WO2007124681A1

WO2007124681A1 - Desulfurizing coke-water slurry and process for preparation thereof

Info

Publication number: WO2007124681A1
Application number: PCT/CN2007/001318
Authority: WO
Inventors: Houchun Chang; Zuqin Li; Ge Ma; Shengbin Geng; Xianjun Li; Dianming Zhang
Original assignee: Guangzhou Devotion Thermal Technology Co., Ltd.
Priority date: 2006-04-24
Filing date: 2007-04-23
Publication date: 2007-11-08
Also published as: CN100556996C; CN101029259A; MY157996A

Abstract

A deslufurizing coke-water slurry and a process for preparation thereof, the slurry comprises 55-75% petroleum coke, 24-44% water and 0.1-2% additives, wherein the additives includes a dispersant for reducing viscosity of slurry, a stabilizer for preventing the sediment of the slurry and a desulfurizing agent for reducing SO2 emission when combustion. The slurry has a good fluidity and a good stability, a reduced SO2 content in smoke when combustion.

Description

Patent cooperation

PCT

International search report

(PCT18 and Rules 43 and 44)

An international search report made by the International Searching Authority in accordance with Treaty 18 is sent to the applicant. A copy of the report is sent to the International Bureau.

This international search report totals 4 pages.

□ It also contains copies of the existing technical documents referenced in this report.

1. The basis of the report

a. About the language, the international search is based on - the language used in the application.

□ The language translation of the application, which is translated for the purpose of international search (rules 12.3(a) and 23.1(b)). b. □ This International Search Report considers the obvious error corrections made by the unit in accordance with Rule 91. (Rule 43.6 bis (a)).

C, □ For the nucleotide and/or amino acid sequence listings disclosed in the international application, see column I.

2. □ Certain claims are considered to be unretrievable (see Box II).

3.□ Lack of invention unity (see column III).

4. Regarding the name of the invention,

□ Agree to the name of the invention filed by the applicant.

13 The name of the invention is determined by the International Searching Authority as follows: Desulfurized water coke and preparation method thereof

5. Regarding the abstract,

□ Agree to the abstract submitted by the applicant.

It is developed by this International Searching Authority in accordance with Rule 38.2(b) (transcribed in Box IV). Within one month from the mailing date of this International Search Report, the applicant may submit an opinion to the unit.

6. Regarding the drawings,

a. The picture published with the pick-up is __1J:

Because of the applicant's agreement.

□ Because the applicant did not recommend a picture.

□ Because the figure can better represent the characteristics of the invention.

B.□ No screenshots

PCT/ISA/210 (page 1) (April 2007) Desulfurized water coke and preparation method thereof

The present invention relates to a water coke for a combustion system and a process for the preparation thereof, and more particularly to a desulfurized water coke which can reduce the release of sulfur dioxide after combustion and a preparation process thereof. Background technique

The water coke slurry is a liquid fuel prepared by a specific process by adding petroleum and coke as a by-product of petroleum refining. It can be used as an alternative fuel for fuel oil and/or gas fueled thermal energy equipment. In general, every 1.18 p屯 petroleum coke can replace 1 ton of crude oil, so the promotion of the application of water coke can save the shortage of petroleum resources. Rational use of resources. Industrial tests have shown that the cost of steam produced by oil-fired boilers is 152.75 yuan / ton of steam (crude oil price is 2350 yuan / ton), while the cost of steam-burning petroleum coke production steam is 96. 52 yuan / ton of steam (oil The price of coke is 810 yuan/ton, plus pulping and other expenses. The fuel-burning coke has a fuel saving cost of 36.81%. The smoke and sulphur dioxide in the flue gas emissions of the water coke pulp are not high (S0 ₂ content is 201. 7mg/m ³ standard, soot content is 43.0 mg / m ³ standard), economic and social benefits are obvious. .

The petroleum coke component is a hydrocarbon, which can be classified into a needle coke, a sponge coke, a projectile coke, and a powder coke in terms of structure and appearance. In a natural dry state, the moisture accounts for about 3%, and the ash content is about 1.12. %, The calorific value is about 30. 35 MJ / kg, the volatile matter is about 11. 03%, and the Haugh Grindability Index (HGI) is 80. Water coke is prepared by mixing petroleum coke with water and adding appropriate additives.

Chinese patent application CN200410014722. 9 discloses a composite inorganic nano-coal slurry I water coke slurry stabilizer, which is composed of fibrous inorganic nanoparticles and spherical inorganic nanoparticles, and has a particle size of 10-100 nm. The aspect ratio of the fibrous inorganic nanoparticles is

1

Confirmation 50-200, the mass percentage of fibrous inorganic nanoparticles and spherical inorganic nanoparticles is 10: 90-90: 10. The water coke slurry stabilizer utilizes the unique surface properties of the nanoparticles to compound the spherical and fibrous nanoparticles, and synergistically exerts various stabilizing effects, which can obviously improve the stability of the water coal/coke slurry.

Chinese patent CN99107794.6 discloses a petroleum coke slurry composition modified with low rank coal, the slurry composition comprising: (1) petroleum coke powder; (2) low grade coal powder, the average particle size of 36- 45 μιη, the amount is 10-100% of the weight of petroleum coke powder; (4) water, the amount of which is 40-60% of the total weight of petroleum coke powder plus low-grade coal powder; (4) additive, the additive is selected from an anion Type of surfactant, including: sulfonate, selected from sodium dodecyl benzoquinone S or sodium polystyrene sulfonate, or phosphate ester, selected from C12-18 alkyl monoester or phosphoric acid C12 — 18 alkyl diester; or a nonionic surfactant such as ethylene oxide and propylene oxide copolymer; or a mixture of two or three of the above various additives, the amount of the additive is 2-10 grams of dry solids per kilogram of solids. The patent mixes pulverized coal in petroleum coke breeze, improves the performance of petroleum coke slurry formation, and improves the stability of the slurry composition.

Chinese patent CN00113911.8 discloses a gasification slurry composed of coal, petroleum coke, additive and water, which is prepared by simultaneously adding coal, petroleum coke, water and additives to a grinding device to prepare a slurry, that is, using a wet grinding process. The pulping process, the particle size of the coal used for preparing the slurry is less than 0.9 mm, 30-80% is less than 0.76, the particle size of the petroleum coke is less than 0.6 mm, and 50-90% is less than 0. G76mtn. The preparation method can directly produce coke coal gasification slurry on the existing coal water slurry preparation device, and can be applied to preparation of raw material gas such as synthetic ammonia and synthetic methanol.

The prior art to date has not provided a water coke slurry which has good stability and can reduce sulfur dioxide emissions after combustion.

Summary of the invention

It is an object of the present invention to provide a smoke that does not undergo hard precipitation and that can be reduced after combustion.

2 Water coke slurry of sulfur dioxide in the gas.

Another object of the present invention is to provide a process for preparing the above water coke slurry.

In order to achieve the above object, in one aspect, the invention 4 provides a desulfurized water coke composition comprising petroleum coke, water and an additive, in terms of mass percentage, the water coke In the composition, the petroleum coke accounts for 55-75%, the water accounts for 24-44%, and the additive accounts for 0.1-2%. The additive in the water coke slurry composition of the present invention further comprises a dispersant for reducing the viscosity of the slurry of the water coke composition, a stabilizer for preventing hard precipitation of the water coke composition, and a desulfurizing agent for reducing sulfur dioxide emissions after combustion.

In the above water coke slurry composition, the dispersing agent may be one or more anionic surfactants, for example: fatty acid oxime ester (taken from oil soap), sodium alkylbenzene sulfonate, alkyl benzene 4 sulfonic acid, sodium dioctyl sulfosuccinate, sodium N-acylmethyltaurate, sodium sulfonated diisooctyl succinate, : ΓΕ-2 emulsifier, high-efficiency dispersant FN, twelve Sodium sulphate, sodium polyoxyethylene sulfate (AES), sodium sulphate polyoxyethylene ether, polyoxyethylene ether phosphate (anionic surfactant), phosphate, tris(2-ethylhexanol) phosphate Wait. Preferred are sulfonated sodium humate and/or sodium lignosulfonate. In the present invention, the main function of the dispersing agent is to lower the viscosity of the water coke slurry to give it a desired fluid type.

In the above water coke slurry composition, the stabilizer may be one or more inorganic salts of a cationic salt such as potassium nitrate or phosphate. Preferred stabilizers are ferrous sulfate and/or sodium tripolyphosphate. In the present invention, the main function of the stabilizer is to compress the electric double layer, reduce the electrostatic repulsive force, and promote the coalescence of the coke particles stably suspended in the water without hard precipitation.

In the above water coke slurry composition, the degreasing agent may be anhydrous calcium chloride or other desulfurizing agents such as activated carbon, zinc oxide, iron oxide or the like. A preferred desulfurizing agent is anhydrous calcium chloride. In the present invention, the main function of the desulfurizing agent is to reduce sulfur dioxide in the flue gas emitted after combustion, and to reduce pollution to the atmosphere.

Further, in the water coke slurry composition of the present invention, by mass percentage, petroleum coke Preferably, it is 60-70%, water is preferably 29-39%, and the additive is preferably Q. 2-1%. Further, in the water-coke composition of the present invention, the dispersant is preferably 0 in terms of mass percentage. 05-0. %。 The sulphurizing agent is preferably 0. 05-0. %.

In addition to petroleum coke, water and additives, the water coke composition of the present invention may further comprise other components such as pulverized coal or other combustibles. In addition to the dispersant, stabilizer, and desulfurizing agent, the additive of the water coke slurry of the present invention may further include other types of additives such as a combustion improver.

In another aspect, the present invention provides a process for preparing the above water coke slurry composition, the method comprising:

(1) mechanically pulverizing the block petroleum coke to obtain petroleum coke powder;

(2) weighing the above petroleum coke powder;

(3) The weighed petroleum coke powder is added into the dispersing agent, the desulfurizing agent and the water in proportion, and is subjected to wet ball milling to form an initial water coke slurry;

(4) filtering and stirring the initial water coke obtained above;

(5) The uniformly stirred initial water coke is homogenized and a stabilizer is added for stirring. In the above process, step (1) can be carried out in two or more steps. If it is carried out in two steps, the first step is to pulverize the block petroleum coke into larger particles of petroleum coke powder, and the second step is to further pulverize the larger particle petroleum coke powder into smaller particles of petroleum coke breeze.

Compared with the prior art, the water coke slurry composition of the present invention has better fluidity and stability due to the inclusion of a dispersant and a stabilizer; the water coke slurry composition of the present invention can be reduced by containing a desulfurizing agent. The oxidation in the flue gas emitted after combustion reduces the pollution of the atmosphere. In addition, due to the low dosage of additives, and non-toxic and harmless, it fully meets environmental protection requirements.

The present invention will be further described with reference to the drawings and specific embodiments, but the present invention is not limited to these specific embodiments, any improvement or substitution in the basic spirit of the present invention, It is still within the scope of the claims as claimed in the invention. DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the process flow for preparing a water coke slurry composition of the present invention. detailed description

Example 1

According to petroleum coke: water: additive - 65. 5: 34: 0. 44 mass percentage of water coke slurry, wherein the specific content of each component in the additive is shown in Table 1. Table 1

Please refer to the pulping process flow chart shown in Figure 1 for the preparation process of the above water coke slurry. The process is:

(1) mechanically crushing the block petroleum coke to a particle size of < 8 mm;

(2) transporting the crushed petroleum coke to the crusher for two times through a belt conveyor to achieve a powder size of < 2 mra;

(3) The pulverized petroleum coke is conveyed to the belt scale through the belt conveyor for continuous weighing;

(4) The weighed petroleum coke powder is added to the additive (dispersant and desulfurizer) in proportion and water is sent to the ball mill for continuous wet ball milling;

(5) petroleum coke powder, water and additives are formed into an initial water coke slurry by a ball mill under strong grinding;

(6) the initial state water coke is filtered through a filter installed in the conveying pipe;

(7) The filtered initial water coke slurry is pumped into a stirred tank equipped with a stirrer by a screw pump;

(8) Stirring the initial state water coke for quality inspection;

(9) Qualified initial water coke is fed into the homogenization tank with a booster pump and added with an additive (stabilizer) in proportion. (The stirring action not only makes the water coke slurry uniform, but also the water coke slurry is repeatedly subjected to the motion shear during the pumping and stirring process of the system, which enhances the interaction between the additive and the petroleum coke powder surface, and effectively improves the slurry flow. transsexual.);

(10) The qualified water coke slurry is pumped into a storage tank equipped with a stirrer or into a daily slurry tank equipped with a stirrer through an in-line filter into the combustion system under agitation.

The quality index of the prepared water coke is tested, and the quality indicators are as follows: Concentration: 66 ± 1% (by mass);

Viscosity: 300 - 800mPa. s;

Fineness: Particles with a particle size greater than 74 μ η are not more than 10°/»;

Proportion: 1. 12 ;

Stability: > 1 month (no hard precipitation occurred).

6 Example 2

According to petroleum coke: water: additive = 65.4: 34: 0.6 by mass of water coke slurry, wherein the specific content of each component in the additive used is shown in Table 1, and the preparation process is the same as in Example 1.

Example 3

According to petroleum coke: Water: Additive - 60.9: 38: 1.1 by mass of water coke slurry, wherein the specific content of each component in the additive used is shown in Table 1, and the preparation process is the same as in Example 1. Example 4

According to petroleum coke: Water: Additive = 68.3: 30: 1.7 mass percentage of water coke slurry, wherein the specific content of each component in the additive used is shown in Table 1, and the preparation process is the same as in Example 1.

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Claims

Rights request

What is claimed is: 1. A dehydrogenated 4-water coke slurry composition comprising petroleum coke, water and an additive, characterized by, in terms of mass percentage, in said water coke slurry composition, said The petroleum coke accounts for 55-75%, the water accounts for 24-44%, and the additive accounts for 0.12%; and the additive further includes reducing the viscosity of the slurry of the water coke composition. A dispersant, a stabilizer for preventing hard precipitation of the water coke composition, and a desulfurizing agent for reducing sulfur dioxide emissions after combustion.

The water coke composition according to claim 1, wherein the dispersing agent is an anionic surfactant.

The water coke slurry composition according to claim 1, wherein the dispersing agent is sodium sulfonated humate and/or sodium lignosulfonate.

The water coke composition according to claim 1, wherein the stabilizer is an inorganic electrolyte of a cationic salt.

The water coke composition according to claim 4, wherein the stabilizer is ferrous sulfate and/or sodium tripolyphosphate.

The water coke composition according to claim 1, wherein the desulfurizing agent is anhydrous calcium chloride.

7. The water coke slurry composition according to claim 1, wherein the mass percentage is 2-1%。 The content of the oil coke composition, the petroleum coke accounted for 60-70%, the water accounted for 29-39% said additive accounted for 0. 2-1%

The amount of the dispersing agent is 0. 05. The dispersing agent is 0. 05. 05-0. %。 The desulfurizer accounted for 0. 05-0. %.

9. A process for the preparation of a water coke composition according to any one of claims 1-8, the method comprising:

(2) weighing the above petroleum coke powder;

(4) filtering and stirring the initial water coke obtained above;

(5) The uniformly stirred initial water coke is homogenized and a stabilizer is added for stirring.

10. The process according to claim 9, wherein the step (1) is carried out in two steps, wherein the first step is to pulverize the block petroleum coke into larger particles of petroleum coke powder. The second step is to further pulverize the larger particle petroleum coke powder into smaller particle petroleum coke powder.

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