CN108467760A - A kind of tannic acid graft copolymer coal water slurry dispersant and preparation method thereof - Google Patents
A kind of tannic acid graft copolymer coal water slurry dispersant and preparation method thereof Download PDFInfo
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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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- 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
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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- C08F228/00—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 a bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/02—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 a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
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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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
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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
- 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
- C10L1/2462—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds
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Abstract
Whole tannic acid, are dissolved in three-necked flask by a kind of tannic acid graft copolymer coal water slurry dispersant and preparation method thereof with appropriate amount of deionized water, form solution, then the oxidant in initiator is added, in certain temperature range, heating stirring makes it fully dissolve, and reacts certain time；A certain amount of R is added in above-mentioned three-necked flask1Corresponding monomer and suitable deionization water as solvent, and reducing agent is added thereto, then R is added dropwise simultaneously in heated material to certain temperature2Mix products after a certain period of time, are cooled to room temperature by corresponding monomer and residual oxidizing agent, reaction；At room temperature, the NaOH aqueous solutions of mix products after cooling in step 2 are adjusted into pH, the tannic acid graft copolymer coal water slurry dispersant synthesized, the dispersant can be substantially reduced slurrying viscosity, improve slurry stability, invention synthesis material is cheap and easy to get simultaneously, environmentally safe after burning, has good development prospect and very high cost performance.
Description
Technical field
The present invention relates to slurries additive agent technical fields, and in particular to a kind of tannic acid graft copolymer effective dispersant
Agent and preparation method thereof.
Background technology
Water-coal-slurry is that one kind being made one by 60%-70% coals, 25%-40% water and a small amount of additive by Physical Processing
In kind novel base generation, expects spontaneously, is a kind of Novel clean-fuel that can replace heavy oil and coal.Water-coal-slurry is in storage, transportational process
Also free from environmental pollution, it is nonflammable, non-explosive during storage, fortune, securely and reliably.But since coal surface is mainly aromatic ring structure
The compound of property has certain hydrophobicity, and agglomeration easily occurs in water, thus system has thermodynamic instability
Property, in order to obtain ideal performance, dispersant plays very important effect.Dispersant has the property of surfactant,
Hydrophobic side is combined with the hydrophobic part of coal grain, and water-wet side stretches in water, and such coal grain just becomes hydrophilic from hydrophobic.Water-coal-slurry
Dispersant can be such that coal particle is uniformly scattered in coal aqueous systems, reduce the viscosity of water-coal-slurry system, be that water-coal-slurry is stablized
It is crucial.
Coal water slurry dispersing agent includes ionic and nonionic.Ionic includes anionic, cationic, amphoteric,
Commonly used is sulfonate, such as naphthalene sulfonate, polycarboxylic-acid, lignosulfonates and humic acid system.Nonionic point
Powder is divided into following two categories polyoxyethylene series, such as：D-sorbite polyoxyethylene ether, ethoxylated dodecyl alcohol etc..These points
That there are dispersion effects is unstable for powder, bin stability is poor, expensive raw material price, cost of manufacture are high and uses process production pair
Environment pollutes, and is unfavorable for energy-saving and emission-reduction.
Invention content
In order to solve the above technical problems, the purpose of the present invention is to propose to a kind of tannic acid graft copolymer effective dispersants
The dispersion effect of agent and preparation method thereof, the slurries additive agent is stablized, and slurrying viscosity can be substantially reduced, and improves slurry and stablizes
Property, while this experiment synthesis material is cheap and easy to get, and it is environmentally safe after burning, there is good development prospect and very high property
Valence ratio.
To achieve the above objectives, the present invention adopts the following technical scheme that：
The structure of a kind of tannic acid graft copolymer coal water slurry dispersant, the tannic acid graft copolymer is：
Wherein R1For Or any one in-H；
R2For Or any one in-H.
The reaction mass of the dispersant according to mass fraction meter tannic acid 40%-60%, mix monomer 30%-50%,
Initiator (redox type initiator) 1%-10% is matched, and mix monomer is by R1And R2Corresponding monomer composition, initiator
(including Oxidizing and Reducing Agents) is hydrogen peroxide-ferrous sulfate, horseradish peroxidase HRP-H2O2, potassium permanganate-lemon
One kind in acid, ammonium persulfate-sodium bisulfite.
A kind of preparation method of tannic acid graft copolymer coal water slurry dispersant, includes the following steps：
Step 1：
Aoxidize tannic acid：Whole tannic acid are dissolved in three-necked flask with appropriate amount of deionized water, form mass fraction
Then the oxidant in initiator is added in the aqueous solution of 5%-20%, in certain temperature range, heating stirring keeps it fully molten
Solution reacts certain time；
Step 2：
Polymerisation：A certain amount of R is added in above-mentioned three-necked flask1Corresponding monomer and suitable deionized water are made molten
Agent, and reducing agent is added thereto, then R is added dropwise simultaneously in heated material to certain temperature2Corresponding monomer and residual oxidizing agent,
Mix products after a certain period of time, are cooled to room temperature by reaction；
Step 3：
Neutralization reaction：At room temperature, the NaOH aqueous solutions of mix products after cooling in step 2 are adjusted into pH, is synthesized
Tannic acid graft copolymer coal water slurry dispersant, discharge to obtain brown clarification lotion (MTA).
Tannic acid molecular weight is 500-3000Da in the step one.
Oxidant used is the 30%-50% of oxidant gross mass in the step one.
The reaction time is 20-30min in the step one；Oxidizing reaction temperature is at 70-90 DEG C.
Tannic acid and step 2 mix monomer R in the step one1And R2The molar ratio of quality summation is 1:10-1:40.
The quality of deionized water (solvent) is the 60%-80% of monomer gross mass in the step two.
The molar ratio of Oxidizing and Reducing Agents is 2 in the step two：1-4:1.
Mix monomer R in the step two1And R2Between molar ratio be 1:1-1:1.5.
Reaction temperature is 80-110 DEG C in the step two；Reaction time is 3-4h.
PH is adjusted in the step three between 6-9；NaOH mass concentrations are 10%-30%.
The R1Corresponding monomer is respectively acrylic acid, acrylamide, methacrylic acid and methyl methacrylate；R2
Corresponding monomer is respectively p styrene sulfonic acid, vinyl sulfonic acid, ethylene methacrylic sulfonic acid and 2- acrylamido -2- methyl-prop sulphurs
Acid.
The monomer is handled through recrystallization purifying.
Beneficial effects of the present invention：
Tannic acid graft copolymer coal water slurry dispersant of the present invention, not only easy to operate, raw material is cheap and easy to get, and
And obtained modified tannin acid dispersant can prepare the good water-coal-slurry of high concentration, low-viscosity, thixotropy, than commercially available dispersant
Correlated performance is far better, and its coal adaptability is good.
Specific implementation mode
Below in conjunction with specific embodiment, the step of the present invention is described in further detail.
Tannic acid source and physicochemical property
Tannic acid, also known as Chinese tannin, tannic acid, Chinese tannin acid.Tannic acid is that plant is primarily present in nature
A kind of polyphenol macromolecular compound in the micro-pipe tissue of leaf, seed and flower.Tannic acid is mainly derived from Chinese gall, pomegranate, smoke tree
In equal plants.In China, Chinese gall and pomegranate play huge effect to the supply of tannic acid.Chinese gall is by extraction, concentration
It can be made into industrial tannic acid afterwards, then medicinal or Reagent tannic acid can be made into after refined.Tannic acid is faint yellow amorphous
Powder or glossiness flakey or spongy solid.Without special odor, there are bitter taste, Bearberry Extract.It is exposed to air and day
Gradual blackening in light.It is dissolved in cold water, can ad infinitum be dissolved in the hot water；It can be dissolved in methanol, ethyl alcohol, acetoneand ethyl acetate, no
It is dissolved in benzene, ether, chloroform, petroleum ether and carbon disulfide.Tannin aqueous acid is weakly acidic, oxidation is easy, in alkaline solution
Faster, solution colour is deeper for middle oxidation.Ferric ion is met, solution is in black-and-blue, generates and sinks with gelatin, alkaloid effect
It forms sediment.Polynuclear complex is generated with Action of Metal Ions such as lead, aluminium, zinc, germanium, the insoluble salt with special color.Tannic acid
It is heated to be decomposed into pyrogallic acid and CO at 210~215 DEG C2。
Research contents and advantage：
More dispersant currently on the market is naphthalene system, the wooden sodium, polycarboxylic acids series.The above two are difficult to prepare highly concentrated
The water-coal-slurry spent and had good stability, and naphthalene system dispersant, because deriving from oil, production and application all generate larger pollution；It is poly-
Carboxylic acid series price and more expensive selectively strong to coal.For these problems, this experiment is naturally big to tannic acid cheap and easy to get
Molecule carry out graft copolymerization, obtained it is strong to coal adaptability, be made stability of coal slurry it is good and be suitable for large-scale production water
Coal-slurry dispersing agent.
Tannic acid is resourceful, cheap, in molecule more unique pyrogallol structure be easily oxidized for
O-quinone structure is the polyphenol macromolecular compound that can be dissolved in water.O-quinone structure is easily with water soluble alkene hydrocarbons in initiator
Effect is lower to occur graft copolymerization.With tannic acid and acrylic acid, acrylamide, methacrylic acid, methacrylate and right
Arbitrary two kinds of mix monomers of styrene sulfonic acid, vinyl sulfonic acid, ethylene methacrylic sulfonic acid, 2- acrylamide-2-methylpro panesulfonic acids
Grafting obtains modified tannin acid.Tannic acid graft copolymer coal water slurry dispersant prepared by the present invention increases its hydrophilicity,
After tannic acid graft copolymer coal water slurry dispersant is added, make coal grain surface have it is hydrophobic become water-wet side, increase it in water
Dispersion stabilization.Anionic group sulfonic group and carboxyl are introduced in the strand of tannic acid, are formed absorption anchor point, are carried simultaneously
For electrostatic repulsion, obtained tannic acid coal water slurry dispersing agent has the advantages that many uniquenesses, is suitable for compounding high concentration, low glutinous
Degree, high-stability coal water slurry, there is a good application effect.This operation is simple, and raw material is cheap and easy to get, and performance is better than commercially available
Dispersant.
Embodiment one：
5.00g tannic acid is dissolved in appropriate amount of deionized water, the aqueous solution that mass fraction is 7% is made in three-necked flask,
Then 0.16g K are added2S2O8, at a temperature of 80 DEG C, heating stirring makes it fully dissolve, and reacts 30min.Then at three mouthfuls
0.25g acrylic acid and 50g deionizations water as solvent are added in flask and 0.14g NaHSO are added3, heated material is to 85 DEG C, so
0.55g vinyl sulfonic acids and 0.24g K is added dropwise simultaneously afterwards2S2O8, rate of addition is controlled, the two is made to be dripped in two hours simultaneously,
After isothermal reaction 4h, mix products are cooled to room temperature.It is 8 that product is adjusted pH with 30% NaOH aqueous solutions, obtains tannin
Sour graft copolymer coal water slurry dispersant.
Embodiment two：
5.00g tannic acid is dissolved in appropriate amount of deionized water be made in three-necked flask mass fraction be 10% it is water-soluble
Then 0.16g K are added in liquid2S2O8, at a temperature of 80 DEG C, heating stirring makes it fully dissolve, and reacts 30min.Then three
0.25g acrylic acid and 50g deionizations water as solvent are added in mouth flask and 0.14g NaHSO are added3, heated material to 85 DEG C,
Then 0.93g is added dropwise to vinyl benzenesulfonic acid and 0.24gK simultaneously2S2O8, rate of addition is controlled, the two is made to be dripped in two hours simultaneously
It adds, after isothermal reaction 4h, mix products is cooled to room temperature.It is 8 that product is adjusted pH with 30% NaOH aqueous solutions, is obtained
Tannic acid graft copolymer coal water slurry dispersant.
Embodiment three：
5.00g tannic acid is dissolved in appropriate amount of deionized water be made in three-necked flask mass fraction be 10% it is water-soluble
Then 0.16g K are added in liquid2S2O8, at a temperature of 80 DEG C, heating stirring makes it fully dissolve, and reacts 30min.It is burnt at three mouthfuls
0.25g acrylamides and 50g deionizations water as solvent are added in bottle and 0.14g NaHSO are added3, heated material is to 85 DEG C, so
0.547g vinyl sulfonic acids and 0.24g K is added dropwise simultaneously afterwards2S2O8, rate of addition is controlled, the two is made to be added dropwise in two hours simultaneously
It is complete, after isothermal reaction 4h, mix products are cooled to room temperature.It is 7 that product is adjusted pH with 30% NaOH aqueous solutions, obtains list
Peaceful acid graft copolymer coal water slurry dispersant.
Example IV：
5.00g tannic acid is dissolved in appropriate distilled water, the aqueous solution that mass fraction is 10% is made in three-necked flask,
Then 0.16g K are added2S2O8, at a temperature of 80 DEG C, heating stirring makes it fully dissolve, and reacts 30min.In three-necked flask
Simultaneously 0.14g NaHSO are added in middle addition 0.25g acrylamides and 50g deionizations water as solvent3, heated material is to 80 DEG C, then
0.547g vinyl sulfonic acids and 0.24g K is added dropwise simultaneously2S2O8, rate of addition is controlled, the two is made to be dripped in two hours simultaneously,
After isothermal reaction 4h, mix products are cooled to room temperature.It is 9 that product is adjusted pH with 30% NaOH aqueous solutions, obtains tannin
Sour graft copolymer coal water slurry dispersant.
Embodiment five：
5.00g tannic acid is dissolved in appropriate distilled water, the aqueous solution that mass fraction is 7% is made in three-necked flask, so
0.16g FeSO are added afterwards4, at a temperature of 80 DEG C, heating stirring makes it fully dissolve, and reacts 30min.In three-necked flask
0.25g acrylic acid and 50g deionizations water as solvent is added and 0.14g H are added2O2, then heated material is added dropwise simultaneously to 85 DEG C
0.93g is to vinyl benzenesulfonic acid and 0.24g FeSO4, rate of addition is controlled, so that the two is dripped in two hours simultaneously, constant temperature is anti-
After answering 4h, mix products are cooled to room temperature.It is 6 that product is adjusted pH with 30% NaOH aqueous solutions, obtains tannic acid grafting
Copolymer coal water slurry dispersing agent.
Embodiment six：
5.00g tannic acid is dissolved in appropriate distilled water, the aqueous solution that mass fraction is 7% is made in three-necked flask, so
0.16g HRP (horseradish peroxidase) are added afterwards, at a temperature of 80 DEG C, heating stirring makes it fully dissolve, reaction
30min.0.25g acrylic acid and 50g deionizations water as solvent are added in three-necked flask and 0.14g H are added2O2, heated material
To 85 DEG C, 0.93g is then added dropwise simultaneously to vinyl benzenesulfonic acid and 0.24g HRP, controls rate of addition, keeps the two small two simultaneously
When it is interior drip, after isothermal reaction 4h, mix products are cooled to room temperature.Product is adjusted pH with 30% NaOH aqueous solutions is
8, obtain tannic acid graft copolymer coal water slurry dispersant.
Embodiment seven：
5.00g tannic acid is dissolved in appropriate distilled water, the water that mass fraction is 7% is made in the three-necked flask of 250mL
Then 0.16g potassium permanganate is added in solution, at a temperature of 80 DEG C, heating stirring makes it fully dissolve, and reacts 30min.Three
0.25g acrylic acid and 50g deionizations water as solvent are added in mouth flask and 0.14g citric acids are added, heated material is to 85 DEG C, so
0.93g is added dropwise simultaneously afterwards to vinyl benzenesulfonic acid and 0.24g potassium permanganate, controls rate of addition, makes the two simultaneously in two hours
It drips, after isothermal reaction 4h, it is 8 that mix products, which are cooled to room temperature product is adjusted pH with 30% NaOH aqueous solutions, is obtained
To tannic acid graft copolymer coal water slurry dispersant.
1 exemplary application performance of table
It is research object to select refined long coal, according to national standard GB/T18856.4-2008 water-coal-slurry test methods, by being crushed,
Water-coal-slurry (mass fraction 63.5%) 300g of same concentrations, the grain-size grade of coal is made in ore grinding, screening and grading after stirring evenly
Match：D50=22 μm；D90=110 μm；<75 μm=80%；<5 μm=20%；Average grain diameter is 45 μm.Tannic acid graft copolymerization
Object coal water slurry dispersing agent (solid content is converted into quality percentage 30% to calculate) additive amount is account for dry coal quality 0.30%, tannin
Sour graft copolymer coal water slurry dispersant is as shown in table 1 to the pulpability test result of refined long coal, and syneresis rate is volume basis
Number, as can be seen from Table 1, tannic acid graft copolymer coal water slurry dispersant of the present invention was in 7 days, 14 days dispersion effects
Stablize, and effect is better than naphthalene system dispersant.
Claims (10)
1. a kind of tannic acid graft copolymer coal water slurry dispersant, which is characterized in that the structure of the tannic acid graft copolymer
For：
Wherein R1For Or any one in-H；
R2For Or any one in-H.
2. a kind of tannic acid graft copolymer coal water slurry dispersant according to claim 1, which is characterized in that the dispersion
The reaction mass of agent according to mass fraction meter tannic acid 40%-60%, mix monomer 30%-50%, initiator 1%-10% into
Row proportioning, mix monomer is by R1And R2Corresponding monomer composition, initiator are hydrogen peroxide-ferrous sulfate, horseradish peroxidase
HRP-H2O2, potassium permanganate-citric acid, one kind in ammonium persulfate-sodium bisulfite, the initiator include oxidant and
Reducing agent.
3. the preparation method based on tannic acid graft copolymer coal water slurry dispersant described in claim 1, which is characterized in that packet
Include following steps：
Step 1：
Aoxidize tannic acid：Whole tannic acid are dissolved in three-necked flask with appropriate amount of deionized water, form mass fraction 5%-
Then the oxidant in initiator is added in 20% aqueous solution, in certain temperature range, heating stirring makes it fully dissolve,
React certain time；
Step 2：
Polymerisation：A certain amount of R is added in above-mentioned three-necked flask1Corresponding monomer and suitable deionization water as solvent, and to
Reducing agent is wherein added, then R is added dropwise simultaneously in heated material to certain temperature2Corresponding monomer and residual oxidizing agent, reaction are certain
After time, mix products are cooled to room temperature；
Step 3：
Neutralization reaction：At room temperature, the NaOH aqueous solutions of mix products after cooling in step 2 are adjusted into pH, the list synthesized
Peaceful acid graft copolymer coal water slurry dispersant, discharge to obtain brown clarification lotion.
4. the preparation method of tannic acid graft copolymer coal water slurry dispersant according to claim 3, which is characterized in that institute
Tannic acid molecular weight is 500-3000Da in the step of stating one.
5. the preparation method of tannic acid graft copolymer coal water slurry dispersant according to claim 3, which is characterized in that institute
Oxidant used is the 30%-50% of oxidant gross mass in the step of stating one；
The reaction time is 20-30min in the step one；Oxidizing reaction temperature is at 70-90 DEG C；
Tannic acid and step 2 mix monomer R in the step one1And R2The molar ratio of quality summation is 1:10-1:40.
6. the preparation method of tannic acid graft copolymer coal water slurry dispersant according to claim 3, which is characterized in that institute
The quality of deionized water is the 60%-80% of monomer gross mass in the step of stating two；
The molar ratio of Oxidizing and Reducing Agents is 2 in the step two:1-4:1；
Mix monomer R in the step two1And R2Between molar ratio be 1:1-1:1.5；
Reaction temperature is 80-110 DEG C in the step two；Reaction time is 3-4h.
7. the preparation method of tannic acid graft copolymer coal water slurry dispersant according to claim 3, which is characterized in that institute
PH is adjusted in the step of stating three between 6-9；NaOH mass concentrations are 10%-30%.
8. the preparation method of tannic acid graft copolymer coal water slurry dispersant according to claim 3, which is characterized in that institute
The R stated1Corresponding monomer is respectively acrylic acid, acrylamide, methacrylic acid and methyl methacrylate；R2Corresponding monomer
Respectively p styrene sulfonic acid, vinyl sulfonic acid, ethylene methacrylic sulfonic acid and 2- acrylamide-2-methylpro panesulfonic acids.
9. the preparation method of tannic acid graft copolymer coal water slurry dispersant according to claim 3, which is characterized in that institute
The monomer stated is handled through recrystallization purifying.
10. the preparation method of tannic acid graft copolymer coal water slurry dispersant according to claim 3, which is characterized in that
The reaction mass is according to mass fraction meter tannic acid 40%-60%, mix monomer 30%-50%, initiator 1%-10%
It is matched, mix monomer is respectively R1And R2Corresponding monomer, initiator are hydrogen peroxide-ferrous sulfate, horseradish peroxidase
HRP-H2O2, potassium permanganate-citric acid, one kind in ammonium persulfate-sodium bisulfite, the initiator include oxidant and
Reducing agent.
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| CN109749008A (en) * | 2018-12-28 | 2019-05-14 | 常州安达环保科技有限公司 | A kind of polymeric dispersant and preparation method thereof that tannic acid is modified |
| CN109762613A (en) * | 2019-02-26 | 2019-05-17 | 太原理工大学 | A kind of method that novel water-coal slurry dispersing agent is prepared by bio oil |
| CN109897135A (en) * | 2019-03-20 | 2019-06-18 | 山东理工大学 | Multifunctional polymer and its preparation method and application |
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| CN109629254A (en) * | 2018-12-28 | 2019-04-16 | 常州安达环保科技有限公司 | A kind of nano-dispersed dye paste and preparation method thereof suitable for terylene printing and dyeing |
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| CN109762613A (en) * | 2019-02-26 | 2019-05-17 | 太原理工大学 | A kind of method that novel water-coal slurry dispersing agent is prepared by bio oil |
| CN109897135A (en) * | 2019-03-20 | 2019-06-18 | 山东理工大学 | Multifunctional polymer and its preparation method and application |
| CN109897135B (en) * | 2019-03-20 | 2021-09-28 | 山东理工大学 | Multifunctional polymer and preparation method and application thereof |
| CN109970910A (en) * | 2019-03-28 | 2019-07-05 | 湖北大学 | A kind of ter-polymers coal water slurry dispersing agent and the application in water-coal-slurry preparation |
| CN109970910B (en) * | 2019-03-28 | 2021-08-27 | 湖北大学 | Terpolymer coal water slurry dispersing agent and application thereof in coal water slurry preparation |
| CN111019060A (en) * | 2019-12-12 | 2020-04-17 | 贵州师范学院 | Preparation method of tannic acid base star-shaped polycarboxylate superplasticizer |
| CN111320728A (en) * | 2020-03-20 | 2020-06-23 | 陕西科技大学 | Amphoteric tannin-based coal tar pitch water slurry dispersing agent and preparation method thereof |
| CN111320728B (en) * | 2020-03-20 | 2022-06-21 | 陕西科技大学 | Amphoteric tannin-based coal tar pitch water slurry dispersing agent and preparation method thereof |
| CN112842983A (en) * | 2021-03-11 | 2021-05-28 | 福州东艺善秀商业有限公司 | Herbal emulsion for sensitive muscle repair and preparation method thereof |
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