CN111690447A - Coal water slurry additive and preparation method and application thereof - Google Patents
Coal water slurry additive and preparation method and application thereof Download PDFInfo
- Publication number
- CN111690447A CN111690447A CN202010389751.2A CN202010389751A CN111690447A CN 111690447 A CN111690447 A CN 111690447A CN 202010389751 A CN202010389751 A CN 202010389751A CN 111690447 A CN111690447 A CN 111690447A
- Authority
- CN
- China
- Prior art keywords
- parts
- coal
- water slurry
- tar
- slurry additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/326—Coal-water suspensions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10L10/00—Use of additives to fuels or fires for particular purposes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a coal water slurry additive which comprises the following raw materials in percentage by mass: 6-9 parts of tar sulfonate formaldehyde condensate, 3-5 parts of polyethylene glycol borate (the structural formula is shown in the specification, n is 2-58), 1-3 parts of auxiliary solvent, 0.3-1.2 parts of ammonia water and ammonium salt, the mass ratio of the ammonia water to the ammonium salt is 1:5-1:15, and 12-45 parts of water.
Description
The technical field is as follows:
the invention relates to a coal water slurry additive, a preparation method thereof and application of the coal water slurry additive as a coal water slurry pulping additive.
Technical background:
the coal water slurry technology is an important component of the clean coal technology in China, and the coal water slurry as a coal-based liquid fuel has the advantages of energy conservation, high-efficiency combustion, low pollution and the like. Under the current situation of energy shortage, the development potential is quite huge.
The coal water slurry additive is the key for preparing the coal water slurry with high concentration and high stability, and the cost of the additive accounts for the second in the raw materials for producing the coal water slurry, so that the cost of the additive is reduced, and the preparation of the coal water slurry with high concentration and high performance is the key subject of the existing coal water slurry preparation technology.
Tar after nitrobenzene hydrogenation is a byproduct of nitrobenzene hydrogenation, and the tar of the conventional production device is mainly treated by burning, so that the resource utilization rate is low, and more nitrogen oxides and other atmospheric pollutants are generated. The coal water slurry additive is prepared by sulfonating tar, which is an environment-friendly and economic waste resource utilization mode.
Patent CN 108865301a discloses a method for preparing a gasified coal water slurry additive, which provides that a coal water slurry additive suitable for low-rank coal is prepared by using papermaking waste liquid and washing oil as main raw materials through methods of sulfonation, condensation and the like, and compared with the method using industrial naphthalene or lignin as a raw material, the production cost is greatly reduced, and the concentration can reach 63% in the case of long flame coal.
Patent application CN107619693A discloses a coal water slurry additive prepared from a sodium beta-naphthalenesulfonate formaldehyde condensate, sodium lignosulfonate and water. Wherein the beta-sodium naphthalenesulfonate formaldehyde condensate accounts for 10 to 30 percent, the sodium lignosulfonate accounts for 10 to 30 percent, and the balance is water; the mass ratio of the total mass of the beta-sodium naphthalenesulfonate formaldehyde condensate and sodium lignosulfonate to the mass of water is 2: 3. After the additive is added, the concentration of the coal water slurry can reach 62 percent by taking the nakedflower coal as an example.
Patent application CN108018094A discloses a preparation method of a polyethylene glycol molybdenum type coal water slurry additive. The polyethylene glycol molybdenum has a special double-ring-shaped '8' -shaped structure, compared with a traditional additive such as a long-chain structure of a lignosulfonic acid system, the polyethylene glycol molybdenum has a better dispersion effect, lower coal slurry viscosity and higher slurry forming concentration, and after the additive is added, taking bituminous coal/sub-bituminous coal as an example, the concentration can reach 65.1%, but the coal water slurry prepared by the additive has poor stability and hard precipitation can occur after long standing time.
Patent application CN105695001 discloses a tar type coal water slurry additive prepared by using composite raw material, said additive contains benzene sulfonate formaldehyde condensate, biphenyl sulfonate formaldehyde condensate, anthracene sulfonate formaldehyde condensate, naphthalene sulfonate formaldehyde condensate, lignin sulfonate and pore-blocking agent carbonate, and the sulfonic acid group is in cyclic beta position. The tar type coal water slurry additive has solid content of 50-70% and good fluidity, and the viscosity of the coal slurry is less than 800mpa.s when the shearing rate of the coal slurry is 20s < -1 > under the condition that the coal-based dosage is less than 1.0%. The coal slurry additive in the application has a good effect on improving the slurry forming performance of low-rank coal, but does not remarkably improve the performance of coal with high coalification degree. Although the technical schemes respectively make some progress in the aspects of reducing the production cost, improving the performance of the coal water slurry and the like, the resource utilization rate is low, the concentration of the coal water slurry cannot be effectively improved, and the performance improvement effect on medium-rank and high-rank coals is poor.
The invention content is as follows:
aiming at the problems, the coal water slurry additive and the preparation method thereof are provided to solve the problems that the cost of raw materials for preparing the coal water slurry additive is high and the improvement effect of the prepared coal water slurry additive on the formed slurry is not obvious in the prior art.
In order to achieve the purpose, the invention provides a scheme for preparing a coal water slurry additive by modifying tar and compounding a boron dispersant, the coal water slurry additive prepared by modifying the tar and compounding polyethylene glycol borate is used for preparing coal water slurry, and finally the tar is used as coal waterThe components of the slurry are combusted or gasified, so that the resource utilization and the environment-friendly treatment of the tar waste liquid are thoroughly realized, and the production cost is greatly reduced. Boron-unhybridized 2p vacant orbital in the structure of the polyethylene glycol borate is easy to accept lone pair electrons on oxygen atoms in free hydroxyl in molecules to form a coordination bond, and valence electron configuration of boron atoms is induced to be changed into thermodynamically stable sp3The hybridized orbit forms a semipolar boron spiral three-dimensional structure, the organic boron dispersing agent is non-toxic, non-corrosive, high in boiling point, non-volatile and quite stable at high temperature, the dispersity and coal slurry concentration of coal can be controlled by changing the polymerization degree of the polyethylene glycol borate, the coal particle excessive aggregation is prevented, the coal slurry performance is prevented from being influenced, and the coal slurry concentration can be increased by 0.8-1.8 wt%. The finally prepared coal slurry additive has low cost, small dosage, better dispersion effect, lower coal slurry viscosity and great effect on improving the performance of the slurry.
The technical scheme provided by the invention is as follows:
the coal water slurry additive is prepared from the following raw materials in percentage by mass: 6-9 parts of tar sulfonate formaldehyde condensate, 3-5 parts of polyethylene glycol borate (the structural formula is shown in the specification, n is 2-58), 1-3 parts of auxiliary solvent, 0.3-1.2 parts of ammonia water and ammonium salt, the mass ratio of the ammonia water to the ammonium salt is 1:5-1:15, and 12-45 parts of water.
Further, it preferably comprises by mass: 6.5-7.5 parts of tar sulfonate formaldehyde condensate, 3.5-4.4 parts of polyethylene glycol borate (the structural formula is shown as the specification, n is 10-36), 1.5-2.5 parts of auxiliary solvent, 0.5-0.8 part of ammonia water and ammonium salt, wherein the concentration of the ammonia water can be 5-10 wt%.
Further, the ammonium salt is one or more of ammonium persulfate, ammonium sulfate, ammonium borate and ammonium carbonate. Ammonium persulfate and ammonium borate are preferred, and can increase the surface charge density of micelles in the coal water slurry, thereby increasing the double electric layers and the electric potential and enhancing the repulsive force among particles.
Further, the auxiliary solvent is one or more of dipropylene glycol, ethylene glycol, propylene glycol and isopropanol. Dipropylene glycol and ethylene glycol are preferred, and the addition of the solvent is favorable for changing the interfacial tension on the surface of the coal particles; and the dispersing effect can be promoted to be better exerted by the uniform distribution of the adsorption points on the surfaces of the dispersing agent and the coal particles.
In the invention, the tar sulfonate formaldehyde condensate is obtained by performing sulfonation polycondensation reaction on tar, sulfuric acid and formaldehyde, wherein the tar is derived from nitrobenzene hydrogenated tar. The tar is a byproduct of nitrobenzene hydrogenation reaction, mainly contains aniline, aromatic hydrocarbon, polycyclic aromatic hydrocarbon, Schiff base, polymer thereof and the like, the nitrobenzene hydrogenation reaction process is not particularly limited, and the tar obtained by any process usually contains the above components.
A preparation method of a coal water slurry additive comprises the following steps: the dosage of each raw material is calculated by the mass portion,
(1) adding 1-1.5 parts, preferably 1-1.2 parts, of concentrated sulfuric acid into 2.5-4 parts, preferably 2.5-3 parts, of tar to perform sulfonation, adding 6-8 parts, preferably 6.5-7.5 parts, of water after full reaction to perform hydrolysis, performing polycondensation reaction on the hydrolysate and 2-3 parts, preferably 2.1-2.5 of formaldehyde, adding 5-6 parts, preferably 5-5.6 parts, of sodium hydroxide with the concentration of 25-30 wt% to perform neutralization to alkalinity, and obtaining a tar sulfonate formaldehyde condensate;
(2) adding 1-1.5 parts, preferably 1.2-1.3 parts of boric acid and 15-25 parts of solvent, preferably 20-25 parts of solvent into 10 parts of polyethylene glycol, mixing and heating to prepare polyethylene glycol borate;
(3) mixing the tar sulfonate formaldehyde condensate, polyethylene glycol borate, an auxiliary solvent and ammonium salt, and heating at constant temperature;
(4) after cooling, adding water, and then adding ammonia water to adjust the pH value to 8-9 to obtain the coal water slurry additive.
Further, the temperature of the sulfonation reaction in the step (1) is 150-. The polycondensation reaction temperature is 70-85 ℃, preferably 75-80 ℃, and the constant temperature reaction is carried out for 4-6 h. The hydrolysis reaction temperature is 55-65 deg.C, preferably 55-60 deg.C, and constant temperature reaction is carried out for 0.5-1 h.
Further, the reaction temperature in the step (2) is 120-130 ℃, preferably 125-130 ℃, and the constant temperature reaction is carried out for 1.5-2 h.
Further, the reaction temperature in the step (3) is 70-80 ℃, preferably 70-75 ℃, and the reaction is carried out for 1-2 hours at constant temperature.
Further, the average molecular weight of the polyethylene glycol in the step (2) is 100-.
Further, the solvent adopted in the step (2) is one or more of benzene, toluene, isopropanol and ethylene glycol.
The coal water slurry additive is used for preparing the coal water slurry: the percentage of the dry basis weight of the coal water slurry additive to the dry basis weight of the coal is 0.25 to 0.8wt percent.
According to the method, the coal water slurry additive is used, taking bituminous coal/sub-bituminous coal as an example, compared with the prior art, the concentration of the coal water slurry is increased by 1.2-1.8 wt%, the achievable concentration is 63.2-66.0 wt%, taking anthracite coal as an example, the concentration of the coal water slurry is increased by 0.8-1.2 wt%, the concentration can reach 67.5-69.0 wt%, the apparent viscosity of the coal slurry is 1000 +/-100 mPa & s, the stability and the fluidity are good, and the coal water slurry can stand for 3 days without unrecoverable hard precipitates. The nitrobenzene hydrogenated tar adopted by the invention has good effect on improving the performance of medium-order and high-order coal types, and the dispersibility and slurrying property of the coal are further improved by compounding the polyethylene glycol borate with a semipolar boron spiral three-dimensional structure.
Detailed Description
The following test methods were used in the examples and comparative examples of the present invention:
an infrared detector: model Is10 (Thermo).
A viscometer: model NXS-4C (national coal water slurry engineering development center)
Quick moisture meter: model M35M (Sidolisi scientific instruments (Beijing) Co., Ltd.)
Indexes such as concentration, viscosity, fluidity and the like of the coal water slurry and detection methods are carried out according to GB-/T18855-2008. Sources of tar: wanhua chemical group Ltd, nitrobenzene apparatus hydrogenation reaction by-products.
Example 1
The coal water slurry additive is prepared from the following raw materials in parts by mass: 7 parts of tar sulfonate formaldehyde condensate, 3.5 parts of polyethylene glycol borate, 2 parts of dipropylene glycol, 0.7 part of ammonium persulfate, 0.08 part of ammonia water and 15 parts of water.
The preparation method of the coal water slurry additive is realized by the following steps:
(1) adding 3 parts of tar into a reaction container, adding 1 part of concentrated sulfuric acid for sulfonation, controlling the temperature to be 160 ℃, carrying out constant temperature reaction at normal pressure for 3 hours, adding 6.5 parts of water for hydrolysis after full reaction, controlling the temperature to be 55 ℃, carrying out constant temperature reaction at normal pressure for 1 hour, adding 2.5 parts of formaldehyde into hydrolysate for polycondensation reaction, controlling the temperature to be 80 ℃, carrying out constant temperature reaction at normal pressure for 4 hours, adding 5 parts of 30 wt% sodium hydroxide, and neutralizing to be alkaline to obtain a tar sulfonate formaldehyde condensate;
(2) adding 10 parts of polyethylene glycol (with the molecular weight of 1000) into a reaction container, adding 1.5 parts of boric acid, adding 22 parts of benzene, mixing and heating, controlling the reaction temperature to be 125 ℃, and reacting at constant temperature under normal pressure for 2 hours to prepare polyethylene glycol borate;
(3) taking 7 parts of the tar sulfonate formaldehyde condensate obtained in the step (1), 3.5 parts of the polyethylene glycol borate obtained in the step (2), 2 parts of dipropylene glycol and 0.7 part of ammonium persulfate. Heating at 70 deg.C and normal pressure for 1 hr;
(4) and reducing the temperature to 25 ℃, adding 5 wt% of ammonia water, adding 15 parts of water, and adjusting the pH to 9 to obtain the coal water slurry additive.
Taking 67.5g of pulverized bituminous coal after crushing and drying and 0.28g of the above coal water slurry additive (dry basis weight), adding water to dilute to 100g, and uniformly stirring to obtain the flowable coal water slurry.
The fluidity is A-detected according to a standard method, the apparent viscosity of the slurry at 25 ℃ is 930mPa & s measured by a viscometer, the concentration of the coal slurry is 64.0 wt% measured by a rapid moisture meter, and the slurry is kept stand for 72 hours without unrecoverable hard precipitates.
Example 2
The coal water slurry additive is prepared from the following raw materials in parts by mass: 9 parts of tar sulfonate formaldehyde condensate, 3.6 parts of polyethylene glycol borate, 1.5 parts of dipropylene glycol, 0.5 part of ammonium borate, 0.04 part of ammonia water and 12 parts of water.
The preparation method of the coal water slurry additive is realized by the following steps:
(1) adding 4 parts of tar into a reaction container, adding 1.5 parts of concentrated sulfuric acid for sulfonation, controlling the temperature to be 155 ℃, carrying out constant temperature reaction at normal pressure for 2.5 hours, adding 7 parts of water for hydrolysis after full reaction, controlling the temperature to be 60 ℃, carrying out constant temperature reaction at normal pressure for 1 hour, adding 3 parts of formaldehyde into hydrolysate for polycondensation reaction, controlling the temperature to be 80 ℃, carrying out constant temperature reaction at normal pressure for 4 hours, adding 5.4 parts of 30 wt% of sodium hydroxide for neutralization to alkalinity, and obtaining a tar sulfonate formaldehyde condensate;
(2) adding 10 parts of polyethylene glycol (molecular weight is 300) into a reaction container, adding 1.5 parts of boric acid, adding 22 parts of benzene, mixing and heating, controlling the reaction temperature to be 125 ℃, and reacting for 2 hours at constant temperature under normal pressure to prepare polyethylene glycol borate;
(3) and (2) taking 9 parts of the tar sulfonate formaldehyde condensate obtained in the step (1), 3.6 parts of the polyethylene glycol borate obtained in the step (2), 1.5 parts of dipropylene glycol and 0.5 part of ammonium borate. Heating at 70 deg.C and normal pressure for 1 hr;
(4) after the temperature is reduced to 25 ℃, 10 wt% of ammonia water is added, 12 parts of water is added, and the pH value is adjusted to 9 to obtain the coal water slurry additive.
Taking 68.0g of pulverized bituminous coal after crushing and drying and 0.32g of the coal water slurry additive (dry basis weight), adding water to dilute the pulverized bituminous coal and the coal water slurry additive to 100g, and uniformly stirring the mixture to obtain the flowable coal water slurry.
And (3) detecting the fluidity B according to a standard method, determining the apparent viscosity of the slurry at 25 ℃ to be 1032mPa & s by using a viscometer, determining the concentration of the coal slurry to be 63.6 wt% by using a rapid moisture meter, and standing for 72 hours without unrecoverable hard precipitates.
Example 3
The coal water slurry additive is prepared from the following raw materials in parts by mass: 6.5 parts of tar sulfonate formaldehyde condensate, 4 parts of polyethylene glycol borate, 2.5 parts of dipropylene glycol, 0.75 part of ammonium persulfate, 0.05 part of ammonia water and 20 parts of water.
The preparation method of the coal water slurry additive is realized by the following steps:
(1) adding 3.5 parts of tar into a reaction container, adding 1.3 parts of concentrated sulfuric acid for sulfonation, controlling the temperature to be 160 ℃, carrying out constant temperature reaction at normal pressure for 3 hours, adding 6.8 parts of water for hydrolysis after full reaction, controlling the temperature to be 65 ℃, carrying out constant temperature reaction at normal pressure for 0.5 hour, adding 2.9 parts of formaldehyde into hydrolysate for polycondensation reaction, controlling the temperature to be 75 ℃, carrying out constant temperature reaction at normal pressure for 5 hours, adding 5.6 parts of 30 wt% of sodium hydroxide for neutralization to alkalinity, and obtaining a tar sulfonate formaldehyde condensate;
(2) adding 10 parts of polyethylene glycol (molecular weight 2000) into a reaction container, adding 1.3 parts of boric acid, adding 25 parts of isopropanol, mixing and heating, controlling the reaction temperature at 130 ℃, and reacting at constant temperature under normal pressure for 2 hours to prepare polyethylene glycol borate;
(3) taking 6.5 parts of the tar sulfonate formaldehyde condensate obtained in the step (1), 4 parts of the polyethylene glycol borate obtained in the step (2), 2.5 parts of dipropylene glycol and 0.75 part of ammonium persulfate. Heating at 70 deg.C and normal pressure for 1.5 h;
(4) after the temperature is reduced to 25 ℃, 10 wt% of ammonia water is added, 20 parts of water is added, and the pH value is adjusted to 9 to obtain the coal water slurry additive.
Taking 68.0g of pulverized bituminous coal after crushing and drying and 0.32g of the coal water slurry additive (dry basis weight), adding water to dilute the pulverized bituminous coal and the coal water slurry additive to 100g, and uniformly stirring the mixture to obtain the flowable coal water slurry.
The fluidity is A according to a standard method, the apparent viscosity of the slurry at 25 ℃ is 905mPa & s by using a viscometer, the concentration of the coal slurry is measured by using a rapid moisture meter to be 65.8 wt%, and the slurry is kept stand for 72 hours without unrecoverable hard precipitates.
Example 4
The coal water slurry additive is prepared from the following raw materials in parts by mass: 8 parts of tar sulfonate formaldehyde condensate, 3 parts of polyethylene glycol borate, 2.5 parts of ethylene glycol, 0.6 part of ammonium borate, 0.08 part of ammonia water and 14 parts of water.
The preparation method of the coal water slurry additive is realized by the following steps:
(1) adding 4 parts of tar into a reaction container, adding 1.5 parts of concentrated sulfuric acid for sulfonation, controlling the temperature to be 155 ℃, performing constant-temperature reaction for 3 hours at normal pressure, adding 8 parts of water for hydrolysis after full reaction, controlling the temperature to be 60 ℃, performing constant-temperature reaction for 0.5 hour at normal pressure, adding 3 parts of formaldehyde into hydrolysate for polycondensation reaction, controlling the temperature to be 80 ℃, performing constant-temperature reaction for 4 hours at normal pressure, adding 5.5 parts of 30 wt% of sodium hydroxide for neutralization to alkalinity, and obtaining a tar sulfonate formaldehyde condensate;
(2) adding 10 parts of polyethylene glycol (with the molecular weight of 2500) into a reaction container, adding 1.0 part of boric acid, adding 20 parts of benzene, mixing and heating, controlling the reaction temperature to be 120 ℃, and reacting at constant temperature under normal pressure for 1.5 hours to prepare polyethylene glycol borate;
(3) and (2) taking 8 parts of the tar sulfonate formaldehyde condensate obtained in the step (1), 3 parts of the polyethylene glycol borate obtained in the step (2), 0.5 part of ethylene glycol and 1.2 parts of ammonium borate. Heating at 70 deg.C and normal pressure for 1 hr;
(4) after the temperature is reduced to 25 ℃, 5 wt% of ammonia water is added, 14 parts of water is added, and the pH value is adjusted to 9 to obtain the coal water slurry additive.
Taking 70g of pulverized anthracite after crushing and drying and 0.25g of the coal water slurry additive (dry basis weight), adding water to dilute the pulverized anthracite and the coal water slurry additive to 100g, and uniformly stirring to obtain the flowable coal water slurry.
The fluidity is A-detected according to a standard method, the apparent viscosity of the slurry at 25 ℃ is 1018mPa & s measured by a viscometer, the concentration of the coal slurry is 68.5 wt% measured by a rapid moisture meter, and the slurry is kept stand for 72 hours without unrecoverable hard precipitates.
COMPARATIVE EXAMPLE 1 (COMPARATIVE WITH EXAMPLE 3)
The coal water slurry additive is prepared from the following raw materials in parts by mass: 6.5 parts of tar sulfonate formaldehyde condensate, 2.5 parts of dipropylene glycol, 0.75 part of ammonium persulfate, 0.05 part of ammonia water and 20 parts of water.
The preparation method of the additive for the coal water slurry of the comparative example is realized by the following steps:
(1) adding 3.5 parts of tar into a reaction container, adding 1.3 parts of concentrated sulfuric acid for sulfonation, controlling the temperature to be 160 ℃, carrying out constant temperature reaction at normal pressure for 3 hours, adding 8 parts of water for hydrolysis after full reaction, controlling the temperature to be 65 ℃, carrying out constant temperature reaction at normal pressure for 0.5 hour, adding 2.9 parts of formaldehyde into hydrolysate for polycondensation reaction, controlling the temperature to be 75 ℃, carrying out constant temperature reaction at normal pressure for 5 hours, adding 5.5 parts of 30 wt% of sodium hydroxide for neutralization to alkalinity, and obtaining a tar sulfonate formaldehyde condensate;
(2) 6.5 parts of the obtained tar sulfonate formaldehyde condensate, 2.5 parts of dipropylene glycol and 0.75 part of ammonium persulfate. Heating at 70 deg.C and normal pressure for 1.5 h;
(3) after the temperature is reduced to 25 ℃, 5 wt% of ammonia water is added, 20 parts of water is added, and the pH value is adjusted to 9 to obtain the coal water slurry additive.
Taking 63.0g of pulverized bituminous coal after crushing and drying and 0.32g of the coal water slurry additive (dry basis weight), adding water to dilute the pulverized bituminous coal and the coal water slurry additive to 100g, and uniformly stirring to obtain the coal water slurry.
And (3) detecting the fluidity to be C according to a standard method, determining the apparent viscosity of the slurry to be 1080mPa & s at 25 ℃ by using a viscometer, determining the concentration of the coal slurry to be 62.1 wt% by using a rapid moisture meter, standing for 24h for soft precipitation, and standing for 72h for unrecoverable hard precipitation.
Comparative example 2
Taking 68.0g of pulverized bituminous coal after crushing and drying and 0.32g of lignin coal water slurry additive (dry basis weight) (Degradization chemical industry), adding 5 wt% of ammonia water and water to dilute to 100g, wherein the pH value is 9, and no flowable slurry is formed after stirring (the system is pasty, the fluidity is D according to a standard method), and the viscosity can not be measured (more than 2000mPa & s).
TABLE 1 evaluation results of slurry formation performance and activity of the coal water slurry prepared
Wherein, the fluidity of the coal water slurry is A > B > C > D.
Claims (10)
1. A coal water slurry additive, which is characterized in that: the material is prepared from the following raw materials in percentage by mass: 6-9 parts of tar sulfonate formaldehyde condensate, preferably 6.5-7.5 parts, 3-5 parts of polyethylene glycol borate, preferably 3.5-4.4 parts, 1-3 parts of auxiliary solvent, preferably 1.5-2.5 parts, 0.3-1.2 parts of ammonia water and ammonium salt, preferably 0.5-0.8 part, the mass ratio of the ammonia water to the ammonium salt is 1:5-1:15, and 12-45 parts of water; the structural formula of the polyethylene glycol borate is shown in the specification, wherein n is 2-58, preferably n is an integer of 10-36,
2. the coal water slurry additive according to claim 1, wherein: the ammonium salt is one or more of ammonium persulfate, ammonium sulfate, ammonium borate and ammonium carbonate.
3. The coal-water slurry additive according to claim 1 or 2, wherein the auxiliary solvent is one or more of dipropylene glycol, ethylene glycol, propylene glycol and isopropyl alcohol.
4. The coal-water slurry additive according to any one of claims 1 to 3, wherein the tar sulfonate formaldehyde condensate is obtained by sulfonating and polycondensing tar, which is derived from nitrobenzene hydrogenated tar, with sulfuric acid and formaldehyde.
5. The method of preparing a coal water slurry additive according to any one of claims 1 to 4, wherein: the method comprises the following steps: the dosage of each raw material is calculated by the mass portion,
(1) adding tar into concentrated sulfuric acid for sulfonation reaction and then hydrolyzing, performing polycondensation reaction on hydrolysate and formaldehyde and then neutralizing to be alkaline to obtain a tar sulfonate formaldehyde condensate, preferably, adding 1-1.5 parts of concentrated sulfuric acid into 2.5-4 parts of tar for sulfonation reaction, adding 6-8 parts of water for hydrolysis after full reaction, performing polycondensation reaction on hydrolysate and 2-3 parts of formaldehyde, and adding 5-6 parts of sodium oxide solution with the concentration of 25-30 wt% for neutralization to be alkaline to obtain the tar sulfonate formaldehyde condensate;
(2) adding 1-1.5 parts of boric acid and a solvent into 10 parts of polyethylene glycol, mixing and heating to prepare polyethylene glycol borate;
(3) mixing the obtained tar sulfonate formaldehyde condensate, polyethylene glycol borate, an auxiliary solvent and ammonium salt, and heating at constant temperature;
(4) after cooling, adding water, and then adding ammonia water to adjust the pH value to be alkalescent, wherein the pH value is preferably 8-9, so as to obtain the coal water slurry additive.
6. The method for preparing a coal water slurry additive according to claim 5, wherein the method comprises the following steps: the temperature of the sulfonation reaction in the step (1) is 150-; and/or, the hydrolysis reaction temperature is 55-65 ℃, and the constant temperature reaction is carried out for 0.5-1 h.
7. The method of claim 5 or 6, wherein the coal water slurry additive is prepared by the following steps: the reaction temperature in the step (2) is 120-.
8. The process for preparing a coal-water slurry additive according to claims 5 to 7, wherein: the heating temperature in the step (3) is 70-80 ℃, and the heating time is 1-2 h.
9. The method of any one of claims 5 to 8 for the preparation of a coal water slurry additive, wherein: the average molecular weight of the polyethylene glycol is between 100 and 3000, preferably 500 and 1500.
10. Use of a coal water slurry additive according to any one of claims 1 to 4 or prepared by the method of any one of claims 5 to 9 as a coal water slurry slurrying additive: wherein the addition amount is 0.25-0.8 wt% of the dry basis weight of the coal water slurry additive and the dry basis weight of coal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010389751.2A CN111690447B (en) | 2020-05-11 | 2020-05-11 | Coal water slurry additive and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010389751.2A CN111690447B (en) | 2020-05-11 | 2020-05-11 | Coal water slurry additive and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111690447A true CN111690447A (en) | 2020-09-22 |
| CN111690447B CN111690447B (en) | 2022-04-22 |
Family
ID=72477525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010389751.2A Active CN111690447B (en) | 2020-05-11 | 2020-05-11 | Coal water slurry additive and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111690447B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114160306A (en) * | 2021-11-18 | 2022-03-11 | 万华化学（宁波）有限公司 | Preparation method of polar high-molecular type coal water slurry additive and residual carbon separation method |
| CN114479969A (en) * | 2020-10-27 | 2022-05-13 | 万华化学集团股份有限公司 | Coal water slurry additive and preparation method thereof |
| CN115404106A (en) * | 2021-05-29 | 2022-11-29 | 中国石油化工股份有限公司 | Method for co-gasifying oily wastewater and inferior heavy oil |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067259A (en) * | 1991-05-28 | 1992-12-23 | 华煤水煤浆技术联合中心 | Tar oil type high-concentration water-coal slurry additive and production technique |
| CN102031168A (en) * | 2010-12-11 | 2011-04-27 | 水煤浆气化及煤化工国家工程研究中心 | Anionic-nonionic complex gasified coal water slurry additive |
| CN102911313A (en) * | 2012-08-14 | 2013-02-06 | 陕西科技大学 | Preparation method of anion sulfonate type coal water slurry dispersant |
| CN105695001A (en) * | 2016-02-17 | 2016-06-22 | 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 | Tar-type coal water slurry additive prepared from composite raw materials and production technology of tar-type coal water slurry additive |
-
2020
- 2020-05-11 CN CN202010389751.2A patent/CN111690447B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067259A (en) * | 1991-05-28 | 1992-12-23 | 华煤水煤浆技术联合中心 | Tar oil type high-concentration water-coal slurry additive and production technique |
| CN102031168A (en) * | 2010-12-11 | 2011-04-27 | 水煤浆气化及煤化工国家工程研究中心 | Anionic-nonionic complex gasified coal water slurry additive |
| CN102911313A (en) * | 2012-08-14 | 2013-02-06 | 陕西科技大学 | Preparation method of anion sulfonate type coal water slurry dispersant |
| CN105695001A (en) * | 2016-02-17 | 2016-06-22 | 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 | Tar-type coal water slurry additive prepared from composite raw materials and production technology of tar-type coal water slurry additive |
Non-Patent Citations (1)
| Title |
|---|
| 张晓松等: "聚乙二醇硼酸酯的合成", 《精细化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479969A (en) * | 2020-10-27 | 2022-05-13 | 万华化学集团股份有限公司 | Coal water slurry additive and preparation method thereof |
| CN114479969B (en) * | 2020-10-27 | 2023-08-11 | 万华化学集团股份有限公司 | Water-coal-slurry additive and preparation method thereof |
| CN115404106A (en) * | 2021-05-29 | 2022-11-29 | 中国石油化工股份有限公司 | Method for co-gasifying oily wastewater and inferior heavy oil |
| CN115404106B (en) * | 2021-05-29 | 2024-04-02 | 中国石油化工股份有限公司 | Co-gasification method of oily wastewater and inferior heavy oil |
| CN114160306A (en) * | 2021-11-18 | 2022-03-11 | 万华化学（宁波）有限公司 | Preparation method of polar high-molecular type coal water slurry additive and residual carbon separation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111690447B (en) | 2022-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111690447B (en) | Coal water slurry additive and preparation method and application thereof | |
| CN101564663B (en) | Amphoteric water-coal-slurry dispersing agent and preparation method thereof | |
| CN104327280A (en) | Preparation method of alkali lignin modified polycarboxylic acid-type coal water slurry dispersant | |
| CN1194802C (en) | Modified lignin sulfosalt dispersant of water coal slurry | |
| CN102260556A (en) | Coal water slurry with brown coal low-temperature modified semi coke as raw material and preparation method thereof | |
| CN102031168A (en) | Anionic-nonionic complex gasified coal water slurry additive | |
| CN103819626A (en) | Preparation method of humic acid-based poly-carboxylic acid type coal water slurry dispersant | |
| CN104152195B (en) | A kind of both sexes humate coal water slurry dispersing agent and preparation and application thereof | |
| CN103265984B (en) | Lignin dispersant for phenol-water coal water slurry, and preparation method and application thereof | |
| CN104946288A (en) | Modified pitch and preparation method thereof | |
| CN102250655A (en) | Preparation method of high-fluidity gasified water-coal slurry dispersant | |
| CN102504893A (en) | Polystyrene-maleic anhydride derivative water-coal-slurry additive and preparation method thereof | |
| CN104774660A (en) | Naphthalene coal water slurry additive and preparation method thereof | |
| CN108456282A (en) | A kind of saponin(e graft copolymer coal water slurry dispersant and preparation method thereof | |
| CN101691511A (en) | Coal-tar pitch fuel composite | |
| CN105695001A (en) | Tar-type coal water slurry additive prepared from composite raw materials and production technology of tar-type coal water slurry additive | |
| CN108218279B (en) | A kind of building trade cement water reducing agent and preparation method thereof containing graphene | |
| CN107312581A (en) | The surface additive and its application process of a kind of biomass coal-water slurry | |
| CN102492074A (en) | Comb type copolymer with side chains grafted with naphthalene sulfonic acid groups, preparation method thereof and application thereof | |
| CN113969197B (en) | Multi-copolymer dispersant based on humic acid, preparation method thereof and application thereof in coal water slurry | |
| CN102559305A (en) | Compound efficient coal water slurry additive and preparation method thereof | |
| CN109776722A (en) | Ternary graft copolymer and its preparation method and application | |
| CN102614809B (en) | Method for preparing dispersing-stabilizing agent by using papermaking sludge | |
| CN115418255A (en) | Synthetic method for preparing coal water slurry additive by oxidizing, grafting and modifying papermaking black liquor and using method thereof | |
| CN108587709B (en) | Method for preparing coal water slurry additive from waste mother liquor and reaction residues of 2-naphthol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 315812 Wanhua Industrial Park, Daxie Development Zone, Ningbo City, Zhejiang Province Patentee after: Wanhua chemical (Ningbo) Co.,Ltd. Patentee after: Wanhua Chemical Group Co.,Ltd. Address before: 315812 Wanhua Industrial Park, 39 Huandao North Road, Daxie Development Zone, Hangzhou City, Zhejiang Province Patentee before: Wanhua chemical (Ningbo) Co.,Ltd. Patentee before: Wanhua Chemical Group Co.,Ltd. |