阅读说明：本技术 一种高硫石油焦浆安全有效的利用方法 (Safe and effective utilization method of high-sulfur petroleum coke slurry ) 是由 郑国栋 王志敏 袁红年 侯茂林 贾博 王亦飞 于广锁 于 2021-09-16 设计创作，主要内容包括：本发明公开的是一种高硫石油焦浆安全有效的利用方法,该方法包括如下步骤：将高硫石油焦破碎后,进入磨机研磨得到焦粉；将焦粉、水、石油焦浆添加剂、稳定剂混合均匀后制得浓度在60-72％的石油焦浆；在气化炉内将石油焦浆与纯氧发生不完全氧化反应,生产获得粗煤气,工艺简单、新颖,能够安全有效利用高硫石油焦,适合推广,绿色环保。(The invention discloses a safe and effective utilization method of high-sulfur petroleum coke slurry, which comprises the following steps: crushing the high-sulfur petroleum coke, and grinding the crushed high-sulfur petroleum coke in a grinder to obtain coke powder; uniformly mixing coke powder, water, petroleum coke slurry additive and stabilizer to prepare petroleum coke slurry with the concentration of 60-72%; the method has the advantages that the petroleum coke slurry and pure oxygen are subjected to incomplete oxidation reaction in the gasification furnace, crude gas is obtained through production, the process is simple and novel, high-sulfur petroleum coke can be safely and effectively utilized, and the method is suitable for popularization and is green and environment-friendly.)

1. A safe and effective utilization method of high-sulfur petroleum coke slurry is characterized by comprising the following steps:

step 1): crushing the high-sulfur petroleum coke, and grinding the crushed high-sulfur petroleum coke in a grinder to obtain coke powder;

step 2): uniformly mixing coke powder, water, petroleum coke slurry additive (lignin dispersant) and stabilizer (carboxymethyl cellulose stabilizer) to obtain petroleum coke slurry with the concentration of 60-72%;

step 3): and carrying out incomplete oxidation reaction on the petroleum coke slurry and pure oxygen in a gasification furnace to produce and obtain crude gas.

2. The safe and effective utilization method of high-sulfur petroleum coke slurry as claimed in claim 1, characterized in that: the raw gas comprises carbon monoxide, hydrogen and carbon dioxide.

3. The safe and effective utilization method of high-sulfur petroleum coke slurry as claimed in claim 1, characterized in that: in the step 1), high-sulfur petroleum coke with the particle size of below 15mm is crushed to the particle size of less than 3mm, and then the crushed petroleum coke enters a grinding machine to be ground to obtain coke powder with proper particle size distribution.

4. The safe and effective utilization method of high-sulfur petroleum coke slurry as claimed in claim 1, characterized in that: the reaction temperature in the gasification furnace in the step 3) is 1400-.

5. The safe and effective utilization method of high-sulfur petroleum coke slurry as claimed in claim 1, characterized in that: the concentration of the petroleum coke slurry in the step 2) is any one of 60%, 65%, 67%, 70% and 72%.

6. A safe and effective utilization method of high-sulfur petroleum coke slurry is characterized by comprising the following steps:

step 1): grinding raw coal to the same particle size distribution as petroleum coke, drying coal powder and petroleum coke powder to remove moisture, and uniformly mixing the coal powder and the petroleum coke powder according to the mass ratio of 90:10, 80:20, 70:30, 50:50, 40:60, 20:80, 10:90 or 0:100 to obtain mixed solid;

step 2): mixing the mixed solid with a lignin dispersant, a carboxymethyl cellulose stabilizer and grey water according to a mass ratio of 60:0.14:0.01:39.85 to obtain mixed slurry;

step 3): stirring the mixed slurry at 50 ℃ and 40rpm for 5min to obtain high-sulfur petroleum coke slurry;

step 4): the high-sulfur petroleum coke slurry and pure oxygen are subjected to incomplete oxidation reaction in a gasification furnace to produce and obtain crude gas.

7. A safe and effective utilization method of high-sulfur petroleum coke slurry is characterized by comprising the following steps:

step 1): uniformly mixing coal powder and petroleum coke powder according to the mass ratio of 70:30 or 60:40 or 50:50 or 20:80 or 10:90 or 0:100 to obtain mixed solid;

step 2): mixing the mixed solid with a lignin dispersant, a carboxymethyl cellulose stabilizer and grey water according to a mass ratio of 65:0.18:0.02:34.8 to obtain mixed slurry;

step 3): stirring at 50 ℃ and 40rpm for 5min to obtain high-sulfur petroleum coke slurry;

step 4): the high-sulfur petroleum coke slurry and pure oxygen are subjected to incomplete oxidation reaction in a gasification furnace to produce and obtain crude gas.

8. A safe and effective utilization method of high-sulfur petroleum coke slurry is characterized by comprising the following steps:

step 1): mixing petroleum coke powder, a lignin dispersant, a carboxymethyl cellulose stabilizer and grey water according to a mass ratio of 65:0.18:0.02:34.8 or 67:0.2:0.02:32.78 or 70:0.21:0.03:29.76 or 72:0.24:0.03:27.73 to obtain mixed slurry;

step 2): stirring at 50 ℃ and 40rpm for 5min to obtain high-sulfur petroleum coke slurry;

step 3): the high-sulfur petroleum coke slurry and pure oxygen are subjected to incomplete oxidation reaction in a gasification furnace to produce and obtain crude gas.

9. A safe and effective utilization method of high-sulfur petroleum coke slurry is characterized by comprising the following steps:

step 1): uniformly mixing the gasification fine slag and the petroleum coke powder according to the mass ratio of 10:90, 8:92, 5:95 or 2:98 to obtain a mixed solid;

step 2): mixing the mixed solid with a lignin dispersant, a carboxymethyl cellulose stabilizer and grey water according to a mass ratio of 65:0.15:0.02:34.83 to obtain mixed slurry;

step 3): stirring the mixed slurry at 50 ℃ and 40rpm for 5min to obtain high-sulfur petroleum coke slurry;

step 4): the high-sulfur petroleum coke slurry and pure oxygen are subjected to incomplete oxidation reaction in a gasification furnace to produce and obtain crude gas.

Technical Field

The invention relates to a method for utilizing petroleum coke slurry, in particular to a safe and effective utilization method of high-sulfur petroleum coke slurry, belonging to the field of petrochemical industry.

Background

Petroleum coke is a byproduct generated by a coking device of an oil refinery, the crude oil processing capacity of the refinery in China is rapidly increased since this century, the coking capacity is increased faster during the period, the yield of the corresponding petroleum coke is increased, and the yield of the petroleum coke in 1-10 months nationwide in 2020 is 2413.2 ten thousand tons. With the increasing global oil demand and the heavy crude oil, the production of petroleum coke is increasing dramatically. The dependence of petroleum in China on the outside is increased from 52% in 2005 to nearly 70% in 2017, and the imported petroleum mainly comprises Western high-sulfur petroleum, so that the proportion of the high-sulfur petroleum coke in the petroleum coke in China is higher and higher. The high-sulfur petroleum coke is mainly applied to combustion power generation, but because the sulfur content of the petroleum coke is high, a large amount of acid gas and waste residues are generated after combustion and are difficult to treat, and equipment is seriously corroded, the safe and effective utilization of the high-sulfur petroleum coke is a hot point problem in the industry in recent years.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a safe and effective utilization method of high-sulfur petroleum coke slurry, which has the technical characteristics of safely and effectively utilizing high-sulfur petroleum coke and the like.

In order to achieve the purpose, the invention is realized by the following technical scheme:

a safe and effective utilization method of high-sulfur petroleum coke slurry comprises the following steps:

step 1): crushing the high-sulfur petroleum coke, and grinding the crushed high-sulfur petroleum coke in a grinder to obtain coke powder;

step 2): uniformly mixing coke powder, water, petroleum coke slurry additive (lignin dispersant) and stabilizer (carboxymethyl cellulose stabilizer) to obtain petroleum coke slurry with the concentration of 60-72%;

step 3): and carrying out incomplete oxidation reaction on the petroleum coke slurry and pure oxygen in a gasification furnace to produce and obtain crude gas.

Preferably, the raw gas comprises carbon monoxide, hydrogen and carbon dioxide.

Preferably, in the step 1), the high-sulfur petroleum coke with the particle size of less than 15mm is crushed to the particle size of less than 3mm, and then the crushed high-sulfur petroleum coke enters a mill to be ground to obtain the coke powder with proper particle size distribution.

Preferably, the reaction temperature in the gasification furnace in step 3) is 1400-.

Preferably, the concentration of the petroleum coke slurry in the step 2) is any one of 60%, 65%, 67%, 70% and 72%.

A safe and effective utilization method of high-sulfur petroleum coke slurry comprises the following steps:

step 1): grinding raw coal to the same particle size distribution as petroleum coke, drying coal powder and petroleum coke powder to remove moisture, and uniformly mixing the coal powder and the petroleum coke powder according to the mass ratio of 90:10, 80:20, 70:30, 50:50, 40:60, 20:80, 10:90 or 0:100 to obtain mixed solid;

step 2): mixing the mixed solid with a lignin dispersant, a carboxymethyl cellulose stabilizer and grey water according to a mass ratio of 60:0.14:0.01:39.85 to obtain mixed slurry;

step 3): stirring the mixed slurry at 50 ℃ and 40rpm for 5min to obtain high-sulfur petroleum coke slurry;

step 4): the high-sulfur petroleum coke slurry and pure oxygen are subjected to incomplete oxidation reaction in a gasification furnace to produce and obtain crude gas.

A safe and effective utilization method of high-sulfur petroleum coke slurry comprises the following steps:

step 1): uniformly mixing coal powder and petroleum coke powder according to the mass ratio of 70:30 or 60:40 or 50:50 or 20:80 or 10:90 or 0:100 to obtain mixed solid;

step 2): mixing the mixed solid with a lignin dispersant, a carboxymethyl cellulose stabilizer and grey water according to a mass ratio of 65:0.18:0.02:34.8 to obtain mixed slurry;

step 3): stirring at 50 ℃ and 40rpm for 5min to obtain high-sulfur petroleum coke slurry;

step 4): the high-sulfur petroleum coke slurry and pure oxygen are subjected to incomplete oxidation reaction in a gasification furnace to produce and obtain crude gas.

A safe and effective utilization method of high-sulfur petroleum coke slurry comprises the following steps:

step 1): mixing petroleum coke powder, lignin dispersant, carboxymethyl cellulose stabilizer and grey water according to the mass ratio of 65:0.18:0.02:34.8 or 67:0.2:0.02:32.78 or 70:0.21:0.03:29.76 or

72:0.24:0.03:27.73 to obtain mixed slurry;

step 2): stirring at 50 ℃ and 40rpm for 5min to obtain high-sulfur petroleum coke slurry;

step 3): the high-sulfur petroleum coke slurry and pure oxygen are subjected to incomplete oxidation reaction in a gasification furnace to produce and obtain crude gas.

A safe and effective utilization method of high-sulfur petroleum coke slurry comprises the following steps:

step 1): uniformly mixing the gasification fine slag and the petroleum coke powder according to the mass ratio of 10:90, 8:92, 5:95 or 2:98 to obtain a mixed solid;

step 2): mixing the mixed solid with a lignin dispersant, a carboxymethyl cellulose stabilizer and grey water according to a mass ratio of 65:0.15:0.02:34.83 to obtain mixed slurry;

step 3): stirring the mixed slurry at 50 ℃ and 40rpm for 5min to obtain high-sulfur petroleum coke slurry;

step 4): the high-sulfur petroleum coke slurry and pure oxygen are subjected to incomplete oxidation reaction in a gasification furnace to produce and obtain crude gas.

Has the advantages that: the process is simple and novel, can safely and effectively utilize the high-sulfur petroleum coke, is suitable for popularization, and is green and environment-friendly.

Detailed Description

The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.

The method is suitable for preparing petroleum coke slurry from raw coal and petroleum coke, gasification fine slag and petroleum coke and pure petroleum coke, and has pioneering significance for efficient utilization of high-sulfur petroleum coke.

The invention adopts petroleum coke to prepare slurry with better fluidity and gasifies the petroleum coke with pure oxygen at high temperature and high pressure, which belongs to the innovative development idea.

The principle is as follows: the following chemical reactions mainly take place in the gasifier:

partial oxidation reaction: CmHnSr + m/2O₂→mCO+(n/2–r)H₂+rH₂S+Q

Combustion reaction of coal: CmHnSr + (m + n/4-r/2) O₂→(m-r)CO2+n/2H2O+rCOS+Q

Coal cracking reaction: CmHnSr → (n/4-r/2) CH4+ (m-n/4-r/2) C + rH₂S-Q

CO2 reduction reaction: c + CO₂→2CO-Q

Complete combustion reaction of carbon: c + O₂→CO₂+Q

Heterogeneous water gas reaction: c + H₂O→H₂+CO-Q

C+2H₂O→2H₂+CO₂-Q

Methane conversion reaction: CH (CH)₄+H₂O→3H₂+CO-Q

Inverse transformation reaction: h₂+CO₂→H₂O+CO-Q

The following side reactions may also occur:

COS+H₂O＝H₂S+CO₂

C+O₂+H₂＝HCOOH

N₂+3H₂＝2NH₃

N₂+H₂+2C＝2HCN

the reaction products are mainly CO and H₂、CO₂、H₂O, and the like. The product gas can be used as synthetic ammonia and synthetic methanol after different processes and different pretreatments in the prior artRaw material gas for power generation and fuel gas.

The invention relates to a safe and effective utilization method of high-sulfur petroleum coke slurry, which comprises the following steps:

step 1): crushing the high-sulfur petroleum coke, and grinding the crushed high-sulfur petroleum coke in a grinder to obtain coke powder; preferably, high-sulfur petroleum coke with the particle size of below 15mm is crushed to the particle size of less than 3mm, and then the crushed petroleum coke enters a grinding machine to be ground to obtain coke powder with proper particle size distribution, wherein the specific distribution is shown in the following table 1;

TABLE 1 coke powder particle size distribution:

step 2): uniformly mixing coke powder, water, a petroleum coke slurry additive (lignin dispersant) and a stabilizer (carboxymethyl cellulose stabilizer) to prepare a petroleum coke slurry with the concentration of 60-72%, wherein the prepared petroleum coke slurry with proper concentration, low viscosity, good fluidity and high stability is the basis and the premise of gasified petroleum coke; preferably, the concentration of the petroleum coke slurry may be any one of 60%, 65%, 67%, 70%, 72%;

step 3): carrying out incomplete oxidation reaction on the petroleum coke slurry and pure oxygen in a gasification furnace to produce and obtain crude gas; the reaction temperature in the gasification furnace is 1400 ℃ and 1550 ℃, and the pressure is about 6.5MPa (G); the crude gas comprises carbon monoxide, hydrogen, carbon dioxide, pure oxygen: the petroleum coke slurry (volume ratio) is 500-: 500. 510, 524, 530, 545, the utilization and further processing of the raw gas after reaction in the gasifier are not what is to be analyzed in this application and therefore not described in detail, and those skilled in the art can make different uses according to the actual needs according to the specific components.

Example 1:

a safe and effective utilization method of high-sulfur petroleum coke slurry comprises the following steps:

step 1): grinding raw coal to the same particle size distribution as petroleum coke, drying coal powder and petroleum coke powder to remove moisture, preparing coal powder and petroleum coke powder into one part respectively according to the mass ratio of 90:10, 80:20, 70:30, 50:50, 40:60, 20:80, 10:90 and 0:100, and uniformly mixing the parts to obtain mixed solids respectively;

step 2): mixing each mixed solid with a lignin dispersing agent, a carboxymethyl cellulose stabilizer and grey water according to a mass ratio of 60:0.14:0.01:39.85 to obtain mixed slurry;

step 3): stirring the mixed slurry at 50 ℃ and 40rpm for 5min to obtain high-sulfur petroleum coke slurry;

step 4): the high-sulfur petroleum coke slurry and pure oxygen are subjected to incomplete oxidation reaction in a gasification furnace to produce and obtain crude gas.

TABLE 2 results of petroleum coke slurry property testing

As can be seen from the data in Table 2, with the increase of the petroleum coke addition ratio, the viscosity of the petroleum coke slurry is obviously reduced, the fluidity is improved, the stability is slightly reduced, the water separation rate is increased, and the method meets the requirements of practical industrial application (the petroleum coke slurry is used for treating high-sulfur petroleum coke by the entrained flow gasification technology).

Example 2

A safe and effective utilization method of high-sulfur petroleum coke slurry comprises the following steps:

step 1): preparing coal powder and petroleum coke powder into one part respectively according to the mass ratio of 70:30, 60:40, 50:50, 20:80, 10:90 and 0:100, and uniformly mixing each part to respectively obtain mixed solids;

step 2): mixing each part of mixed solid with a lignin dispersing agent, a carboxymethyl cellulose stabilizer and grey water according to a mass ratio of 65:0.18:0.02:34.8 to obtain mixed slurry;

step 3): stirring at 50 ℃ and 40rpm for 5min respectively to obtain high-sulfur petroleum coke slurry;

step 4): the high-sulfur petroleum coke slurry and pure oxygen are subjected to incomplete oxidation reaction in a gasification furnace to produce and obtain crude gas.

TABLE 3 results of petroleum coke slurry Properties testing

As can be seen from the results in Table 3, the petroleum coke slurry with the concentration of 65 percent has reduced viscosity and better fluidity along with the increase of the proportion of the petroleum coke, and meets the requirements of industrial application.

Example 3

A safe and effective utilization method of high-sulfur petroleum coke slurry comprises the following steps:

step 1): mixing petroleum coke powder, lignin dispersant, carboxymethyl cellulose stabilizer and grey water according to the mass ratio of 65:0.18:0.02:34.8, 67:0.2:0.02:32.78, 70:0.21:0.03:29.76

72:0.24:0.03:27.73 to obtain a mixed slurry;

step 2): stirring at 50 ℃ and 40rpm for 5min respectively to obtain high-sulfur petroleum coke slurry;

step 3): the high-sulfur petroleum coke slurry and pure oxygen are subjected to incomplete oxidation reaction in a gasification furnace to produce and obtain crude gas.

TABLE 4 results of petroleum coke slurry property testing

As can be seen from the results in Table 4, the viscosity, fluidity, stability and water separation rate of the petroleum coke slurry with the concentrations of 65%, 67%, 70% and 72% all meet the requirements of industrial application.

Example 4

A safe and effective utilization method of high-sulfur petroleum coke slurry comprises the following steps:

step 1): preparing gasification fine slag and petroleum coke powder in parts by mass ratio of 10:90, 8:92, 5:95 and 2:98, and uniformly mixing the parts to obtain mixed solids respectively;

step 2): mixing each part of mixed solid with a lignin dispersing agent, a carboxymethyl cellulose stabilizer and grey water according to a mass ratio of 65:0.15:0.02:34.83 to obtain mixed slurry;

step 3): stirring the mixed slurry at 50 ℃ and 40rpm for 5min to obtain high-sulfur petroleum coke slurry;

step 4): the high-sulfur petroleum coke slurry and pure oxygen are subjected to incomplete oxidation reaction in a gasification furnace to produce and obtain crude gas.

TABLE 5 results of petroleum coke slurry Properties test

As can be seen from the results in Table 5, the viscosity, fluidity, stability and water separation rate of the petroleum coke slurry with the concentration of 65% after being mixed with the gasified fine slag meet the requirements of industrial application.

Finally, it should be noted that the present invention is not limited to the above embodiments, and many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.