CN114196452B - Method for preparing high-alkali coal water slurry from coking wastewater - Google Patents
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
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- C10L1/18—Organic compounds containing oxygen
- C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
- C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
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- C10L1/1857—Aldehydes; Ketones
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2381—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds polyamides; polyamide-esters; polyurethane, polyureas
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
- C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
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Abstract
The invention discloses a method for preparing high-alkali coal water slurry from coking wastewater, which comprises the following steps: mixing and stirring the high-alkali coal powder, the coking wastewater and the additive 3 to prepare coal water slurry; the additive comprises a stabilizer, formaldehyde aqueous solution, a dispersing agent, an emulsifying agent and the like. Compared with the prior art, the invention can realize low-cost treatment of coking wastewater and viscose fiber wastewater while preparing the water-coal-slurry by using high-alkali coal, obviously improve the gasification efficiency of the obtained water-coal-slurry, ensure that the obtained water-coal-slurry has ideal slurry concentration, stability and fluidity, and better meet the process requirements of a gasification furnace.
Description
Technical Field
The invention belongs to the technical field of coal water slurry, and particularly relates to a method for preparing high-alkali coal water slurry from coking wastewater.
Background
The high alkali coal is coal with high alkali metal Na content, and is distributed in the Xinjiang eastern region of China, and the storage amount is huge and reaches over 3900 hundred million tons. The eastern coal field is the largest whole coal field in China, and has the unique advantage of developing the coal conversion process of coal electricity, coal chemical industry and the like in eastern and peripheral areas. However, the high-alkali coal has some defects, such as pollution and slag bonding phenomena of different degrees on the heating surface of the boiler when the high-alkali coal is used as the coal for power, which affects the application range of the high-alkali coal to a certain extent.
The high-alkali coal is made into the coal water slurry, which is helpful for expanding the application range. In general, additives such as a stabilizer, a dispersant, an emulsifier and the like must be added in the preparation process of the coal water slurry. However, when the high-alkali coal is used for preparing the water-coal-slurry, the conventional water-coal-slurry additive has inadaptation in various aspects, such as high cost, low concentration of the prepared water-coal-slurry, poor fluidity, easy sedimentation of coal dust, unsatisfactory gasification efficiency and the like.
Disclosure of Invention
The invention mainly aims to provide a method for preparing high-alkali coal water-coal slurry from coking wastewater, so as to overcome the defects in the prior art.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a method for preparing high-alkali coal water slurry from coking wastewater comprises the following steps: mixing and stirring 60-65 parts by weight of high-alkali coal powder with the particle size smaller than 200 mu m, 30-37 parts by weight of coking wastewater and 3-5 parts by weight of additive at the temperature of 80-90 ℃ to prepare the coal water slurry.
Wherein, the additive comprises the following components in parts by weight:
1-3 parts of a stabilizer,
3-5 parts of formaldehyde aqueous solution with the concentration of 30-35 wt%,
0.05-0.2 part of dispersing agent
0.05-0.1 part of emulsifying agent.
In a preferred embodiment, the additive comprises, in parts by weight:
2-3 parts of a stabilizing agent,
4 to 5 parts of formaldehyde aqueous solution with the concentration of 32 to 35 weight percent,
0.1 to 0.2 part of dispersant, and
0.06-0.1 part of emulsifying agent.
In a preferred embodiment, the stabilizer is polyacrylamide or carboxymethyl cellulose.
More preferably, the stabilizer adopts the mass ratio of 0.5:2-3 with polyacrylamide or carboxymethyl cellulose.
In a preferred embodiment, the dispersant comprises 5-6 parts by weight sodium lignin sulfonate and 3-4 parts by weight sodium naphthalene sulfonate.
In a preferred embodiment, the emulsifier comprises 6-8 parts by weight acetic acid and 1-2 parts by weight sulfuric acid.
In a preferred embodiment, the method specifically comprises: 60-65 parts by weight of high-alkali coal with the grain diameter smaller than 200 mu m, 30-37 parts by weight of coking wastewater, 5-10 parts by weight of viscose fiber acid wastewater and 3-5 parts by weight of additive are mixed and stirred at the temperature of 80-90 ℃ to prepare the coal water slurry.
In a preferred embodiment, the method comprises: 62 to 65 weight portions of confetti coal dust smaller than 200 mu m, 32 to 37 weight portions of coking wastewater and 3 to 4 weight portions of additives are stirred at the temperature of 80 to 90 ℃ to prepare the coal water slurry.
In a preferred embodiment, the method comprises: 62 to 65 weight portions of confetti coal dust smaller than 200 mu m, 32 to 37 weight portions of coking wastewater, 6 to 8 weight portions of viscose fiber acid wastewater and 3 to 4 weight portions of additive are stirred at the temperature of 80 to 90 ℃ to prepare the coal water slurry.
In a preferred embodiment, the high alkali coal includes inorganic sodium salts and organic sodium salts, such as NaCl, na 2 SO 4 And sodium-containing carboxylates and the like.
The coking wastewater is wastewater generated in the high-temperature carbonization and gas purification processes of raw coal, and contains a large amount of organic pollutants and inorganic pollutants, wherein the organic pollutants comprise benzene, phenols and other organic compounds, and the inorganic pollutants comprise cyanide, sulfide, ammonia and the like; in addition, there are generally finer coke breeze and coal ash solids. Because the coking wastewater has complex components, the process for treating the coking wastewater is also complex, the treatment time is long, and the treatment cost is high.
In a preferred embodiment, the ammonia nitrogen content in the coking wastewater is 2684-2690 mg/L, the phenolic content is 3105-3110 mg/L, and the COD is 21000-22000 mg/L.
In a preferred embodiment, the viscose acid waste water is treated by stripping and desulfurizing, the pH value=2-3, and the COD content is 1500-3000mg/L.
In a preferred embodiment, the concentration of the coal water slurry is 56-60 wt% and the apparent viscosity is 1150-1160 MPa/s.
The invention combines the high alkali coal with the coking wastewater, and utilizes formaldehyde therein to generate polymerization reaction with phenolic compounds in the coking wastewater to generate high molecular polymers, and utilizes acetic acid and sulfuric acid therein to dissolve out metal alkali and the like in the high alkali coal to achieve the function of an emulsifier, so that phenolic components in the existing coking wastewater and sodium in the high sodium coal can be effectively utilized, the coking wastewater is treated with low cost while sodium-containing components in the high alkali coal are utilized, organic components in the coking wastewater are gasified, the gasification efficiency is improved, and the requirement of a gasification furnace on coal water slurry is met.
In particular, the inventor also surprisingly found that after the high-alkali coal, the coking wastewater, a small amount of viscose fiber acidic wastewater subjected to stripping desulfurization treatment and the additives are combined, the slurry concentration of the obtained water-coal-slurry can be further improved, and the stability and the fluidity are also greatly improved.
In a word, compared with the prior art, the invention can realize low-cost treatment of coking wastewater and viscose fiber acid wastewater while preparing the water-coal-slurry by using high-alkali coal, obviously improve the concentration, fluidity, stability and gasification efficiency of the obtained water-coal-slurry, and better meet the technological requirements of a gasification furnace.
Detailed Description
The invention will be more fully understood by the following examples. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which may be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
Example 1
In preparing the coal water slurry, the high alkali coal is Xinjiang Zhundong Wucaiwan coal, which is ground and sieved to a particle size of less than 200 μm, and the industrial analysis and ash components of the Wucaiwan coal are shown in the following tables 1 and 2 respectively.
Table 1 five color bay coal industry analysis/%
In Table 1, M ar Indicating moisture of coal, FC ar Represents coal fixed carbon, A ar Represents coal ash, V daf Indicating coal volatiles.
TABLE 2 ash composition analysis/%
From the ash content of table 2, the alkali metal Na content of the confetti coal was far higher than that of the normal coal.
The adopted coking wastewater is tested, the ammonia nitrogen content in the coking wastewater is 2684mg/L, the phenolic content is 3105mg/L, and the COD (chemical oxygen demand) is 21000mg/L.
The additives used included 2 parts of stabilizer (parts by weight unless otherwise specified below), 0.1 part of dispersant, 0.1 part of emulsifier and 4 parts of aqueous formaldehyde solution having a concentration of 35% (weight% unless otherwise specified below). Wherein, the stabilizer adopts polyacrylamide. The dispersant comprises 5 parts of sodium lignin sulfonate and 3 parts of sodium naphthalene sulfonate. The emulsifier comprises 6 parts acetic acid and 1 part sulfuric acid.
During preparation, 65 parts of the five-color bay coal dust smaller than 200 mu m, 32 parts of coking wastewater and 3 parts of additives are stirred at 90 ℃ to prepare the coal water slurry.
Example 2
When preparing the water-coal slurry, the high-alkali coal is prepared from the Xinjiang Guandong Wucaiwan coal, and is ground and sieved to the particle size of below 200 mu m.
The adopted coking wastewater is tested, the ammonia nitrogen content in the coking wastewater is 2684mg/L, the phenolic content is 3105mg/L, and the COD (chemical oxygen demand) is 21000mg/L.
The additive comprises 1 part of stabilizer, 0.05 part of dispersing agent, 0.07 part of emulsifying agent and 3 parts of formaldehyde aqueous solution with concentration of 35%, wherein the stabilizing agent adopts polyacrylamide, the dispersing agent comprises 6 parts of sodium lignin sulfonate and 4 parts of sodium naphthalene sulfonate, and the emulsifying agent comprises 8 parts of acetic acid and 2 parts of sulfuric acid.
During preparation, 60 parts of the five-color bay coal dust smaller than 200 mu m, 30 parts of coking wastewater and 4 parts of additives are stirred at 80 ℃ to prepare the coal water slurry.
In example 2, the concentration of the prepared coal water slurry was 56%, the apparent viscosity was 1160MPa/s, and the gasification efficiency at the temperature of 1200 to 1300℃was 80%.
Example 3
When preparing the water-coal slurry, the high-alkali coal is prepared from the Xinjiang Guandong Wucaiwan coal, and is ground and sieved to the particle size of below 200 mu m.
The adopted coking wastewater is tested, the ammonia nitrogen content in the coking wastewater is 2684mg/L, the phenolic content is 3105mg/L, and the COD (chemical oxygen demand) is 21000mg/L.
The additive comprises 3 parts of stabilizer, 0.2 part of dispersing agent, 0.08 part of emulsifying agent and 5 parts of formaldehyde aqueous solution with concentration of 35%, wherein the stabilizing agent adopts polyacrylamide, the dispersing agent comprises 5.5 parts of sodium lignin sulfonate and 3.5 parts of sodium naphthalene sulfonate, and the emulsifying agent comprises 7 parts of acetic acid and 1.5 parts of sulfuric acid.
During preparation, 63 parts of the five-color bay coal dust smaller than 200 mu m, 37 parts of coking wastewater and 5 parts of additives are stirred at the temperature of 85 ℃ to prepare the coal water slurry.
In example 3, the concentration of the obtained coal water slurry was 60%, the apparent viscosity was 1150MPa/s, and the gasification efficiency at a temperature of 1200 to 1300℃was 85%.
Example 4 this example is substantially identical to example 1 with the difference that:
during preparation, 65 parts of confetti coal dust smaller than 200 mu m, 32 parts of coking wastewater, 8 parts of viscose fiber acid wastewater and 3 parts of additives are stirred at 90 ℃ to prepare the coal water slurry.
The viscose fiber acid wastewater mainly originates from a spinning workshop and an acid station, and comprises plasticizing bath overflow water, spinning machine washing water, acid station filter washing water, silk washing water, post-treatment acid washing water and the like, wherein the viscose fiber acid wastewater is subjected to stripping desulfurization treatment, the pH value is about 3, and the COD content is about 2000mg/L.
Example 5 this example is substantially identical to example 4, except that: wherein the mass ratio of the stabilizer is 0.5:3, a combination of attapulgite clay and polyacrylamide.
Comparative example 1: the high alkali coal and additives used in this comparative example were the same as those used in example 1, but the following method was used to prepare a coal water slurry:
the additive comprises 3 parts of stabilizer, 0.1 part of dispersing agent, 0.08 part of emulsifying agent and 4 parts of formaldehyde aqueous solution with concentration of 35%, wherein the stabilizing agent adopts polyacrylamide, the dispersing agent comprises 5.5 parts of sodium lignin sulfonate and 3.5 parts of sodium naphthalene sulfonate, and the emulsifying agent comprises 7 parts of acetic acid and 1.5 parts of sulfuric acid.
During preparation, 60 parts of the five-color bay coal powder smaller than 200 mu m, 37 parts of water and 5 parts of additives are stirred at 80 ℃ to prepare the coal water slurry.
Table 1 performance data for coal water slurries of examples 1-5 and comparative example 1
The gasification efficiency in the above table was tested at a temperature of 1200-1300 ℃.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (9)
1. A method for preparing high-alkali coal water slurry from coking wastewater is characterized by comprising the following steps: mixing 60-65 parts by weight of high-alkali coal powder with the particle size smaller than 200 mu m, 30-37 parts by weight of coking wastewater and 3-5 parts by weight of additive at the temperature of 80-90 ℃ and stirring to prepare coal water slurry; wherein the additive comprises the following components in parts by weight: 1-3 parts of stabilizer, 3-5 parts of formaldehyde aqueous solution with concentration of 30-35 wt%, 0.05-0.2 part of dispersing agent and 0.05-0.1 part of emulsifier; the emulsifier comprises 6-8 parts by weight of acetic acid and 1-2 parts by weight of sulfuric acid.
2. The method for preparing high-alkali coal water slurry from coking wastewater according to claim 1, wherein the additive consists of the following components in parts by weight: 2-3 parts of stabilizer, 4-5 parts of formaldehyde aqueous solution with concentration of 32-35 wt%, 0.1-0.2 part of dispersant and 0.06-0.1 part of emulsifier.
3. The method for preparing high-alkali coal water slurry from coking wastewater according to claim 1 or 2, wherein the stabilizer comprises polyacrylamide or carboxymethyl cellulose.
4. The method for preparing high-alkali coal water slurry from coking wastewater according to claim 1 or 2, wherein the dispersing agent comprises 5-6 parts by weight of sodium lignin sulfonate and 3-4 parts by weight of sodium naphthalene sulfonate.
5. The method for preparing high-alkali coal water slurry from coking wastewater according to claim 1, which comprises the following steps: and (3) stirring 62-65 parts by weight of confetti coal dust smaller than 200 mu m, 32-37 parts by weight of coking wastewater and 3-4 parts by weight of additive at the temperature of 80-90 ℃ to prepare the coal water slurry.
6. The method for preparing high-alkali coal water slurry from coking wastewater according to claim 1, which is characterized by comprising the following steps: 60-65 parts by weight of high-alkali coal with the grain diameter smaller than 200 mu m, 30-37 parts by weight of coking wastewater, 5-10 parts by weight of viscose fiber acid wastewater and 3-5 parts by weight of additive are mixed and stirred at the temperature of 80-90 ℃ to prepare the coal water slurry.
7. The method for preparing high-alkali coal water slurry from coking wastewater according to claim 6, wherein the viscose fiber acidic wastewater is treated by stripping and desulfurizing, the pH value is=2-3, and the COD content is 1500-3000mg/L.
8. The method for preparing high-alkali coal water slurry from coking wastewater according to claim 1, wherein the content of ammonia nitrogen in the coking wastewater is 2684-2690 mg/L, the content of phenols is 3105-3110 mg/L, and the COD is 21000-22000 mg/L.
9. The method for preparing high-alkali coal water slurry from coking wastewater according to claim 1, wherein the concentration of the water slurry is 56-60wt% and the apparent viscosity is 1150-1160 MPa/s.
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| CN107285512A (en) * | 2017-06-29 | 2017-10-24 | 中国矿业大学 | A kind of method and system of Treatment of Wastewater in Coking |
| CN109179628A (en) * | 2018-09-14 | 2019-01-11 | 中国科学院青岛生物能源与过程研究所 | A method of reducing phenol wastewater phenol content |
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