KR20160078060A - Petroleum slurry composition comprising polyurethane based gelling agent - Google Patents

Abstract

The present invention relates to a petroleum coke slurry composition comprising: a polyurethane-based gelling agent; a stabilizing agent; a dispersing agent; petroleum coke; and water. The petroleum coke slurry composition according to the present invention has stable physical properties and storage stability over a long time.

Description

[0001] The present invention relates to a petroleum coke slurry composition containing a polyurethane gelling agent,

The present invention relates to a petroleum coke slurry composition, and more particularly, to a petroleum coke slurry composition comprising a polyurethane gelling agent.

Due to the depletion of petroleum resources, petroleum coke has been re-recognized and various methods for its utilization have been examined. However, since petroleum coke is solid other than petroleum liquid fuel, it is difficult to transport by ordinary pipeline or tanker. For this reason, a technique has been proposed in which the petroleum coke is pulverized and dispersed in water to prepare a slurry to be similar to a liquid.

However, the petroleum coke slurry dispersed in water significantly increases the viscosity of the slurry from which the petroleum coke content in the slurry is obtained. The slurry with increased viscosity has insufficient flowability, which makes it difficult to handle and transport through the pipe. Reduced viscosity of the petroleum coke slurry can be achieved by lowering the content of petroleum coke in the slurry. However, the slurry having such a low content of energy is low in energy density (or calorie), and further processing such as dewatering is required to be used as a fuel in the future. In order to solve such problems, methods such as addition of a dispersant or adjustment of particle size distribution of petroleum coke have been used.

Petroleum coke slurries with a high content of petroleum coke with reduced viscosity according to conventional known methods must be stored for a long period of time during transport to the tank lorry. The petroleum coke slurry tends to precipitate petroleum coke particles over a long period of time. Also, the sedimented particles are compacted under dehydration to form solidified material, and it is very difficult to redisperse them for use as petroleum coke slurry.

As described above, in order to replace the petroleum coke slurry fuel with the liquid fuel of petroleum, it is most important to secure the storage stability. This is because the petroleum coke slurry is a mixture of solid and liquid, which causes serious problems in the above-mentioned separation or precipitation.

As a stabilizer used in conventional petroleum coke slurry, it is difficult to secure stability for more than one week. Therefore, it is necessary to establish new measures to ensure stability over 4 weeks for stable fuel operation.

The present invention provides a petroleum coke slurry which can maintain stability for a longer period of time than conventional petroleum coke slurry having a stability of about one week.

The petroleum cokes slurry composition according to one embodiment of the present invention may include a polyurethane gelling agent, a dispersant, a stabilizer, a petroleum coke, and water.

In one embodiment of the present invention, the polyurethane gelling agent may contain 30% to 35% of a water-soluble polyurethane polymer.

In one embodiment of the present invention, the polyurethane gelling agent may have a self-bonding structure in aqueous solution in the form of a polymer having hydrophobic-hydrophilic groups repeated and having a hydrophobic end.

In one embodiment of the present invention, the content of the polyurethane gelling agent may be 0.03-0.2 wt% based on the total wt% of the petroleum coke slurry composition.

In one embodiment of the present invention, the dispersant is selected from the group consisting of a polynaphthalene sulfonic acid dispersant, a lignosulfonic acid dispersant, a polyalkylene oxide nonionic surfactant, a polycarbonate dispersant, a polystyrene dispersant, a polyisoprene dispersant, And a dispersing agent. Specifically, the dispersing agent may be a polyethylene oxide-polypropylene oxide block copolymer.

The content of the dispersant may be up to 1 wt% based on the total wt% of the petroleum coke slurry composition.

In one embodiment of the invention, the stabilizer is selected from the group consisting of alkali metal salts of carboxymethylcellulose (CMC), hydroxyethylcellulose (HEC), polyvinylalcohol, polyacrylamide, carboxymethylcellulose, hydroxyethylcellulose, , Guar gum, cellulose gum, gum arabic, tara gum, locust bean gum, starch, glue, bentonite, atepurite, sepalite and insole asbestos.

The content of the stabilizer may be up to 0.2 wt% based on the total wt% of the petroleum coke slurry composition.

In one embodiment of the present invention, the content of the petroleum coke may be 50-80 wt%, based on the total wt% of the petroleum coke slurry composition.

In one embodiment of the present invention, the composition may further comprise at least one additive selected from the group consisting of a defoaming agent, a bactericide, a freezing point depressant, and a chelating agent.

In one embodiment of the present invention, the composition may have a viscosity of 1000 cp or less at a shear rate of 100 / s at 25 ° C.

The petroleum cokes slurry composition according to one embodiment of the present invention can be used as a stable fuel because separation or precipitation does not occur even after a long time passes.

The petroleum coke slurry composition according to one embodiment of the present invention has stable physical properties of 4 weeks or more and storage stability of 8 weeks or more.

1 is a view showing a petroleum coke slurry prepared without using a gelling agent after one week.
FIG. 2 is a view showing a petroleum coke slurry manufactured according to an embodiment of the present invention after one week.
3 is a graph showing viscosity changes of the petroleum coke slurry produced without using a gelling agent with the lapse of time.
4 is a graph showing changes in viscosity of a petroleum coke slurry produced according to an embodiment of the present invention with time.

In one embodiment of the invention, the petroleum coke slurry composition comprises a polyurethane gelling agent, a dispersant, a stabilizer, a petroleum coke, and water.

The petroleum coke slurry produced according to one embodiment of the present invention is preferably in terms of fuel in terms of the viscosity of 1000 cp or less when the shear rate is 100 / s at room temperature (25 ° C) based on the conventional commercialized coal slurry .

Petroleum coke is a residue obtained by distilling petroleum and is a by-product solid residue produced by pyrolysis of heavy residues of crude oil and production of gas oil by the Delay-Cocer method and the like. Since the ash content is low and the degree of graphitization is high, It is a coke obtained by pyrolyzing a heavy oil fraction of petroleum which is also used as a raw material for an electric motor brush and the like at a high temperature. It is hardly wetted by water as compared with a coal containing an inorganic substance in general.

In one embodiment of the invention, the content of the petroleum coke may be about 50-80 wt%, more specifically about 60-70 wt%, based on the total wt% of the petroleum coke slurry composition. The petroleum coke used in the present invention may be pulverized by a dry method or a wet method which is carried out in water. The wet process is good because there is no problem of powder dust.

The particle size of the petroleum coke may be any particle size as long as it is powder. For example, powder having a particle diameter of not more than 200 mesh and not more than 75% of petroleum coke may be used.

In one embodiment of the invention, the petroleum coke slurry composition comprises a polyurethane based gelling agent. The polyurethane-based gelling agent used in the composition prevents the precipitation by inducing gelation of water as a solvent while maintaining the existing physical properties.

Wherein the polyurethane gelling agent contains about 30% to about 35% of a water-soluble polyurethane polymer, specifically about 30% of a water-soluble polyurethane polymer, wherein the hydrophobic-hydrophilic group is repeated and the polymer having a hydrophobic end- And has a self-associative structure in the form of an aqueous solution. In addition, the hydrophobic termini of the polymer interacts with the petroleum coke having a hydrophobic surface to affect structure stability, and the hydrophilic moiety in the polymer interacts with water to induce gelation. The slurry containing such a gelling agent gels at a high viscosity at the stationary phase, and the yield stress is very low, so that the viscosity increase effect of the mobile phase is insignificant.

On the other hand, although a general industrial gelling agent (for example, a Carbomer of Lubrizol) is gelled by ionic bonding with anion (carboxyl group) of a polymer and a cation of a neutralizing agent to be added, the gelling agent has a structural characteristic of a polyurethane polymer Gelling with water is carried out by van der Waals force by a hydrophilic group. Since a general gelling agent is based on ionic bonding, the higher the surface electron density of the dispersed particles, the stronger the interaction with the gelling agent becomes, and the structural stabilization can be achieved. When the above general gelling agent is used in a petroleum coke slurry, since the surface electron density of the petroleum coke is low and the particles are difficult to participate in such ionic bonding, the use of the above general gelling agent does not sufficiently secure the stability of the petroleum coke slurry There is a problem that can not be done.

The inventors of the present invention have conducted intensive studies to solve the above problems. As a result, the inventors have found that when a polyurethane gelling agent is used, the van der Waals force (hydrophobic group) of the polyurethane polymer is lower than that of petroleum coke particles having a low surface electron density And can contribute to the organic slurry structure stabilization.

The polyurethane gelling agent may be commercially available, for example, Dispercoll of Byer, ACRYSOL of DOW, Borchi Gel of Borchers, ADEKANOL of ADEKA, TANAVIS of Tanatex, and the like. The content of the polyurethane gelling agent may be 0.03-0.2 wt% based on the total wt% of the petroleum coke slurry composition. Specifically, it may be 0.03-0.15 wt%, 0.03-0.1 wt%, 0.05-0.15 wt%, and 0.05-0.1 wt%.

In one embodiment of the present invention, the dispersing agent is selected from the group consisting of a polynaphthalenesulfonic acid dispersant, a lignosulfonic acid dispersant, a polyalkylene oxide nonionic surfactant, a polycarbonate dispersant, a polystyrene dispersant, a polyisoprene dispersant and a polymethacrylic acid- ≪ / RTI > More specifically, the dispersing agent may be a polyethylene oxide-polypropylene oxide block copolymer.

As the amount of the dispersing agent is increased, the viscosity of the slurry is lowered, so that the amount of the slurry can be changed depending on the desired viscosity. For example, 1 wt% or less based on the total wt% of the petroleum coke slurry composition can be used. Specifically, 0.03-0.7 wt% can be used.

The nonionic surfactants to be optionally used in the slurry composition of the present invention include, for example, alkyl polyether alcohols, alkylaryl polyether alcohols, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyalkylene oxide block copolymers And commercially available products prepared by mixing ethylene oxide type, diethanolamine type, anhydrous sorbitol type, glycoside type, glucoamide type, glycerol type, glycidol type and the like can also be used as a dispersant.

In one embodiment of the present invention, the stabilizer may be a conventional organic or inorganic stabilizer. Examples of organic stabilizers include alkali metal salts of carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), polyvinyl alcohol, polyacrylamide , Carboxymethylcellulose, hydroxyethylcellulose, natural gums (for example, xanthan gum, guar gum, cellulose gum, arabic gum, tara gum and locust bean gum), starch, glue and the like. , At perpiteite, sepalite, and asbestos-based asbestos. The content of the stabilizer may be up to 0.2 wt% based on the total wt% of the petroleum coke slurry composition. Specifically, it may be 0.03-0.15 wt%, 0.03-0.1 wt%, 0.05-0.15 wt%, and 0.05-0.1 wt%.

In one embodiment of the invention, the petroleum coke slurry composition comprises 60-70 wt% petroleum coke, 0.03-1 wt% dispersant, 0.03-0.2 wt% stabilizer, 0.03-0.2 wt% polyurethane gelling agent, and The remaining water may be included.

In one embodiment of the present invention, the composition may further include additives such as antifoaming agents, bactericides, freezing point depressants, chelating agents, and the like.

Specifically, a defoaming agent may be added to suppress foaming. As the antifoaming agent, for example, silica silicon, metal soap, amide, ester or polyether emulsions can be used.

In order to prevent freezing of the winter season, it is also possible to add a freezing point depressant. As the solidifying-point depressant, for example, a lower alcohol such as ethylene glycol or a polyhydric alcohol may be used.

The additive of the present invention may be added all at once from the beginning when the slurry composition is prepared, or may be added in portions during the production process. It may also be added after the preparation of the petroleum coke slurry composition.

The method for producing the slurry composition of the present invention is not particularly limited, and it can be produced by mixing water, a stabilizer, a dispersant, and a polyurethane gelling agent into petroleum coke.

The present invention can be all accomplished by the following description. The following description should be understood to describe preferred embodiments of the present invention, but the present invention is not necessarily limited thereto.

Comparative Example 1

Powders having a particle size of not less than 200 mesh and 75% or more of the undifferentiated petroleum coke were used. 0.4 wt% of a polyethylene oxide-polypropylene oxide block copolymer as a dispersant in water and the undifferentiated petroleum coke powder were put into a mixer and stirred at 500 rpm for 30 minutes to obtain a petroleum coke content of 65 wt% based on the total wt% of the petroleum coke slurry .

Comparative Example 2

In the same manner as in Comparative Example 1, except that 0.01 wt% of xanthan gum was further added as a stabilizer in Comparative Example 1.

Comparative Example 3

In the same manner as in Comparative Example 1, except that 0.03 wt% of xanthan gum was further added as a stabilizer in the above Comparative Example 1.

Comparative Example 4

In the same manner as in Comparative Example 1, except that 0.05 wt% of xanthan gum was further added as a stabilizer in Comparative Example 1.

Comparative Example 5

In the same manner as in Comparative Example 1, except that 0.07 wt% of xanthan gum was added as a stabilizer in Comparative Example 1,

Comparative Example 6

In the same manner as in Comparative Example 1, except that 0.1 wt% of xanthan gum was further added as a stabilizer in Comparative Example 1.

Comparative Example 7

Except that 0.5% by weight of xanthan gum as a stabilizer, 0.01% by weight of Carbomer by Lubrizol Company as an anionic gelling agent, and 0.015% by weight of triethanolamine (hereinafter abbreviated as TEA) as a neutralizing agent were further added in Comparative Example 1 The same experiment as in Comparative Example 1 was conducted.

Comparative Example 8

The same tests as in Comparative Example 1 were carried out except that 0.5% by weight of xanthan gum as a stabilizer in Comparative Example 1, 0.03% by weight of Carbomer of Lubrizol Company as an anionic gelling agent and 0.045% by weight of TEA as a neutralizing agent were added.

Comparative Example 9

In the same manner as in Comparative Example 1, except that 0.5% by weight of xanthan gum as a stabilizer, 0.05% by weight of Carbomer by Lubrizol Co., and 0.075% by weight of TEA as a neutralizer were added as Comparative Example 1.

Comparative Example 10

The same tests as in Comparative Example 1 were carried out, except that the stabilizer in Comparative Example 1 was further added with xanthan gum at 0.5 wt%, an anionic gelling agent at 0.07 wt% of Carbomer by Lubrizol, and 0.105 wt% of TEA as a neutralizer.

Comparative Example 11

The same tests as in Comparative Example 1 were carried out, except that 0.5 wt% of xanthan gum as a stabilizer, 0.1 wt% of Carbomer of Lubrizol Co., and 0.15 wt% of TEA as a neutralizer were added as Comparative Example 1.

Example 1

In the same manner as in Comparative Example 1, except that 0.05 wt% of xanthan gum and 0.01 wt% of polyurethane gelling agent were added as the stabilizer in Comparative Example 1.

Example 2

In the same manner as in Comparative Example 1, except that 0.05 wt% of xanthan gum and 0.03 wt% of polyurethane gelling agent were added as the stabilizer in Comparative Example 1.

Example 3

In the same manner as in Comparative Example 1, except that 0.05 wt% of xanthan gum and 0.05 wt% of polyurethane gelling agent were added as the stabilizer in Comparative Example 1,

Example 4

In the same manner as in Comparative Example 1, except that 0.05 wt% of xanthan gum and 0.07 wt% of polyurethane gelling agent were added as the stabilizer in Comparative Example 1,

Example 5

In the same manner as in Comparative Example 1, except that 0.05 wt% of xanthan gum and 0.1 wt% of polyurethane gelling agent were added as the stabilizer in Comparative Example 1,

The results of measuring the amount of the upper water layer and the lower precipitation after 1 week of the petroleum coke slurry prepared according to Comparative Examples 1 to 11 and Examples 1 to 5 are shown in Table 1-3.

In the upper water layer, the separated water layer in 100 ml of the slurry was visually observed, and the scale was divided into 100 equal parts. The lower part of the water layer was measured by the penetration method using a rod.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Dispersant content
(wt%) 0.4 0.4 0.4 0.4 0.4 0.4 Stabilizer content
(wt%) 0 0.01 0.03 0.05 0.07 0.1 Gelling agent content
(wt%) 0 0 0 0 0 0 The upper water layer
(x / 100) 5 5 3 2 One One Sub-sedimentation
(x / 100) 8 5 One 0
(Lower density is high. Soft Packing) Initial viscosity
(at 100 / s) 61 208 528 573 660 1050

Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Dispersant content
(wt%) 0.4 0.4 0.4 0.4 0.4 Stabilizer content
(wt%) 0.05 0.05 0.05 0.05 0.05 Anionic gelling agent content
(wt%) 0.01 0.03 0.05 0.07 0.1 The upper water layer
(x / 100) 2 2 2


Viscosity is too high to manufacture Sub-sedimentation
(x / 100) 0 Hard clustering as a whole. No flow.
(Hard Packing) Initial viscosity
(at 100 / s) 625 941 1363

Example 1 Example 2 Example 3 Example 4 Example 5 Dispersant content
(wt%) 0.4 0.4 0.4 0.4 0.4 Stabilizer content
(wt%) 0.05 0.05 0.05 0.05 0.05 Polyurethane gelling agent content
(wt%) 0.01 0.03 0.05 0.07 0.1 The upper water layer
(x / 100) 2 0 0 0 0 Sub-sedimentation
(x / 100) 0
(Lower density is high. Soft Packing) 0 0 0 Initial viscosity
(at 100 / s) 508 416 459 533 852

As can be seen from Table 1, in Comparative Examples 1 to 6 in which the gelling agent was not added, it can be seen that the water layer separation occurred. In addition, it was confirmed that even if the content of the stabilizer is increased, it is difficult to secure the stability of physical properties over one week.

As can be seen from Table 2, in Comparative Examples 7 to 11 in which the anionic gelling agent was added, separation of the water layer occurred, and it was difficult to secure the stability of physical properties over one week, and it was difficult to control the physical properties due to rapid gelation .

In addition, Comparative Example 6 and Comparative Examples 9-11 have a high viscosity, which exceeds the standard of the slurry and has a usability limitation.

As can be seen from Table 3, except for Example 1 which is out of the appropriate range according to the embodiment of the present invention, in the remaining Examples 2 to 5, it is confirmed that the water layer separation does not occur and the lower precipitation does not occur there was.

1 also shows a petroleum coke slurry after one week of the petroleum coke slurry produced according to Comparative Example 4, and Fig. 2 shows a petroleum coke slurry after one week of the petroleum coke slurry prepared according to Example 3. Fig. In Fig. 1, it was confirmed that the water layer separation occurred. In Fig. 2, it was confirmed that the water layer separation did not occur, and the stable state was maintained for more than 8 weeks.

FIG. 3 shows the physical properties of the petroleum coke slurry according to Comparative Example 4, and FIG. 4 shows the physical properties of the petroleum coke slurry after the preparation of the petroleum coke slurry according to Example 3. In case of separation, the sample was hand-mixed for 10 minutes with a spatula for viscosity measurement. In FIG. 3, it was confirmed that the viscosity did not rapidly recover after 3 weeks, and the physical properties were not recovered. However, it was confirmed that no change in physical properties was observed after 4 weeks in FIG.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

Claims (11)

A petroleum coke slurry composition including a polyurethane gelling agent, a dispersant, a stabilizer, a petroleum coke, and water.
The method according to claim 1,
Wherein the polyurethane gelling agent contains 30 to 35% of a water-soluble polyurethane polymer.
The method according to claim 1,
Wherein the polyurethane gelling agent has a hydrophobic-hydrophilic group repeated and has a self-bonding structure in an aqueous solution in the form of a polymer having a hydrophobic end.
The method according to claim 1,
Wherein the content of the polyurethane gelling agent is 0.03 to 0.2 wt% based on the total wt% of the petroleum coke slurry composition.
The method according to claim 1,
Wherein the dispersant is selected from the group consisting of a polynaphthalene sulfonic acid dispersant, a lignosulfonic acid dispersant, a polyalkylene oxide nonionic surfactant, a polycarbonate dispersant, a polystyrene dispersant, a polyisoprene dispersant and a polymethacrylic acid- Slurry composition.
The method according to claim 1,
Wherein the dispersant is a polyethylene oxide-polypropylene oxide block copolymer.
The method according to claim 1,
Wherein the content of the dispersant is 1 wt% or less based on the total wt% of the petroleum coke slurry composition.
The method according to claim 1,
The stabilizer may be selected from the group consisting of alkali metal salts of carboxymethylcellulose (CMC), hydroxyethylcellulose (HEC), polyvinyl alcohol, polyacrylamide, carboxymethylcellulose, hydroxyethylcellulose, xanthan gum, guar gum, cellulose gum, A petroleum coke slurry composition is selected from the group consisting of gum, tara gum, locust gum, starch, glue, bentonite, perphosphite, sepalite, and onyx asbestos.
The method according to claim 1,
Wherein the stabilizer content is 0.2 wt% or less based on the total wt% of the petroleum coke slurry composition.
The method according to claim 1,
Wherein the content of the petroleum coke is 50-80 wt% based on the total wt% of the petroleum coke slurry composition.
The method according to claim 1,
Wherein the composition has a viscosity of 1000 cp or less at a shear rate of 100 / s at 25 캜.

Images