CN108315068B - Method for reducing viscosity of coal water slurry - Google Patents
Method for reducing viscosity of coal water slurry Download PDFInfo
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- CN108315068B CN108315068B CN201810299473.4A CN201810299473A CN108315068B CN 108315068 B CN108315068 B CN 108315068B CN 201810299473 A CN201810299473 A CN 201810299473A CN 108315068 B CN108315068 B CN 108315068B
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- 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
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- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
Abstract
The invention relates to a method for reducing viscosity of coal water slurry, which mainly solves the problem of poor viscosity reducing effect of the existing coal water slurry viscosity reducer, and adopts the method for reducing the viscosity of the coal water slurry, and comprises the steps of obviously reducing apparent viscosity and yield stress of the coal water slurry and greatly improving the flow property in the presence of the viscosity reducer, wherein the preparation of the viscosity reducer comprises the steps of synthesizing an intermediate product by free radical polymerization, synthesizing the viscosity reducer by chemical modification and purifying and drying, and the general formula of the raw material of the viscosity reducer is M αxSyAaBbCcDdWherein M is maleic anhydride, α is α -alkene, S is styrene, A is initiating agent, B is modifier, C is catalyst, D is the technical scheme of solvent, has solved this technical matter well, can apply to industrial coal water slurry and store steadily and pump in the transportation.
Description
Technical Field
The invention relates to a method for reducing viscosity of coal water slurry.
Background
Since the innovation was opened, the Chinese economy continues to grow at a high speed, and in 2010, the Chinese economy becomes the second economic entity in the world beyond Japan all at once. In 2015, the world economy continues to be low, and in China, under the new normal state of structure adjustment and transformation upgrading, the GDP still keeps at the high-speed development level of 6.9%, and is still the main power for promoting the development of the world economy, thereby making a significant contribution to the world economy. The back of the rapid development of Chinese economy not only needs scientific support, but also has an increasing demand for fossil energy. The continuous development in China continuously expands the demand on energy, and leads the limited energy resources to be exhausted increasingly. According to the world energy statistics, the reserves of coal in Chinese petrochemical energy are more abundant than those of petroleum and natural gas, but the reserves are estimated to be only dozens of years, so that the reasonable and efficient utilization becomes a great trend.
The energy production and energy consumption conditions in China are determined by the energy structure in China, the proportion of coal in the energy production structure in the last ten years in China is as high as about 85%, and the proportion of coal consumption in the consumed petrochemical energy is as high as more than 70%. The traditional large-scale coal burning mode inevitably generates a large amount of waste gas (CO)2、NOX、SOX) And dust (such as PM 2.5) cause serious environmental pollution problems such as acid rain, greenhouse effect, haze and the like. In order to solve the contradiction between development and environment, China puts forward a series of policies and laws and regulations, on one hand, the utilization of renewable energy sources (such as wind energy, solar energy, nuclear energy and the like) is increased, and on the other hand, the existing coal resources are cleanedThe cleaning agent can be used efficiently. Therefore, Chinese researchers have proposed a series of clean coal technologies, such as coal water slurry, coal liquefaction, coal gasification, fluidized bed combustion, integrated gasification combined cycle power generation (IGCC), flue gas purification, fuel cells and the like. The coal water slurry is the best result of coal liquefaction and the cheapest practical technology for clean utilization of coal, and can effectively reduce environmental pollution by being used as oil-replacing fuel. The coal water slurry technology originated in the world oil crisis in the 70 th 20 th century, and people realized that clean energy such as petroleum and natural gas is inexhaustible. Currently, many countries in the world already have very mature technologies, such as the united states, russia, japan. China also uses the coal water slurry technology as an important national science and technology project for many times, obtains rich technical achievements, is in the leading position of the world, still needs to be intensively researched, and makes the coal water slurry technology in China more perfect and mature.
In a narrow sense, the coal water slurry is a coal-based fluid fuel obtained by physically processing 60-70% of coal, 29-39% of water and about 1% of chemical additives; in a broad sense, with the development of the coal water slurry technology, novel mixed coal water slurry is derived, such as sludge coal water slurry, oil-water coal slurry, fatty alcohol coal water slurry and the like. The coal water slurry can replace the conventional energy, has the advantages of high efficiency, environmental protection, convenience and the like, has a calorific value which is half of that of fuel oil, and is widely applied to various boilers at present. The water-coal-slurry technology mainly comprises a preparation technology, a storage and transportation technology, a combustion utilization technology and an environment-friendly technology, wherein the four technologies respectively represent four stages of water-coal-slurry application, the performance of the prepared water-coal-slurry directly influences the difficulty of loading, unloading, transportation and the combustion utilization efficiency, and the combustion efficiency is directly related to the environment protection. Therefore, the preparation technology is an important part of the whole process, and is one of the reasons that the preparation technology is concerned by researchers. The additive is an essential chemical substance in the process of pulping, plays an important role although the dosage of the additive is less than one percent of that of the coal water slurry, and not only can the apparent viscosity of the coal water slurry be reduced and the fluidity and the stability be improved, but also the additive is beneficial to preparing the high-concentration coal water slurry and improving the heat value. The viscosity reducer is the most main coal water slurry additive, can disperse coal particles and reduce viscosity, thereby reducing transportation resistance, and simultaneously has a stabilizing effect; the viscosity reducer mainly prevents coal slurry from layering, and prolongs the storage time. Therefore, research and development of a novel low-cost viscosity reducer have great significance on development of a coal water slurry technology.
The efficient viscosity reducer is a key means for preparing high-concentration water-coal-slurry, and particularly has obvious influence on the quality (such as concentration, viscosity, stability, rheological property and the like) of a water-coal-slurry product due to the difficulty in slurrying low-rank coal. G. The atecook et al uses a wet process for pulping, uses two viscosity reducers of sodium polystyrene sulfonate and naphthalene sulfonic acid formaldehyde polycondensate to respectively pulp with two coals, and researches show that after the viscosity reducers are added in the pulping process, the grindability is improved, the viscosity of the slurry is reduced, and the cost of the pulping process is greatly saved. However, as the coal types for pulping are increasingly diversified, the pulping process is gradually developed and perfected, and the viscosity reduction and stability performance of the viscosity reducer cannot completely adapt to the change requirements of the coal types and the process. Therefore, the coal water slurry viscosity reducer with good viscosity reduction effect and good stability has to be developed in a targeted manner.
Disclosure of Invention
The invention aims to solve the technical problem of poor viscosity reduction effect of the existing coal water slurry viscosity reducer, and provides a novel method for reducing the viscosity of the coal water slurry.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the method for reducing viscosity of coal water slurry comprises the steps of obviously reducing apparent viscosity and yield stress of the coal water slurry and greatly improving flow property in the presence of a viscosity reducer, wherein the preparation of the viscosity reducer comprises the steps of synthesizing an intermediate product by free radical polymerization, chemically modifying and synthesizing the viscosity reducer and purifying and drying, and the general formula of the raw material of the viscosity reducer is M αxSyAaBbCcDdWherein M is maleic anhydride, α is α -olefin (one or more selected from dodecene to eicosene), S is styrene, A is initiator selected from cyclohexanone peroxide, dibenzoyl peroxide, dimethyl methylThe modifier B is one or more of ethanol, propanol, butanol, isobutanol, isoamyl alcohol, active amyl alcohol, phenethyl alcohol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butanediol, polybutylene glycol, pentanediol, glycerol, undecanol-eicosanediol, undecylamine-eicosamine, fatty alcohol polyoxyethylene ether, alkylphenol ethoxylate, anionic polyacrylamide, sodium sulfamate, sodium cyclamate, aminobenzenesulfonate, aminobenzenesulfonic acid and salts thereof, sulfamoyl benzene sulfonic acid and salts thereof, aminonaphthalene sulfonic acid and salts thereof, aminohydroxynaphthalene sulfonic acid and salts thereof, aminonaphthalene sulfonic acid and salts thereof, one or more of dimethylnaphthalene sulfonic acid and salts thereof, a catalyst for dimethylnaphthalene sulfonic acid, a catalyst for dimethylbenzene sulfonic acid anhydride, a, 0.01-0.5 molar ratio of maleic anhydride, 0.01-0.5 molar ratio of dimethyl benzene sulfonic acid anhydride, 0-0.5 molar percent of maleic anhydride, 0.5 molar ratio of dimethyl benzene sulfonic acid anhydride, 0.5-0.5 molar percent of maleic anhydride, 0.01-0 molar percent of acetic anhydride, 0-2 molar percent of maleic anhydride, 0-2-0-2-0-5 molar ratio of maleic anhydride, and a of maleic anhydride, and a-0-5 molar ratio of maleic anhydride, and a-0-5-0-5 molar ratio of maleic anhydride, and a-5-2-0-2-0-5-0-2-5-0-5-0.
In the technical scheme, the coal water slurry sample is from Shanxi elm forest Shenfu coal.
In the technical scheme, after the coal water slurry viscosity reducer is added, a rheometer is adopted to test the viscosity and the yield stress change.
In the technical scheme, the mass fraction of the coal water slurry viscosity reducer is 0.01-3%, and preferably 0.2-0.8%.
In the technical scheme, the testing temperature of the viscosity and the yield stress is-20-200 ℃, and the viscosity and the yield stress are measured at 20 ℃ for example, so as to be convenient for practical application.
In the technical scheme, the testing time of the viscosity and the yield stress is preferably 1-50 min.
In the above technical scheme, as one of the preferable technical schemes, B preferably simultaneously comprises polytetramethylene glycol and aminonaphthalenesulfonic acid, and the polytetramethylene glycol and the aminonaphthalenesulfonic acid have a synergistic effect in improving the viscosity reduction of the coal water slurry.
In the above technical scheme, as a second preferred technical scheme, B preferably includes polytetramethylene glycol and aminohydroxynaphthalene sulfonic acid at the same time, and the polytetramethylene glycol and aminohydroxynaphthalene sulfonic acid have a synergistic effect in improving the viscosity reduction of the coal water slurry.
In the above technical scheme, as a third preferred technical scheme, B preferably simultaneously comprises polytetramethylene glycol and dimethylamino naphthalenesulfonic acid, and the polytetramethylene glycol and the dimethylamino naphthalenesulfonic acid have a synergistic effect in improving the viscosity reduction of the coal water slurry.
In the above technical scheme, as one of more preferable technical schemes, B simultaneously comprises polytetramethylene glycol, aminonaphthalenesulfonic acid and aminohydroxynaphthalenesulfonic acid, and the three have a synergistic effect of ternary combination in improving viscosity reduction of coal water slurry.
In the above technical scheme, as a second more preferable technical scheme, B simultaneously comprises polytetramethylene glycol, aminonaphthalenesulfonic acid and dimethylaminonaphthalenesulfonic acid, and the three have a synergistic effect of ternary combination in improving the viscosity reduction of the coal water slurry.
In the above technical scheme, as a third more preferable technical scheme, B simultaneously comprises polytetramethylene glycol, aminohydroxynaphthalene sulfonic acid and dimethylamino naphthalene sulfonic acid, and the three have a synergistic effect of ternary combination in improving the viscosity reduction of the coal water slurry.
In the above technical solution, as a fourth preferred technical solution, B simultaneously includes polytetramethylene glycol, aminonaphthalenesulfonic acid, aminohydroxynaphthalenesulfonic acid, and dimethylaminonaphthalenesulfonic acid, and the fourth has a quaternary combination synergistic effect in improving viscosity reduction of coal water slurry.
In the above technical scheme, a more specific example of the composition general formula of the raw material of the viscosity reducer can be, but is not limited to:
[ maleic anhydride ]][ dodecene ]]0.2~5.0[ styrene ]]0.2~5.0[ lauroyl peroxide ]]0.01~2.0[ polytetramethylene glycol ]]0.1~2.5[ Aminonaphthalenesulfonic acid ]]0.1~2.5[ p-methylbenzenesulfonic acid]0.005~1.0[ Potassium hydroxide]0.005~1.0[ chloroform ]]5.0~20.0
[ maleic anhydride ]][ dodecene ]]0.2~5.0[ styrene ]]0.2~5.0[ lauroyl peroxide ]]0.01~2.0[ polytetramethylene glycol ]]0.1~2.5[ aminohydroxynaphthalenesulfonic acid]0.1~2.5[ p-methylbenzenesulfonic acid]0.005~1.0[ Potassium hydroxide]0.005~1.0[ chloroform ]]5.0~20.0
[ maleic anhydride ]][ dodecene ]]0.2~5.0[ styrene ]]0.2~5.0[ lauroyl peroxide ]]0.01~2.0[ polytetramethylene glycol ]]0.1~2.5[ Dimethylaminonaphthalenesulfonic acid ]]0.1~2.5[ p-methylbenzenesulfonic acid]0.005~1.0[ Potassium hydroxide]0.005~1.0[ chloroform ]]5.0~20.0
[ maleic anhydride ]][ dodecene ]]0.2~5.0[ styrene ]]0.2~5.0[ lauroyl peroxide ]]0.01~2.0[ polytetramethylene glycol ]]0.1~2.0[ Aminonaphthalenesulfonic acid ]]0.05~1.5[ aminohydroxynaphthalenesulfonic acid]0.05~1.5[ p-methylbenzenesulfonic acid]0.005~1.0[ Potassium hydroxide]0.005~1.0[ chloroform ]]5.0~20.0
[ maleic anhydride ]][ dodecene ]]0.2~5.0[ styrene ]]0.2~5.0[ lauroyl peroxide ]]0.01~2.0[ polytetramethylene glycol ]]0.1~2.0[ Aminonaphthalenesulfonic acid ]]0.05~1.5[ Dimethylaminonaphthalenesulfonic acid ]]0.05~1.5[ p-methylbenzenesulfonic acid]0.005~1.0[ Potassium hydroxide]0.005~1.0[ chloroform ]]5.0~20.0
[ maleic anhydride ]][ dodecene ]]0.2~5.0[ styrene ]]0.2~5.0[ lauroyl peroxide ]]0.01~2.0[ polytetramethylene glycol ]]0.1~2.0[ aminohydroxynaphthalenesulfonic acid]0.05~1.5[ Dimethylaminonaphthalenesulfonic acid ]]0.05~1.5[ p-methylbenzenesulfonic acid]0.005~1.0[ Potassium hydroxide]0.005~1.0[ chloroform ]]5.0~20.0
[ maleic anhydride ]][ dodecene ]]0.2~5.0[ styrene ]]0.2~5.0[ lauroyl peroxide ]]0.01~2.0[ polytetramethylene glycol ]]0.1~2.0[ Aminonaphthalenesulfonic acid ]]0.03~1.0[ aminohydroxynaphthalenesulfonic acid]0.03~1.0[ Dimethylaminonaphthalenesulfonic acid ]]0.04~1.0[ p-methylbenzenesulfonic acid]0.005~1.0[ Potassium hydroxide]0.005~1.0[ chloroform ]]5.0~20.0
In the technical scheme, the molecular weight of the coal water slurry viscosity reducer is 1000-100000.
In the technical scheme, the esterification degree of the coal water slurry viscosity reducer is 0.1-5.0.
In the above technical scheme, how to dissolve the raw material components and the order of addition are not particularly limited, and all the raw material components can obtain comparable technical effects, for which, a person skilled in the art can reasonably select. In order to facilitate the comparison, the raw material components of the specific embodiment of the invention are mixed and dissolved.
In the technical scheme, the preparation steps of the high-efficiency coal water slurry viscosity reducer comprise:
free radical polymerization to synthesize intermediate product;
chemically modifying and synthesizing the viscosity reducer;
purifying and drying.
In the above technical scheme, the purification method is not particularly limited as long as unreacted raw materials or byproducts in the above viscosity reducer can be removed, and those skilled in the art can reasonably select and apply the purification method.
In the above technical solution, the drying conditions are not particularly limited as long as the viscosity reducer can be changed from the emulsion state to the solid powder state, and those skilled in the art can reasonably select the drying conditions without creative labor.
In the above technical scheme, the temperature of the free radical polymerization reaction is 30-180 ℃, and the reaction time is 0.5-12 hours, for example only.
In the above technical scheme, the chemical modification reaction temperature is 30 to 180 ℃, and the reaction time is 0.5 to 12 hours, by way of example only.
In the technical scheme, the high-efficiency coal water slurry viscosity reducer can be prepared in the following way:
1. free radical polymerization synthesis intermediate
Maleic anhydride, α -olefin, styrene, an initiator and a solvent are added into a reactor, the mixture is mechanically stirred to be completely dissolved, and the mixture reacts for 0.5 to 12 hours at the temperature of between 30 and 180 ℃ to obtain an intermediate product.
2. Chemical modification synthesis viscosity reducer
And (3) continuously adding a modifier and a catalyst into the reactor 1, and reacting at 30-180 ℃ for 0.5-12 hours to obtain the viscosity reducer. The dissolution step and the temperature-controlling step are not particularly limited, and the specific dissolution and temperature-controlling procedures and process conditions can be appropriately selected by those skilled in the art.
3. Purifying and drying
And (3) reducing the temperature of the viscosity reducer in the step (2) to 20-90 ℃, adding the viscosity reducer into an organic solvent (such as methanol, ethanol, propanol and the like), adding the precipitated solid into water at 20-90 ℃, washing for multiple times, and finally filtering and drying to obtain solid powder of the viscosity reducer.
The coal water slurry viscosity reducer prepared by the method is surprisingly good in viscosity reduction effect.
The viscosity reducer evaluation method of the invention is as follows:
a rheometer: an Anton Paar Physica MCR 501 advanced rotational rheometer, Austria, using a coaxial cylinder and a cross-bladed rotor ST-22-4V-40;
filling amount of the viscosity reducer: 50 g;
and (3) testing temperature: 20 ℃;
testingThe method comprises the following steps: apparent viscosity (one): at a shear rate of 100s-1Next, 3s takes one datum, tests for 3min totally, and takes the last point as a result; (II) yield stress: the shear stress increases logarithmically from 1Pa to 1000Pa, taking the corresponding viscosity value, and when the viscosity suddenly drops, the corresponding shear stress is the yield stress.
By adopting the viscosity reducer, the viscosity reducing effect of a coal water slurry sample can reach 95%, a better technical effect is obtained, and the viscosity reducer can be used for stable storage and pumping transportation of industrial coal water slurry.
Drawings
The following is a further description of the invention with reference to the figures and examples.
FIG. 1 is a graph of the rate of decrease in viscosity and the rate of decrease in yield stress of the coal-water slurry as a function of the number of examples.
Detailed Description
[ example 1 ]
1. Free radical polymerization synthesis intermediate
Adding 1mol of chloroform into a 500ml three-neck flask, then respectively adding 0.1mol of maleic anhydride, 0.12mol of dodecene and 0.03mol of lauroyl peroxide, mechanically stirring to completely dissolve the materials, reacting for 2 hours at 100 ℃, then cooling to 70 ℃, slowly adding 0.12mol of styrene, and continuing to react for 5 hours to obtain an intermediate product.
2. Chemical modification synthesis viscosity reducer
And continuously adding 0.06mol of polytetramethylene glycol and 0.02mol of p-toluenesulfonic acid into the three-neck flask, stirring for dissolving, and continuously reacting for 5 hours at 100 ℃ to obtain the viscosity reducer.
3. Purifying and drying
Reducing the temperature of the viscosity reducer in the step 2 to 30 ℃, then adding the viscosity reducer into ethanol, then adding the precipitated solid into 30 ℃ water for cleaning, repeating the cleaning for multiple times, and finally performing suction filtration and drying to obtain the viscosity reducer with the following raw materials:
[ maleic anhydride ]][ dodecene ]]1.2[ styrene ]]1.2[ lauroyl peroxide ]]0.3[ polytetramethylene glycol ]]0.6[ p-methylbenzenesulfonic acid]0.2[ chloroform ]]10.0
4. Viscosity reducer evaluation
And (5) inspecting the viscosity reduction rate and yield stress reduction rate of the coal water slurry. The viscosity reducer raw material composition and the evaluation results are shown in FIG. 1 for convenience of comparison.
[ example 2 ]
1. Free radical polymerization synthesis intermediate
Adding 1mol of chloroform into a 500ml three-neck flask, then respectively adding 0.1mol of maleic anhydride, 0.12mol of dodecene and 0.03mol of lauroyl peroxide, mechanically stirring to completely dissolve the materials, reacting for 2 hours at 100 ℃, then cooling to 70 ℃, slowly adding 0.12mol of styrene, and continuing to react for 5 hours to obtain an intermediate product.
2. Chemical modification synthesis viscosity reducer
And (3) continuously adding 0.06mol of aminonaphthalene sulfonic acid and 0.02mol of potassium hydroxide into the three-neck flask, stirring and dissolving, and continuously reacting for 5 hours at 100 ℃ to obtain the viscosity reducer.
3. Purifying and drying
Reducing the temperature of the viscosity reducer in the step 2 to 30 ℃, then adding the viscosity reducer into ethanol, then adding the precipitated solid into 30 ℃ water for cleaning, repeating the cleaning for multiple times, and finally performing suction filtration and drying to obtain the viscosity reducer with the following raw materials:
[ maleic anhydride ]][ dodecene ]]1.2[ styrene ]]1.2[ lauroyl peroxide ]]0.3[ Aminonaphthalenesulfonic acid ]]0.6[ Potassium hydroxide]0.2[ chloroform ]]10.0
4. Viscosity reducer evaluation
And (5) inspecting the viscosity reduction rate and yield stress reduction rate of the coal water slurry. The viscosity reducer raw material composition and the evaluation results are shown in FIG. 1 for convenience of comparison.
[ example 3 ]
1. Free radical polymerization synthesis intermediate
Adding 1mol of chloroform into a 500ml three-neck flask, then respectively adding 0.1mol of maleic anhydride, 0.12mol of dodecene and 0.03mol of lauroyl peroxide, mechanically stirring to completely dissolve the materials, reacting for 2 hours at 100 ℃, then cooling to 70 ℃, slowly adding 0.12mol of styrene, and continuing to react for 5 hours to obtain an intermediate product.
2. Chemical modification synthesis viscosity reducer
And (3) continuously adding 0.06mol of aminohydroxynaphthalene sulfonic acid and 0.02mol of potassium hydroxide into the three-neck flask, stirring and dissolving, and continuously reacting for 5 hours at 100 ℃ to obtain the viscosity reducer.
3. Purifying and drying
Reducing the temperature of the viscosity reducer in the step 2 to 30 ℃, then adding the viscosity reducer into ethanol, then adding the precipitated solid into 30 ℃ water for cleaning, repeating the cleaning for multiple times, and finally performing suction filtration and drying to obtain the viscosity reducer with the following raw materials:
[ maleic anhydride ]][ dodecene ]]1.2[ styrene ]]1.2[ lauroyl peroxide ]]0.3[ aminohydroxynaphthalenesulfonic acid]0.6[ Potassium hydroxide]0.2[ chloroform ]]10.0
4. Viscosity reducer evaluation
And (5) inspecting the viscosity reduction rate and yield stress reduction rate of the coal water slurry. The viscosity reducer raw material composition and the evaluation results are shown in FIG. 1 for convenience of comparison.
[ example 4 ]
1. Free radical polymerization synthesis intermediate
Adding 1mol of chloroform into a 500ml three-neck flask, then respectively adding 0.1mol of maleic anhydride, 0.12mol of dodecene and 0.03mol of lauroyl peroxide, mechanically stirring to completely dissolve the materials, reacting for 2 hours at 100 ℃, then cooling to 70 ℃, slowly adding 0.12mol of styrene, and continuing to react for 5 hours to obtain an intermediate product.
2. Chemical modification synthesis viscosity reducer
And continuously adding 0.06mol of dimethylamino naphthalene sulfonic acid and 0.02mol of potassium hydroxide into the three-neck flask, stirring for dissolving, and continuously reacting for 5 hours at 100 ℃ to obtain the viscosity reducer.
3. Purifying and drying
Reducing the temperature of the viscosity reducer in the step 2 to 30 ℃, then adding the viscosity reducer into ethanol, then adding the precipitated solid into 30 ℃ water for cleaning, repeating the cleaning for multiple times, and finally performing suction filtration and drying to obtain the viscosity reducer with the following raw materials:
[ maleic anhydride ]][ dodecene ]]1.2[ styrene ]]1.2[ lauroyl peroxide ]]0.3[ Dimethylaminonaphthalenesulfonic acid ]]0.6[ Potassium hydroxide]0.2[ chloroform ]]10.0
4. Viscosity reducer evaluation
And (5) inspecting the viscosity reduction rate and yield stress reduction rate of the coal water slurry. The viscosity reducer raw material composition and the evaluation results are shown in FIG. 1 for convenience of comparison.
[ example 5 ]
1. Free radical polymerization synthesis intermediate
Adding 1mol of chloroform into a 500ml three-neck flask, then respectively adding 0.1mol of maleic anhydride, 0.12mol of dodecene and 0.03mol of lauroyl peroxide, mechanically stirring to completely dissolve the materials, reacting for 2 hours at 100 ℃, then cooling to 70 ℃, slowly adding 0.12mol of styrene, and continuing to react for 5 hours to obtain an intermediate product.
2. Chemical modification synthesis viscosity reducer
And (2) continuously adding 0.03mol of polytetramethylene glycol and 0.01mol of p-toluenesulfonic acid into the three-neck flask, stirring for dissolving, reacting at 100 ℃ for 3 hours, then adding 0.03mol of aminonaphthalene sulfonic acid and 0.01mol of potassium hydroxide, and reacting at 100 ℃ for 3 hours to obtain the viscosity reducer.
3. Purifying and drying
Reducing the temperature of the viscosity reducer in the step 2 to 30 ℃, then adding the viscosity reducer into ethanol, then adding the precipitated solid into 30 ℃ water for cleaning, repeating the cleaning for multiple times, and finally performing suction filtration and drying to obtain the viscosity reducer with the following raw materials:
[ maleic anhydride ]][ dodecene ]]1.2[ styrene ]]1.2[ lauroyl peroxide ]]0.3[ polytetramethylene glycol ]]0.3[ Aminonaphthalenesulfonic acid ]]0.3[ p-methylbenzenesulfonic acid]0.1[ Potassium hydroxide]0.1[ chloroform ]]10.0
4. Viscosity reducer evaluation
And (5) inspecting the viscosity reduction rate and yield stress reduction rate of the coal water slurry. The viscosity reducer raw material composition and the evaluation results are shown in FIG. 1 for convenience of comparison.
[ example 6 ]
1. Free radical polymerization synthesis intermediate
Adding 1mol of chloroform into a 500ml three-neck flask, then respectively adding 0.1mol of maleic anhydride, 0.12mol of dodecene and 0.03mol of lauroyl peroxide, mechanically stirring to completely dissolve the materials, reacting for 2 hours at 100 ℃, then cooling to 70 ℃, slowly adding 0.12mol of styrene, and continuing to react for 5 hours to obtain an intermediate product.
2. Chemical modification synthesis viscosity reducer
And (2) continuously adding 0.03mol of polytetramethylene glycol and 0.01mol of p-toluenesulfonic acid into the three-neck flask, stirring for dissolving, reacting at 100 ℃ for 3 hours, then adding 0.03mol of aminohydroxynaphthalene sulfonic acid and 0.01mol of potassium hydroxide, and reacting at 100 ℃ for 3 hours to obtain the viscosity reducer.
3. Purifying and drying
Reducing the temperature of the viscosity reducer in the step 2 to 30 ℃, then adding the viscosity reducer into ethanol, then adding the precipitated solid into 30 ℃ water for cleaning, repeating the cleaning for multiple times, and finally performing suction filtration and drying to obtain the viscosity reducer with the following raw materials:
[ maleic anhydride ]][ dodecene ]]1.2[ styrene ]]1.2[ lauroyl peroxide ]]0.3[ polytetramethylene glycol ]]0.3[ aminohydroxynaphthalenesulfonic acid]0.3[ p-methylbenzenesulfonic acid]0.1[ Potassium hydroxide]0.1[ chloroform ]]10.0
4. Viscosity reducer evaluation
And (5) inspecting the viscosity reduction rate and yield stress reduction rate of the coal water slurry. The viscosity reducer raw material composition and the evaluation results are shown in FIG. 1 for convenience of comparison.
[ example 7 ]
1. Free radical polymerization synthesis intermediate
Adding 1mol of chloroform into a 500ml three-neck flask, then respectively adding 0.1mol of maleic anhydride, 0.12mol of dodecene and 0.03mol of lauroyl peroxide, mechanically stirring to completely dissolve the materials, reacting for 2 hours at 100 ℃, then cooling to 70 ℃, slowly adding 0.12mol of styrene, and continuing to react for 5 hours to obtain an intermediate product.
2. Chemical modification synthesis viscosity reducer
And (2) continuously adding 0.03mol of polytetramethylene glycol and 0.01mol of p-toluenesulfonic acid into the three-neck flask, stirring for dissolving, reacting at 100 ℃ for 3 hours, then adding 0.03mol of dimethylamino naphthalene sulfonic acid and 0.01mol of potassium hydroxide, and reacting at 100 ℃ for 3 hours to obtain the viscosity reducer.
3. Purifying and drying
Reducing the temperature of the viscosity reducer in the step 2 to 30 ℃, then adding the viscosity reducer into ethanol, then adding the precipitated solid into 30 ℃ water for cleaning, repeating the cleaning for multiple times, and finally performing suction filtration and drying to obtain the viscosity reducer with the following raw materials:
[ maleic anhydride ]][ dodecene ]]1.2[ styrene ]]1.2[ lauroyl peroxide ]]0.3[ polytetramethylene glycol ]]0.3[ Dimethylaminonaphthalenesulfonic acid ]]0.3[ p-methylbenzenesulfonic acid]0.1[ Potassium hydroxide]0.1[ chloroform ]]10.0
4. Viscosity reducer evaluation
And (5) inspecting the viscosity reduction rate and yield stress reduction rate of the coal water slurry. The viscosity reducer raw material composition and the evaluation results are shown in FIG. 1 for convenience of comparison.
[ example 8 ]
1. Free radical polymerization synthesis intermediate
Adding 1mol of chloroform into a 500ml three-neck flask, then respectively adding 0.1mol of maleic anhydride, 0.12mol of dodecene and 0.03mol of lauroyl peroxide, mechanically stirring to completely dissolve the materials, reacting for 2 hours at 100 ℃, then cooling to 70 ℃, slowly adding 0.12mol of styrene, and continuing to react for 5 hours to obtain an intermediate product.
2. Chemical modification synthesis viscosity reducer
And (2) continuously adding 0.03mol of polytetramethylene glycol and 0.01mol of p-methylbenzenesulfonic acid into the three-neck flask, stirring and dissolving, reacting at 100 ℃ for 3 hours, then adding 0.015mol of aminonaphthalene sulfonic acid, 0.015mol of aminohydroxynaphthalene sulfonic acid and 0.01mol of potassium hydroxide, and reacting at 100 ℃ for 3 hours to obtain the viscosity reducer.
3. Purifying and drying
Reducing the temperature of the viscosity reducer in the step 2 to 30 ℃, then adding the viscosity reducer into ethanol, then adding the precipitated solid into 30 ℃ water for cleaning, repeating the cleaning for multiple times, and finally performing suction filtration and drying to obtain the viscosity reducer with the following raw materials:
[ maleic anhydride ]][ dodecene ]]1.2[ styrene ]]1.2[ lauroyl peroxide ]]0.3[ polytetramethylene glycol ]]0.3[ Aminonaphthalenesulfonic acid ]]0.15[ aminohydroxynaphthalenesulfonic acid]0.15[ p-methylbenzenesulfonic acid]0.1[ Potassium hydroxide]0.1[ chloroform ]]10.0
4. Viscosity reducer evaluation
And (5) inspecting the viscosity reduction rate and yield stress reduction rate of the coal water slurry. The viscosity reducer raw material composition and the evaluation results are shown in FIG. 1 for convenience of comparison.
[ example 9 ]
1. Free radical polymerization synthesis intermediate
Adding 1mol of chloroform into a 500ml three-neck flask, then respectively adding 0.1mol of maleic anhydride, 0.12mol of dodecene and 0.03mol of lauroyl peroxide, mechanically stirring to completely dissolve the materials, reacting for 2 hours at 100 ℃, then cooling to 70 ℃, slowly adding 0.12mol of styrene, and continuing to react for 5 hours to obtain an intermediate product.
2. Chemical modification synthesis viscosity reducer
And (2) continuously adding 0.03mol of polytetramethylene glycol and 0.01mol of p-toluenesulfonic acid into the three-neck flask, stirring and dissolving, reacting at 100 ℃ for 3 hours, then adding 0.015mol of aminonaphthalene sulfonic acid, 0.015mol of dimethylaminonaphthalene sulfonic acid and 0.01mol of potassium hydroxide, and reacting at 100 ℃ for 3 hours to obtain the viscosity reducer.
3. Purifying and drying
Reducing the temperature of the viscosity reducer in the step 2 to 30 ℃, then adding the viscosity reducer into ethanol, then adding the precipitated solid into 30 ℃ water for cleaning, repeating the cleaning for multiple times, and finally performing suction filtration and drying to obtain the viscosity reducer with the following raw materials:
[ maleic anhydride ]][ dodecene ]]1.2[ styrene ]]1.2[ lauroyl peroxide ]]0.3[ polytetramethylene glycol ]]0.3[ Aminonaphthalenesulfonic acid ]]0.15[ Dimethylaminonaphthalenesulfonic acid ]]0.15[ p-methylbenzenesulfonic acid]0.1[ Potassium hydroxide]0.1[ chloroform ]]10.0
4. Viscosity reducer evaluation
And (5) inspecting the viscosity reduction rate and yield stress reduction rate of the coal water slurry. The viscosity reducer raw material composition and the evaluation results are shown in FIG. 1 for convenience of comparison.
[ example 10 ]
1. Free radical polymerization synthesis intermediate
Adding 1mol of chloroform into a 500ml three-neck flask, then respectively adding 0.1mol of maleic anhydride, 0.12mol of dodecene and 0.03mol of lauroyl peroxide, mechanically stirring to completely dissolve the materials, reacting for 2 hours at 100 ℃, then cooling to 70 ℃, slowly adding 0.12mol of styrene, and continuing to react for 5 hours to obtain an intermediate product.
2. Chemical modification synthesis viscosity reducer
And (2) continuously adding 0.03mol of polytetramethylene glycol and 0.01mol of p-toluenesulfonic acid into the three-neck flask, stirring and dissolving, reacting at 100 ℃ for 3 hours, then adding 0.015mol of aminohydroxynaphthalene sulfonic acid, 0.015mol of dimethylaminonaphthalene sulfonic acid and 0.01mol of potassium hydroxide, and reacting at 100 ℃ for 3 hours to obtain the viscosity reducer.
3. Purifying and drying
Reducing the temperature of the viscosity reducer in the step 2 to 30 ℃, then adding the viscosity reducer into ethanol, then adding the precipitated solid into 30 ℃ water for cleaning, repeating the cleaning for multiple times, and finally performing suction filtration and drying to obtain the viscosity reducer with the following raw materials:
[ maleic anhydride ]][ dodecene ]]1.2[ styrene ]]1.2[ lauroyl peroxide ]]0.3[ polytetramethylene glycol ]]0.3[ aminohydroxynaphthalenesulfonic acid]0.15[ Dimethylaminonaphthalenesulfonic acid ]]0.15[ p-methylbenzenesulfonic acid]0.1[ Potassium hydroxide]0.1[ chloroform ]]10.0
4. Viscosity reducer evaluation
And (5) inspecting the viscosity reduction rate and yield stress reduction rate of the coal water slurry. The viscosity reducer raw material composition and the evaluation results are shown in FIG. 1 for convenience of comparison.
[ example 11 ]
1. Free radical polymerization synthesis intermediate
Adding 1mol of chloroform into a 500ml three-neck flask, then respectively adding 0.1mol of maleic anhydride, 0.12mol of dodecene and 0.03mol of lauroyl peroxide, mechanically stirring to completely dissolve the materials, reacting for 2 hours at 100 ℃, then cooling to 70 ℃, slowly adding 0.12mol of styrene, and continuing to react for 5 hours to obtain an intermediate product.
2. Chemical modification synthesis viscosity reducer
And (2) continuously adding 0.03mol of polytetramethylene glycol and 0.01mol of p-methylbenzenesulfonic acid into the three-neck flask, stirring and dissolving, reacting for 3 hours at 100 ℃, then adding 0.01mol of aminonaphthalene sulfonic acid, 0.01mol of aminohydroxynaphthalene sulfonic acid, 0.01mol of dimethylamino naphthalene sulfonic acid and 0.01mol of potassium hydroxide, and reacting for 3 hours at 100 ℃ to obtain the viscosity reducer.
3. Purifying and drying
Reducing the temperature of the viscosity reducer in the step 2 to 30 ℃, then adding the viscosity reducer into ethanol, then adding the precipitated solid into 30 ℃ water for cleaning, repeating the cleaning for multiple times, and finally performing suction filtration and drying to obtain the viscosity reducer with the following raw materials:
[ maleic anhydride ]][ dodecene ]]1.2[ styrene ]]1.2[ lauroyl peroxide ]]0.3[ polytetramethylene glycol ]]0.3[ Aminonaphthalenesulfonic acid ]]0.1[ aminohydroxynaphthalenesulfonic acid]0.1[ Dimethylaminonaphthalenesulfonic acid ]]0.1[ p-methylbenzenesulfonic acid]0.1[ Potassium hydroxide]0.1[ chloroform ]]10.0
4. Viscosity reducer evaluation
And (5) inspecting the viscosity reduction rate and yield stress reduction rate of the coal water slurry. The viscosity reducer raw material composition and the evaluation results are shown in FIG. 1 for convenience of comparison.
Claims (8)
1. The method for reducing viscosity of coal water slurry comprises the steps of obviously reducing apparent viscosity and yield stress of the coal water slurry and greatly improving flow property in the presence of a viscosity reducer, wherein the preparation of the viscosity reducer comprises the steps of synthesizing an intermediate product by free radical polymerization, chemically modifying and synthesizing the viscosity reducer and purifying and drying, and the general formula of the raw material of the viscosity reducer is M αxSyAaBbCcDdWherein M is maleic anhydride, α is α -olefin selected from dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, S is styrene, A is an initiator selected from cyclohexanone peroxide, dibenzoyl peroxide, dimethylformamide, lauroyl peroxide, benzoyl tert-butyl peroxide, ditert-butyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, diisopropyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azodiisobutyrate, diisobutyl chloride, diisobutyl imidazoline hydrochloride, azobiscyanovaleric acid, and diisopropyl azoimidazoline, B is a modifier selected from ethanol, propanol, butanol, isobutanol, isoamyl alcohol, active amyl alcohol, phenethyl alcohol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, pentanediol, glycerol, undecyl alcohol to behenyl alcohol, undecyl amine, polyoxyethylene etherIn the ratio, b takes a value of 0.2-5.0; c is the molar ratio of the catalyst to the maleic anhydride, and the value of c is 0.01-2.0; d is the molar ratio of the solvent to the maleic anhydride, and the value of d is 5.0-20.0.
2. The method for reducing the viscosity of water-coal-slurry according to claim 1, wherein the viscosity and yield stress changes are measured by a rheometer after the water-coal-slurry viscosity reducer is added.
3. The method for reducing the viscosity of the coal water slurry according to claim 1, wherein the mass fraction of the coal water slurry viscosity reducer is 0.01-3%.
4. The method for reducing the viscosity of the coal water slurry according to claim 1, wherein the test temperature of the viscosity and the yield stress is-20 to 200 ℃.
5. The method for reducing the viscosity of the coal water slurry according to claim 1, wherein the test time of the viscosity and the yield stress is preferably 1min to 50 min.
6. The method for reducing the viscosity of the water-coal-slurry according to claim 1, wherein the molecular weight of the water-coal-slurry viscosity reducer is 1000-100000, and the degree of esterification is 0.1-5.0.
7. The method for reducing the viscosity of the coal water slurry according to claim 1, wherein the temperature of the free radical polymerization reaction is 30-180 ℃ and the reaction time is 0.5-12 hours.
8. The method for reducing the viscosity of the coal water slurry according to claim 1, wherein the chemical modification reaction temperature is 30-180 ℃ and the reaction time is 0.5-12 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60250096A (en) * | 1984-05-28 | 1985-12-10 | Kao Corp | Additive for coal-water slurry |
| CN86106954A (en) * | 1985-11-02 | 1987-04-29 | 希尔斯股份公司 | Reduce the method for viscosity in aqueous coal slurries with partial esters of polycarboxylic acids |
| CA1304224C (en) * | 1986-02-06 | 1992-06-30 | Anthony E. Gross | Coal water slurry viscosity reduction using sulphonate containing water-soluble terpolymers |
| CN104893770A (en) * | 2014-08-05 | 2015-09-09 | 浙江煤科清洁能源有限公司 | Process for preparing slurry by mixing Shenhua coal and Pingyi coal |
-
2018
- 2018-04-04 CN CN201810299473.4A patent/CN108315068B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60250096A (en) * | 1984-05-28 | 1985-12-10 | Kao Corp | Additive for coal-water slurry |
| CN86106954A (en) * | 1985-11-02 | 1987-04-29 | 希尔斯股份公司 | Reduce the method for viscosity in aqueous coal slurries with partial esters of polycarboxylic acids |
| CA1304224C (en) * | 1986-02-06 | 1992-06-30 | Anthony E. Gross | Coal water slurry viscosity reduction using sulphonate containing water-soluble terpolymers |
| CN104893770A (en) * | 2014-08-05 | 2015-09-09 | 浙江煤科清洁能源有限公司 | Process for preparing slurry by mixing Shenhua coal and Pingyi coal |
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