersant or petroleum coke polymer τ) 4+: rτ interlayer i? 11. Examples of anionic surfactants include dotesylbenzenesulfonate, olein M Lj+L , -
j-rugylbenzene sulfonate, dialkyl sulfo=
I Haku AW kg, IJ Risulfonate, alcohol etquin sulfate, 2nd H7 lucane x
Carboxylic acid-based products include luphonate+-, α-olefin sulfonic acid, and tamol.

Sulfuric acid esters and sulfonic acid 9me esters can be used.

There are two examples of Shuka 11, chelate cutting for polyvalent gold 4 traps, specifically 1ThlJTA, l-ribolysodium phosphate, potassium tetrapolyphosphate, sodium citrate,
Examples include sodium gluconate, sodium polyacrylate, and polycarboxylic acid. Moreover, antifoaming M11 can also be added to suppress foaming.

For example, silicon emulsion is used for cutting and cutting.

Freezing point 1 laxative added to prevent winter freezing
As the freezing point depressant, for example, a lower alcohol such as ethylene glycol or a hanging alcohol can be used.

Furthermore, it may contain solutions such as γ alcohol and hydrocarbons, gelling agents, rust preventives, preservatives, and the like.

The petroleum coke that is the object of the present invention may be crushed by either a dry method or a wet method carried out in water, but the wet method is free from the problem of dust generation. The particle size of petroleum coke is not determined in particular, but it is not affected by passing through a 200-metre run of 70 weight or more, and is excellent for petroleum coke powder of any particle size. Add 1 point to the effect. .

The method of applying the dispersant used in the present invention is as follows: dry & crushed stone t) 1) In the case of coke dispersion, powder 4 + ' + iJ
Alternatively, a force of 11 may be applied to the mill in f'tr (S~), or 16 bubbles may be added to the slurry after pulverization.

If a stable slurry cannot be obtained using the dispersant used in the present invention by pulverization in water or ordinary stirring, mixing is performed using a stirrer such as a homogenizer or line mixer with strong shearing force.

Before dispersion used in the present invention, a very small amount of addition to the 9 petroleum coke slurry gives high fluidity.

Furthermore, since it has the effect of stably dispersing petroleum coke in water over a long period of time, the stone l11 coke slurry of the present invention facilitates ilj control when supplied to a water gas generator.

Examples are shown below. The values in the examples are based on weight.

Reference Examples 1 to 15 "Production method of dispersant Reference row 1 400 g of 11-hexane and 4 g of boron trifluoride/phenol complex were placed in a three-necked flask equipped with a reflux condenser and a stirring device, and the temperature was raised to 50°C. After warming,
While stirring, add 95% pure dicyclopentadiene 140.
gk was added dropwise over about 1 hour, and the reaction was further carried out at this temperature for 2 hours. At the end of the reaction stage, after cleaning the catalyst with an aqueous sodium carbonate solution and washing it with water, the outside of the oil layer was drained.
11-hexane and unreacted 7-cyclopentadiene were removed by distillation under t. The weight of the obtained residue was 78 g.

The number average molecular weight of this residue was 2100, -). Further, when the remaining two-bond bonds in the residue were determined by iodometric titration, it was found that 0.83 equivalents of double bonds remained per mole of reacted dicyclopentadiene.

20 g of the above residue, 30 g of I-toluene, and 20 g of sodium bisulfite were then placed in a 1:1 stainless steel autoclave equipped with a stirrer and a thermometer.
g, potassium nitrate 2g, inzolovir algol 300
Add mj and 50k of distilled water and hold at room temperature. 1- Internal pressure in the crepe is 1.0F=y/crd (gauge pressure)
After supplying air until it reaches , close the valve.

The reaction was carried out at a temperature of 110'C for 5 hours while mixing under strong stirring. After that, it was left to cool to room temperature, and most of the inzorobil alcohol was removed by distillation. Then, distilled water 1E and petroleum ether 154 were added and thoroughly mixed, and the separated petroleum needle layer and precipitate were removed to obtain water. The layers were concentrated and evaporated to dryness. This was dissolved in glacial acetic acid, and the acetic acid-insoluble portion consisting of inorganic salts was removed from door to door. The resulting acetic acid soluble content was condensed to give a white gel (18.7 g of colored solid, 44 g). This was designated as "Sample 1" 1° Reference Example 2 The same procedure as in Reference Example 1 was repeated except that cyclopentadiene was used instead of dicyclopentadiene and the reaction was carried out at a temperature of 30°C to obtain 168 g of residue. The number average molecular weight of this residue was 5,600. Further, when the remaining double bonds in this residue were quantified in the same manner as in Reference 1, it was found that 0.90 equivalents of double bonds remained per mole of butalopentadiene reacted.

Next, sulfonation treatment was performed in the same manner as in Reference Example 1 to obtain 14.3 g of a white-yellow solid. This will be referred to as "Sample 2."

Reference tide 3 Capacity 3 with source cooler and 4%: pushing device! ! !
1,270 g of toluene and 12 g of boron trifluoride/phenol complex were placed in a three-necked flask and the temperature was raised to 5°C. 4J was lowered for about 1 hour, and the reaction was further continued at this temperature for 2 hours.After the reaction was completed, the catalyst was decomposed with an IJ solution and washed with water, and the outside of the oil layer was decompressed under reduced pressure. 1,360 g of unreacted toluene and 35 g of dicyclopentadiene were distilled off to obtain a residue of 601 g'f6.When the remaining double bonds in this residue were examined by iodometric titration, 9 reacted ions/chloro 0.96 equivalents of double bonds remained per mole of pentadiene.When the molecular weight distribution of the shredded residue was investigated by OP O (Kel.)g-meation chromatography), it was found that dicyclopentadiene The lower limit is the molecular weight of a compound (approximately 63 tons) in which 1 mole of toluene is subdivided into 1 mole, and the molecular weight of polystyrene is 22.1. It existed.

Next, it is equipped with a stirrer + ri + and an additional device.
Duplicate residue 20 g in a stainless steel autoclave with t' 3 g + llj sodium bisulfate 20 g
g, potassium nitrate 2g, inzorobil alcohol: 3
(Pour 10'ml' and 50 g of 0° distilled water into an autoclave at room temperature.
After supplying air until the temperature reaches i (gauge 1 mo, ), close the valve and mix with high-speed stirring at a temperature of 11 ()C.
The reaction was carried out for 3 hours.

After that, the room was allowed to cool to TI+7+, and most of the isozorobyl alcohol was removed by distillation, then 1β of distilled water and 1.54% of petroleum ether were added and thoroughly mixed, and the separated petroleum ether I- and precipitate # were removed. The aqueous layer obtained was concentrated and evaporated to dryness. This was dissolved in glacial acetic acid, and the acetic acid-insoluble fraction consisting of inorganic soil was separated from each other. The obtained acetic acid-soluble molecules were concentrated to a yellow color. 25.8 g of solid material was obtained.This total is referred to as 1-Sample 3.

Fir ≧ Consideration ・l Reference 1 Prepared first in Tari 3] ・Ruen 1
Ethylbenzene 151 (Ig.

tIX+-1 toluene/: 320 g replaced with 32 ethylbenzene t) g' (unreacted j, 6, ethylbenzene, reacted in the same manner as in reference column 3 except that l- was used) 59
52 g of 0 g todi7 clopentazoene was distilled off to obtain 588 g of a residue. When this residue was examined by residual double bond keiodine titration, it was found that 0.95 equivalents of 211 bonds remained per mole of dicyclopentadiene reacted with 9.

When the molecular weight distribution of the residue was examined in the same manner as in Reference Example:
kj (238f lower limit, polystyrene equivalent molecular meter 11
000, and a compound with a divine molecular weight was present.Next, sulfonation treatment was carried out in the same manner as in Reference v/113, and 3.8 g of yellow solid 2 was obtained. This will be referred to as 1-Sample 4.

Reference example 5 mmol, hol, aldehyde 30 mmol + I + A
Charge 30 mmol of Cp and 270 mmol of distilled water.

The condensation reaction was carried out in one li+i'i vessel at 80C for 24 hours. After adding 100 g of distilled water to the obtained reaction product,
Stir the Cal/Rum carbonate until the pH is 7, then turn the power to 11.

The resulting mixture was then filtered to remove water. Furthermore, if you have added 1) soda carbonate to this p solution by stirring it until II becomes 9, then θ dilute it to obtain solution 05. This p liquid was dried to obtain 116 g of brown powder.

This will be referred to as "Sample 5."

The molecular 1is distribution of this sample 5 was calculated using aqueous OPC (gel).
tlt1 by Myein Yong, Chromatography)
When 1' was examined, the total quintuosity of compounds with one molecular weight of 500 or less was less than %μ, and a large peak occurred at a molecular weight of 11.300.

Doctor 1+lJ 6 iY; 4111r, cooling Otsu and 4;゛L stirring device 'j-'
E 1iii and 7) W'Q: 3, put 1270 g of toluene and 12 g of boron trifluoride in the three-bottle flask of Q: I:
', 50 degrees ('ff, f!, 1't) After stirring, dicyclopentadiene 117g and tolueno 3
Mixing 20g, tolerance is about 1 +: 2 between g1 and i1X
+i, and the reaction was further continued at this temperature for 2 hours.

After completion of the reaction, the catalyst was separated into 11 parts with an aqueous sodium carbonate solution and washed with water.The oil layer was distilled under reduced pressure to obtain -12:3 g of dicyclopentadiene toluene;
Ta.

Next, in a stainless steel autoclave with a capacity of 3e and equipped with a stirrer and a thermometer, 200 g of the above-mentioned dicyclopentadiene toluene 4"J' 7J [I body, average value f, 97.8 g of hydrogen-absorbed storium, and potassium nitrate were added. l, 3
．． Qg.

Isopropyl alcohol 1.360 nl and distilled water 2
00m1. f and the internal pressure in the autoclave at room temperature is 1.
．． Air was supplied until the pressure reached OKy/C111 (gauge pressure).Then, the valve was sealed and the reaction was carried out at a temperature of 11 (1') for 5 hours while mixing under strong stirring. After leaving to cool at step 1, the reaction mixture was taken out for 14'y, 50 ml of distilled water and stone 7111 x-chill J 5
(1 (11111f) was added, mixed thoroughly for 9 minutes +++1+ The remainder after removing the petroleum ether layer and the precipitate was evaporated to dryness, and 1341 g of pale j, lj colored powder was obtained. The powder was extracted and removed with petroleum ether using a Sox 1 extractor for 1 hour.The IS material was extracted and removed, and the remaining amount was dried in freshwater acetic acid in a 300 meK bath (=L).

The acetic acid-insoluble matter, which consists of inorganic salts, was collected from house to house. Obtained acetic acid 1
By condensing the soluble matter, 129 g of a 111° yellow solid was obtained. This solid was extracted with ethanol to obtain a sulfonated product of the toluene adduct of Ncropentaje 7, Liui.

Next, the above sodium i + ui, J O
mmol, formaldehyde 30 mmol, sulfuric acid 30,
? Prepare 270 mmol of rimole and distilled water.

r! 1. The condensation reaction was carried out at 80'C for 2-1 hours. After adding 100 g of distilled water to the resulting reaction product,
I] 11 charcoal/umu until l-1 becomes 7 (beat 11 charcoal from Hayabusa.

Next is A4? The θ-liquid was filtered through the I/C mixture.
Ta.

Add soda carbonate to this d-liquid so that 1]11 becomes 9:
I didn't worship the tatami, so I got 1 grade, and I passed the liquid.

This C5 liquid was dried to obtain 112 g of brown powder. This will be referred to as Xun 1-Sample 6-1.

When the molecule-1-11 was measured by an aqueous C2l'O('y'le.)P-Mie/Yong Chroma 1 graphi, the number average molecular weight was ll ll f) 0.

Reference 1ull 7 In Reference Example 6, instead of toluene, Ki/Shi/1060
This was reacted with 350 g of dicyclopentadiene in the same manner as in Reference Example 6 to obtain 340 g of xylene added to dicyclopentadiene.

12-1 g of the sulfonated sulfonated product of the kylene adduct of synchropentanene was obtained in the same manner as in Reference Series 6, except that 200 g of this kylene adduct was used. This is referred to as "Sample 7-1.

Next, a condensation reaction was carried out in the same manner as in Reference Example 6 using Tonosu thorium salt to obtain 103 g of brown powder.

In addition, the molecular weight was determined by aqueous (') PC.

The number average molecule f44 is 511. It was OO.

Reference Example 8 Into a 30 g stainless steel autoclave using a stirring device and a 711.114 degree meter (Iiii), synchropentadiene: 30001f, 1llj (1888 g of sodium hydrogen saturated oxide, potassium nitrate!), 1.7 g, Inopropyl alcohol 12e and distilled water: 3000
g, and the internal pressure in the autoclave at room temperature is 1. OK
Supply nitrogen until y/c#i (gauge 1 King), then close the valve.

511. at 110C while mixing under high m41'. Two reactions were performed between i. After that, it was left to cool at room temperature 1, and after removing most of the isopropyl alcohol by distillation, distilled water and petroleum ether were added and thoroughly mixed, and the separated petroleum ether layer and precipitate were removed. It was concentrated and distilled to dryness. Dissolve this in 1 portion of wood vinegar for 11 hours, and remove the acetic acid-insoluble portion consisting of inorganic J'm using a centrifuge.
did. (After converting the acetic acid solution obtained from 4j to the acid form by condensing the acetic acid solution, the water was concentrated to dryness, and then the reflux condenser and stirring device were installed. 300
The above sulfonated product l (1
5g of sulfuric acid and 688g of sulfuric acid were added, and a 11x reaction was carried out at a temperature of 120°C for 26 hours. After the completion of the reaction, Limin Soar/=I was carried out, and the amount of solid obtained was 155 g, and the number average molecular weight of this polymer was 1.
It was 0,000. This will be referred to as "Sample 8."

Reference Example 9 A polymer having a number average molecular weight of 1600 was obtained by carrying out the same treatment as in Reference Example 8 except that sulfonated compound A was used. This will be referred to as “Trial 4” 9.

Reference 2 Li 10 In Reference Example 8, the polymerization reaction was performed by sulfonation '+'/JA
30g f ticf'12] 25g,
Water 1. l ll gl put in.

The polymer was stirred for 28 hours at a temperature of 170℃.
00's i "Merge 4..This is l-Test IS) l O
-1.

Reference t91111 Reflux condenser and stirring device (iii): 1'
c :') Q Qm B's sulfonated 'h A K l 3 g.

2 g of synchropentagene, partial j14'2.6.8
Contains 8g.

The co-Φ synthesis reaction was carried out for 20111I at a temperature of +20'C. Reaction trowel, liming, nutee7. The solid mass obtained was 15.0. , helip ζ at f.

This is referred to as Sample 11J.

Reference Example 12 '8i+j with reflux condenser and stirring device added to 11ii+
Into a 300 ml three-north flask, put 15 g of sulfonated hydroloxozine clopenxyeno (a compound that is M211 in the above general 1F+) and 688 g of sulfuric acid, and heat at 20" L for 23 hours. After the reaction was completed, living was performed using C+IC(')3+(S Cj37% was removed and M
== H becomes M2Ca. ) Na0(J,,
When I performed n-te/yon using f, (j\I =
:: (y = + becomes 1 =, : Na.) The amount of b'ii + f6 that was added is 15.5 g, and the number average molecule 'a of this polymer is] fl, 01) (l
Met. This is 1 sample 12''.

Reference 1 row 1: 8-segment 300+I equipped with brewing cooler and (W pushing device 6
++! 3] In a 20-ml flask, add a sulfonated product of hydrocyclopenta/ene (+1! In general formula ([)).

M! 8 g of compound No. 11) and a sulfonated product of synchropentadiene were added, and a copolymerization reaction was carried out at a temperature of 120° C. for 2 hours. After the reaction, liming and sowing were performed, and the amount of solid obtained was 15.5 g. This will be referred to as 1-sample 13.

Reference example 14 Vessel equipped with reflux condenser and stirring device: 3 U.

A sulfonated product of hydroxydi/lylopentadiene (in the general formula (1) above) was placed in a MC three-so-1 flask.

1:3 g of compound (where 1'vl = H), 2 g of acrylic acid and 88-g of Li sulfate were added, and the temperature was 120'.
A copolymerization reaction was carried out for 2 hours at C. After reaction, liming.

When I performed Sawzone - + ノ, the obtained outside body was 1
1, which was 51Ig, will be referred to as "Sample 1.1".

) Reference Example 15 A reflux condenser and a stirrer (1.270 g of toluene and 1.270 g of toluene were added to an 8-3E three-tube flask),
Add 12g of boron chloride/phenol complex and temperature 50'C.
After raising the temperature to
A mixed solution of 7 g and 320 g of toluene was added dropwise over about 1 hour, and the reaction was further continued at this temperature for 2 hours.

After the reaction was completed, the catalyst was decomposed in a sodium carbonate water bath, washed with water, and then distilled under an oil layer with a low concentration of 0 to obtain 423 g of synchropentadiene toluene.

Next, a valley 1ij comprising a stirring device + a G flow meter,
:3.9 Into a stainless steel autoclave, add 200 g of synchropentadiene toluene (J).
, flj (+ifj oxyhydrogen!・lium 97.8
g, potassium nitrate 80g.

Inzorovir alcohol 1360 ml and distilled water 2
Add U Ome, and the internal pressure of the autoclave is 1 at room temperature.
After supplying air until the pressure reached 0 &77 clll (gauge pressure), the valve was sealed and the reaction was carried out at a temperature of 110'C for 5 hours while mixing under strong stirring. After that, the reaction mixture was left to cool in a room, and 50 ml of distilled water and 15 (10 mJ) of petroleum ether were added and thoroughly mixed.The remaining part after removing the separated petroleum ether layer and precipitate was concentrated and evaporated to dryness to give a pale yellow color. 13-9 g of powder was obtained. This powder was extracted with petroleum ether for 1 hour using a Cucumber L-extractor to remove unreacted substances, and the remaining liquid was dried and drained with RFL, 3
00 ml, and the acetic acid insoluble portion consisting of inorganic salts was removed from door to door. By concentrating the obtained 11"J solution in vinegar, 129g of the white-yellow isomer was obtained (44). This solid was purified by ethanol extraction to obtain the sulfonated product of di/clopentadiene-toluene:J A sulfonated product of this dicyclopentadiene-toluene salt was designated as product A'.

Next, a capacity 0.2e equipped with a stirring device and a thermometer
The above products Δ'110m~I and +
(Insert lltc Shun 80 +n~1, and 1 degree 1
The reaction was carried out at 00°C for 3 hours. That r & l (i
React for 2 hours at 110°C.
]-hebutane (100 C) was overflowed, and further, n-hebutane and water were removed by azeotropy at a temperature of 80° C. under reduced pressure. The product obtained by this reaction (4) is designated as B'.

Next, 6.3 g of water was added to this product B', and the temperature was 80'C.
535g of formaldehyde aqueous solution (6
6mM) was added dropwise for 3 hours, and then 1tl of this was added.
When the temperature was raised to 0° C. and the condensation reaction was continued for 20 hours, a viscous reaction product was obtained. This is designated as product C'. After adding 00 g of water to this product C' and dissolving it, OaO03
Add 11 gf to make solution f, p l-17.

The generated white sediment is sent from house to house, and Na2CO3 is added to the P solution.
The white precipitate formed was poured into 3.2gr.

Then, the obtained (pa) was dried and 1-Sample 15J
shall be.

The number average molecular weight of this sample was 6300 as measured by C) PC.

[Implementation Criteria 1-19. Comparative Examples 1 to 3] Contains 20Ll mesh pass portion at 97%, ash content is 067%
Petroleum coke containing 0.36% sulfur was used. The dispersant listed in Table 1 is added to water in advance, and the specified 11 petroleum cokes are gradually added to the water. The degree of dispersion and the addition of dispersant (Ti') are shown in Table-1.

At the slurry viscosity f25'C obtained in this way, the results are shown in Table 1.
ni small/ko. Also, the slurry viscosity was measured after the slurry was left to stand for 1! From Table 1, petroleum coke-water slurry of the present invention 4.1[
You can see that the family 1 is loved by 1.

[Examples 20 to 23] It is a petroleum containing 84% of the 200 mesh pass portion.

Table-2 Patent applicant: Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] (1) A petroleum coke-water slurry composition characterized by containing a compound essentially containing a drinkloacane or tricyclodecene skeleton and a sulfonic acid group in the molecule, petroleum coke, and water.