CN115417616B - Grinding aid for vertical mill cement and preparation method thereof - Google Patents
Grinding aid for vertical mill cement and preparation method thereof Download PDFInfo
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- CN115417616B CN115417616B CN202211221608.8A CN202211221608A CN115417616B CN 115417616 B CN115417616 B CN 115417616B CN 202211221608 A CN202211221608 A CN 202211221608A CN 115417616 B CN115417616 B CN 115417616B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/52—Grinding aids; Additives added during grinding
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Disintegrating Or Milling (AREA)
Abstract
The invention discloses a grinding aid for vertical mill cement and a preparation method thereof, and belongs to the technical field of cement additives. The grinding aid is prepared from alcohol amine substances, copolymer, polyglycerol, triethylene glycol and water. The copolymer prepared by the invention has the advantages of asymmetric molecular mechanism, high polarity, better adsorptivity to the surface of cement particles and good grinding assisting effect, and the molecular structure of the copolymer has amino and hydroxyl. The obtained grinding aid has a good material layer stabilizing effect, and meanwhile, the proper molecular weight does not influence the dispersing effect of the grinding aid. The grinding aid for the vertical mill cement has the design mixing amount of 0.08-0.15%, can reduce the water spraying amount for stabilizing the material layer in the cement production process, improves the quality of cement, improves the 3d strength of cement by more than 4MPa, and improves the output of a mill by about 20% in a machine hour.
Description
Technical Field
The invention belongs to the technical field of cement additives, and particularly relates to a grinding aid for vertical mill cement and a preparation method thereof.
Background
In the cement grinding process, the grinding processes of adopting a ball mill and a vertical mill have certain differences. In the ball mill, the materials are crushed by impact and friction; the grinding force of the material in the vertical mill is mainly extrusion, and grinding is auxiliary; the vertical mill has high grinding efficiency and saves the power consumption of grinding. Typically, the vertical mill can save 30% -40% of electricity compared with ball milling. The vertical mill is adopted to grind cement, and the fineness requirement of cement grinding products is high, the material circulation quantity is large, the circulating material is fine, the fluidity is good, and the cement is quickly taken away by high-speed air flow blown out by an air ring outside the millstone under the action of the running centrifugal force of the millstone, so that a stable material layer is difficult to form.
The traditional cement grinding aid is mainly prepared from alcohol amine micromolecule substances, has a good dispersing effect on cement, and can effectively improve the problem of cement agglomeration in the cement production process of the ball mill. In the vertical mill cement production process, the cement is required to have better material layer stability in the stay time of the grinding disc, so that the grinding roller is convenient to do work. The cement enters the upper powder selecting area and requires better dispersibility, so that the powder selecting efficiency of the powder selecting machine is improved, and the content of qualified fine powder in the returned powder is reduced. In the vertical mill cement production process, water spraying is needed on the surface of the material layer to stabilize the material layer, so that the cement quality can be influenced. The traditional small molecule grinding aid has good dispersing effect, but has great influence on the stability of a material layer, can not meet the use requirement of vertical mill cement, and is particularly important to develop the grinding aid capable of taking the stability and the dispersibility of the material layer into consideration.
Disclosure of Invention
The invention mainly aims at solving the problem that the conventional small molecular grinding aid cannot achieve both material layer stability and powder dispersion in the process of grinding cement by a vertical mill. The inventor realizes the balance of the stabilizing and dispersing effects of the additive on the material layer in the process of grinding cement by a vertical mill by synthesizing methallyl alcohol, acrylamide and unsaturated polyether copolymer with small molecular weight.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the grinding aid for the vertical mill cement comprises the following raw materials in parts by weight: 4-8 parts of alcohol amine substances, 20-40 parts of copolymers, 10-20 parts of polyglycerol, 10-20 parts of triethylene glycol and 40-65 parts of water.
Preferably, the alcohol amine substance is one or two of triethanolamine, diethanol monoisopropanolamine and monoethanol diisopropanolamine.
Preferably, the polyglycerol is a waste material containing both diglycerol and triglycerol produced during the glycerol distillation.
Preferably, the preparation method of the copolymer comprises the following steps:
(1) 20 parts of methallyl alcohol and 10 parts of acrylamide are weighed and placed in a container a, 70 parts of water is added, and the mixture is dissolved by shaking and is used as a material A for standby.
(2) 1 part of E51 reducer, 4-8 parts of mercaptopropionic acid and 70 parts of water are weighed and placed in a container B, and the container B is shaken and dissolved to serve as a material B for standby.
(3) 360 parts of unsaturated polyether are weighed and placed in a container c, and 300 parts of water is added; stirring for dissolving, heating to 35 ℃, and adding 5 parts of hydrogen peroxide; then simultaneously starting to dropwise add the material A and the material B into the container c, and uniformly dropwise adding the material A for 120min and the material B for 150min for control time; the temperature is controlled to rise by 1.5 ℃ every 15 min; after the completion of the dropwise addition, the temperature is kept for 1h, and finally, the pH value is adjusted to 8.0 by sodium hydroxide to obtain the copolymer.
Preferably, the mass concentration of the hydrogen peroxide in the step (3) is 30%.
Preferably, the unsaturated polyether of step (3) has a molecular weight of 600 and a purity of 99%.
The mixing amount of the grinding aid is 0.08-0.12% of the weight of cement when the grinding aid is used.
Preferably, the purity of the triethanolamine in the alcohol amine substance is 85%.
Preferably, the purity of the diethanol monoisopropanolamine in the alcohol amine substance is 85%.
Preferably, the purity of the alcohol amine type monoethanol diisopropanolamine is 85%.
Preferably, the polyglycerol is 70% pure.
Preferably, the purity of the triethylene glycol is 99%.
Preferably, the methallyl alcohol purity is 99.9%.
Preferably, the acrylamide has a purity of 99%.
Preferably, the E51 reducing agent is 95% pure.
Preferably, the mercaptopropionic acid has a purity of 99%.
The preparation method of the grinding aid for the vertical mill cement comprises the following preparation steps:
(1) Adding alcohol amine substances, copolymer and water into a stirring kettle, and uniformly stirring;
(2) Then adding polyglycerol and triethylene glycol into the stirring kettle, and rapidly and uniformly stirring;
(3) And (3) filtering the material obtained in the step (2) through 100-mesh cloth to obtain the grinding aid for the vertical mill cement.
Advantageous effects
(1) The copolymer prepared by the invention has the advantages of asymmetric molecular mechanism, high polarity, better adsorptivity to the surface of cement particles and good grinding assisting effect, and the molecular structure of the copolymer has amino and hydroxyl. The obtained grinding aid has a good material layer stabilizing effect, and meanwhile, the proper molecular weight does not influence the dispersing effect of the grinding aid.
(2) According to the invention, the industrial glycerol distillation residue polyglycerol is compounded and introduced as an effective grinding-assisting reinforcing component, and the triglycerol, the diglycerol and the glycerol contained in the grinding-assisting agent can effectively improve the stability of the vertical grinding material layer, and meanwhile, the grinding-assisting agent has better dispersibility and effectively improves the efficiency of grinding cement by the vertical mill.
(3) The grinding aid for the vertical mill cement has the design mixing amount of 0.08-0.15%, can reduce the water spraying amount for stabilizing the material layer in the cement production process, improves the quality of cement, improves the 3d strength of cement by more than 4MPa, and improves the output of a mill by about 20% in a machine hour.
Detailed Description
The technical scheme of the present invention is further described below with reference to specific examples, but is not limited thereto.
Example 1
The grinding aid for the vertical mill cement comprises the following raw materials in parts by weight: 8 parts of alcohol amine substance, 30 parts of copolymer, 10 parts of polymerized glycerol, 10 parts of triethylene glycol and 42 parts of water.
The copolymer is prepared by the following steps:
(1) Weighing 20 parts of methallyl alcohol and 10 parts of acrylamide, placing into a 250ml conical flask, adding 70 parts of water, shaking for dissolving, and taking the mixture as a material A for later use;
(2) 1 part of E51 reducer, 4 parts of mercaptopropionic acid and 70 parts of water are weighed and placed in a 250ml conical flask, and the mixture is dissolved by shaking and is used as a material B for standby;
(3) 360 parts of unsaturated polyether are weighed and placed in a 1000ml four-neck flask, and 300 parts of water is added; stirring for dissolution, heating to 35 ℃, and adding 5 parts of hydrogen peroxide (mass concentration is 30%); then, the material A and the material B are simultaneously dripped into the four-mouth flask, the dripping time is controlled at a constant speed, the material A is 120min, and the material B is 150min. The temperature is controlled to rise by 1.5 ℃ every 15 min; after the completion of the dropwise addition, the temperature is kept for 1h, and finally, the pH value is adjusted to 8.0 by sodium hydroxide to obtain the copolymer.
The purity of the triethanolamine in the alcohol amine substances is 85 percent.
The purity of the diethanol monoisopropanolamine in the alcohol amine substance is 85 percent.
The purity of the monoethanol diisopropanolamine in the alcohol amine substance is 85 percent.
The content of the polyglycerol is 70%.
The content of triethylene glycol is 99%.
The methallyl alcohol purity was 99.9%.
The acrylamide purity was 99%.
The E51 reductant purity was 95%.
The purity of the mercaptopropionic acid was 99%.
The molecular weight of the non-sum polyether is 600, and the purity is 99%.
The grinding aid for vertical mill cement has a mixing amount of 0.08-0.12% of the cement weight.
The preparation method of the grinding aid for the vertical mill cement comprises the following preparation steps:
(1) Adding the alcohol amine, the copolymer and water into a stirring kettle, and uniformly stirring;
(2) Then adding polyglycerol and triethylene glycol into the stirring kettle, and rapidly and uniformly stirring;
(3) And (3) filtering the material obtained in the step (2) through 100-mesh cloth to obtain the grinding aid for the vertical mill cement.
Example 2
The grinding aid for the vertical mill cement comprises the following raw materials in parts by weight: 6 parts of alcohol amine substance, 40 parts of copolymer, 10 parts of polymerized glycerol, 10 parts of triethylene glycol and 34 parts of water.
The copolymer is prepared by the following steps:
(1) Weighing 20 parts of methallyl alcohol and 10 parts of acrylamide, placing into a 250ml conical flask, adding 70 parts of water, shaking for dissolving, and taking the mixture as a material A for later use;
(2) 1 part of E51 reducer, 6 parts of mercaptopropionic acid and 70 parts of water are weighed and placed in a 250ml conical flask, and the mixture is dissolved by shaking and is used as a material B for standby;
(3) 360 parts of unsaturated polyether are weighed and placed in a 1000ml four-neck flask, and 300 parts of water is added; stirring for dissolution, heating to 35 ℃, and adding 5 parts of hydrogen peroxide (mass concentration is 30%); then, simultaneously starting to dropwise add the material A and the material B into the four-mouth flask, and uniformly dropwise adding the material A for 120min and the material B for 150min for control time; the temperature is controlled to rise by 1.5 ℃ every 15 min; after the completion of the dropwise addition, the temperature is kept for 1h, and finally, the pH value is adjusted to 8.0 by sodium hydroxide to obtain the copolymer.
The purity of the triethanolamine in the alcohol amine substances is 85 percent.
The purity of the diethanol monoisopropanolamine in the alcohol amine substance is 85 percent.
The purity of the monoethanol diisopropanolamine in the alcohol amine substance is 85 percent.
The content of the polyglycerol is 70%.
The content of triethylene glycol is 99%.
The methallyl alcohol purity was 99.9%.
The acrylamide purity was 99%.
The E51 reductant purity was 95%.
The purity of the mercaptopropionic acid was 99%.
The molecular weight of the non-sum polyether is 600, and the purity is 99%.
The grinding aid for vertical mill cement has a mixing amount of 0.08-0.12% of the cement weight.
The preparation method of the grinding aid for the vertical mill cement comprises the following preparation steps:
(1) Adding the alcohol amine, the copolymer and water into a stirring kettle, and uniformly stirring;
(2) Then adding polyglycerol and triethylene glycol into the stirring kettle, and rapidly and uniformly stirring;
(3) And (3) filtering the material obtained in the step (2) through 100-mesh cloth to obtain the grinding aid for the vertical mill cement.
Example 3
The grinding aid for the vertical mill cement comprises the following raw materials in parts by weight: 8 parts of alcohol amine substance, 40 parts of copolymer, 10 parts of polymerized glycerol, 10 parts of triethylene glycol and 32 parts of water.
The copolymer is prepared by the following steps:
(1) Weighing 20 parts of methallyl alcohol and 10 parts of acrylamide, placing into a 250ml conical flask, adding 70 parts of water, shaking for dissolving, and taking the mixture as a material A for later use;
(2) 1 part of E51 reducer, 8 parts of mercaptopropionic acid and 70 parts of water are weighed and placed in a 250ml conical flask, and the mixture is dissolved by shaking and is used as a material B for standby;
(3) 360 parts of unsaturated polyether are weighed and placed in a 1000ml four-neck flask, and 300 parts of water is added; stirring for dissolution, heating to 35 ℃, and adding 5 parts of hydrogen peroxide (mass concentration is 30%); then, simultaneously starting to dropwise add the material A and the material B into the four-mouth flask, and uniformly dropwise adding the material A for 120min and the material B for 150min for control time; the temperature is controlled to rise by 1.5 ℃ every 15 min; after the completion of the dropwise addition, the temperature is kept for 1h, and finally, the pH value is adjusted to 8.0 by sodium hydroxide to obtain the copolymer.
The purity of the triethanolamine in the alcohol amine substances is 85 percent.
The purity of the diethanol monoisopropanolamine in the alcohol amine substance is 85 percent.
The purity of the monoethanol diisopropanolamine in the alcohol amine substance is 85 percent.
The content of the polyglycerol is 70%.
The content of triethylene glycol is 99%.
The methallyl alcohol purity was 99.9%.
The acrylamide purity was 99%.
The E51 reductant purity was 95%.
The purity of the mercaptopropionic acid was 99%.
The molecular weight of the non-sum polyether is 600, and the purity is 99%.
The grinding aid for vertical mill cement has a mixing amount of 0.08-0.12% of the cement weight.
The preparation method of the grinding aid for the vertical mill cement comprises the following preparation steps:
(1) Adding the alcohol amine, the copolymer and water into a stirring kettle, and uniformly stirring;
(2) Then adding polyglycerol and triethylene glycol into the stirring kettle, and rapidly and uniformly stirring;
(3) And (3) filtering the material obtained in the step (2) through 100-mesh cloth to obtain the grinding aid for the vertical mill cement.
Performance testing
In order to further verify the use effect of the grinding aid of the invention, the grinding aids of the examples 1-3 and the general grinding aid sold in the market are respectively doped into cement, the doping amount is 0.08%, and a blank comparative example is provided, namely no grinding aid is added; and (3) carrying out statistics and comparison on various performances, wherein:
the cement materials are proportioned: 82% of clinker, 4% of limestone, 4% of fly ash, 5% of desulfurized gypsum and 5% of mixed materials.
Test procedure: the samples were compared in 4 test groups using 0.08% of the conventional grinding aid (HLA-G010 grinding aid type) of examples 1-3. The cement performance detection is carried out according to the cement mortar strength detection method of the national standard GB/T17671-1999, and the cement standard consistency water consumption, the setting time and other performances are detected according to the national standard GB/T1346-2011. The test results are shown in table 1:
TABLE 1 results of Performance test of the test samples of the macromill
As can be seen from the data in Table 1, the cement grinding aids obtained in examples 1-3 according to the invention have significantly higher 3d and 28d strengths than the blank and commercial general grinding aids, and the commercial general grinding aids have higher mill vibration values than the examples during the test, indicating that the copolymer according to the invention has a significant stabilizing effect on the mill bed, while it is seen from the cement stand-time yield and the specific surface area values that it has no negative effect on the dispersion of cement.
It should be noted that the above-mentioned embodiments are merely some, but not all embodiments of the preferred mode of carrying out the invention. It is evident that all other embodiments obtained by a person skilled in the art without making any inventive effort, based on the above-described embodiments of the invention, shall fall within the scope of protection of the invention.
Claims (6)
1. The grinding aid for the vertical mill cement is characterized by comprising the following raw materials in parts by weight: 4-8 parts of alcohol amine substances, 20-40 parts of copolymers, 10-20 parts of polyglycerol, 10-20 parts of triethylene glycol and 40-65 parts of water; the preparation method of the copolymer comprises the following steps:
(1) Weighing 20 parts of methallyl alcohol and 10 parts of acrylamide, placing the mixture in a container a, adding 70 parts of water, and shaking for dissolving to prepare a material A for later use;
(2) 1 part of E51 reducer, 4-8 parts of mercaptopropionic acid and 70 parts of water are weighed and placed in a container B, and shaking is carried out to dissolve the materials to be used as a material B for standby;
(3) 360 parts of unsaturated polyether are weighed and placed in a container c, and 300 parts of water is added; stirring for dissolving, heating to 35 ℃, and adding 5 parts of hydrogen peroxide; then simultaneously starting to dropwise add the material A and the material B into the container c at a constant speed, controlling the time, wherein the material A is 120min and the material B is 150min; the temperature is controlled to rise to 1.5 ℃ every 15 min; preserving heat for 1h after the dripping is finished, and finally, regulating the pH value to 8.0 by sodium hydroxide to obtain a copolymer;
the polyglycerol is waste material containing diglycerol and triglycerol generated in the glycerol distillation process.
2. The grinding aid for vertical mill cement according to claim 1, wherein the alcohol amine substance is one or two of triethanolamine, diethanol monoisopropanolamine and monoethanol diisopropanolamine.
3. The grinding aid for vertical mill cement according to claim 1, wherein the mass concentration of the hydrogen peroxide in the step (3) is 30%.
4. The grinding aid for vertical mill cement according to claim 1, wherein the unsaturated polyether of step (3) has a molecular weight of 600 and a purity of 99%.
5. The grinding aid for vertical mill cement according to claim 1, wherein the mixing amount of the grinding aid in use is 0.08-0.12% of the weight of the cement.
6. A method of preparing a grinding aid for a vertical mill cement as claimed in any one of claims 1 to 5, comprising the steps of:
(1) Adding alcohol amine substances, copolymer and water into a stirring kettle, and uniformly stirring;
(2) Then adding polyglycerol and triethylene glycol into the stirring kettle, and rapidly and uniformly stirring;
(3) And (3) filtering the material obtained in the step (2) through 100-mesh cloth to obtain the grinding aid for the vertical mill cement.
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Address after: 276000 Room 301, Floor 3, Building 14, Dongcheng Jingu, Intersection of Beijing East Road and Dongxing Road, Jiuqu Street, Linyi City, Shandong Province Applicant after: Linyi conch New Material Technology Co.,Ltd. Applicant after: Anhui Conch Material Technology Co.,Ltd. Address before: 276000 Room 301, Floor 3, Building 14, Dongcheng Jingu, Intersection of Beijing East Road and Dongxing Road, Jiuqu Street, Linyi City, Shandong Province Applicant before: Linyi conch New Material Technology Co.,Ltd. Applicant before: Anhui Conch New Materials Technology Co.,Ltd. |
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| GR01 | Patent grant | ||
| GR01 | Patent grant |