CN115651113B - Preparation process of gypsum retarder - Google Patents
Preparation process of gypsum retarder Download PDFInfo
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- CN115651113B CN115651113B CN202211423353.3A CN202211423353A CN115651113B CN 115651113 B CN115651113 B CN 115651113B CN 202211423353 A CN202211423353 A CN 202211423353A CN 115651113 B CN115651113 B CN 115651113B
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention relates to the field of building materials, in particular to a preparation process of a gypsum retarder for prolonging the setting time of gypsum mortar, gypsum board and gypsum blocks, which comprises the steps of preparing a gypsum retarder intermediate product, preparing a gypsum retarder mother solution and preparing gypsum retarder powder. Through amidation reaction of acrylic ester and aliphatic polyamine, intermediate product of gypsum retarder is synthesized, and the intermediate product is further copolymerized with olefin sulfonic acid (salt) and acrylic acid monomer to produce macromolecular copolymer gypsum retarder with proper molecular weight. The gypsum retarder prepared by the process has the advantages that the molecular structure contains carbonyl, acyl, sulfonic, carboxylic and other groups, the complexing performance on calcium ions is improved, the solubility of gypsum is reduced, the formation of crystal nuclei is delayed, the setting time is effectively prolonged under low doping amount, and the strength loss is effectively reduced through electrostatic repulsion and long side chain steric hindrance.
Description
Technical Field
The invention relates to the field of building materials, in particular to a preparation process of a gypsum retarder for prolonging the setting time of gypsum mortar, gypsum board and gypsum blocks.
Background
The main component of gypsum is calcium sulfate, which is an industrial material and building material with wide application, the mineral resource reserves of natural gypsum in China are relatively abundant, and the various determined gypsum reserves are about 70430Mt, and the place is the first place in the world. The industrial by-product gypsum refers to by-products or waste residues which are generated in industrial production and take calcium sulfate as a main component, namely chemical gypsum or industrial waste gypsum, and the accumulated accumulation and accumulation quantity of the industrial by-product gypsum in China is over 1100Mt at present, and the by-product gypsum mainly comprises desulfurized gypsum, phosphogypsum, titanium gypsum, fluorine gypsum and the like. The total production of industrial by-product gypsum in 2020 is about 200Mt, wherein the production of desulfurized gypsum, phosphogypsum, titanium gypsum and neutralization gypsum is more than 90% of the total industrial by-product gypsum. The industrial byproduct gypsum has poor quality, contains heavy metals, organic impurities and inorganic impurities, is difficult to recycle, occupies a large amount of land by piling, and has the risk of polluting water and soil. At present, the utilization amount of the byproduct gypsum in the industry in China is about 120Mt/a, the overall comprehensive utilization rate is about 60 percent, but the comprehensive utilization rate of complex and difficult byproduct gypsum such as phosphogypsum, titanium gypsum, fluorgypsum and the like is low. The industrial by-product gypsum is mainly used for preparing cement retarder, thistle board, plastering gypsum, gypsum lath, gypsum brick, gypsum block, self-leveling gypsum and the like, and is an indispensable component part because the gypsum is quickly solidified and hardened and can be used only after the operation time is prolonged when the industrial by-product gypsum is used for preparing gypsum mortar, gypsum board and gypsum block.
The common gypsum retarder mainly comprises 3 kinds of organic acid, soluble salt thereof, alkaline phosphate and protein retarder. The organic acid and the retarder of the soluble salts thereof are mainly adsorbed on the surfaces of the semi-hydrated gypsum particles to prevent the semi-hydrated gypsum from being dissolved, so that the supersaturation degree of liquid phase is reduced, the crystal nucleus forming speed is slowed down, the crystal habit is changed, the microstructure is loose, the pore structure of a hardening body is deteriorated, the coagulation time is prolonged, and the strength is reduced. The action mechanism of the alkaline phosphate retarder is mainly that insoluble salt generated by the reaction of calcium ions in the solution covers the surfaces of the semi-hydrated gypsum and the crystalline dihydrate gypsum crystal nucleus, so that the liquid phase supersaturation degree is reduced, the nucleation probability of the dihydrate gypsum crystal nucleus is reduced, the crystal habit of the dihydrate gypsum is changed, the pore structure is deteriorated, the coagulation time is prolonged, and the strength is reduced. The protein retarder mainly has the action mechanism that colloid formed after being dissolved in water covers the surface of hydrated ions, so that the free energy of a system is reduced, the formation of critical crystal nucleus is slowed down, or the gel is adsorbed on the surface of formed crystal nucleus, the surface energy of the crystal nucleus is reduced, the crystal nucleus is difficult to grow up in a certain period of time, the induction period of gypsum hydration is delayed, the coagulation time is prolonged macroscopically, the semi-hydrated gypsum in the initial stage is dissolved, and the formation of supersaturated solution of the dihydrate gypsum and the growth process of crystal grains in the hydration acceleration stage are not obviously influenced.
From the above, it can be seen that: organic acid, soluble salt, alkaline phosphate retarder, low retarding efficiency, high doping amount, change of crystal habit of dihydrate gypsum, degradation of pore structure and great negative influence on strength; the protein retarder has high retarding efficiency and low doping amount, does not have obvious influence on the semi-hydrated gypsum dissolution in the initial stage, the formation of the supersaturated dihydrate gypsum solution and the growth process of crystal grains in the hydration acceleration stage, has small influence on the strength, but has unstable product performance and large batch-to-batch fluctuation, and mainly adopts leftovers containing protein components such as animal feathers, bean pulp, zein and the like to hydrolyze due to high protein raw material cost.
Disclosure of Invention
The invention aims to solve the technical problems that: in order to overcome the defects in the prior art, a preparation process of the gypsum retarder is provided.
The technical scheme adopted by the invention is as follows: the preparation process of the gypsum retarder is characterized by comprising the following steps of:
s1, preparing an intermediate product of a gypsum retarder
Adding acrylic ester and aliphatic polyamine into a container, adding a proper amount of catalyst and polymerization inhibitor, carrying out amidation reaction at 100-110 ℃ for 4-6 hours, and forming an intermediate product; s2, preparing mother solution of gypsum retarder
Taking an aqueous solution formed by the intermediate product prepared in the step S1, olefin sulfonic acid (salt) and water as a base material, adding a chain transfer agent, respectively dropwise adding an initiator, a reducing agent and an acrylic acid monomer, carrying out free radical copolymerization reaction at normal temperature, controlling the dropwise adding time to be 1-1.5h, continuing to react for 1.5-2h after the dropwise adding is finished to obtain a copolymer, adding an alkali substance to neutralize to pH 6-8, and obtaining a gypsum retarder mother solution;
s3, preparing gypsum retarder powder
And (3) carrying out spray drying on the gypsum retarder mother liquor prepared in the step (S2) to form gypsum retarder powder, namely conveying the gypsum retarder mother liquor into a spray drying tower, atomizing and spraying from an atomizer at the top of the spray drying tower, controlling the temperature of a feed inlet of the spray drying tower to be 180-200 ℃, adding fumed silica to serve as a separating agent, adjusting the introducing speed of the fumed silica, controlling the temperature of an air outlet to be 85-95 ℃, cooling the materials, and packaging to obtain the gypsum retarder powder.
Through amidation reaction of acrylic ester and aliphatic polyamine, active intermediate product containing multiple carbonyl groups, acyl groups and other groups is synthesized, and the intermediate product is further copolymerized with olefin sulfonic acid (salt) and acrylic acid monomer to produce macromolecular copolymer retarder with proper molecular weight, and simultaneously sulfonic acid group and carboxylic acid group are introduced. Firstly, the gypsum retarder reduces the solubility of gypsum and delays the formation of crystal nucleus through the complexing performance of carbonyl, acyl, sulfonic acid and carboxylic acid groups on calcium ions; secondly, the gypsum retarder improves the complexing strength by controlling the molecular weight of the synthetic polymer, effectively prolongs the setting time under low doping amount, has small molecular weight, ensures that calcium ions are easy to break loose from binding, has poor retarding effect and large molecular weight, and ensures that the complex forms a bottom easily; finally, the gypsum retarder is adsorbed on the surface of gypsum particles, so that the surface of cement particles has the same charge to form electrostatic repulsion, and a long side chain has a steric hindrance effect, thereby reducing the water demand of gypsum and effectively reducing the strength loss caused by the deterioration of gypsum pore structure.
In the S1, the acrylic ester is one of methyl acrylate and hydroxyethyl acrylate;
the aliphatic polyamine is one of N, N' -dimethyl-1, 3-propylene diamine and N, N-dimethyl ethylenediamine;
the catalyst is one of dibutyl tin dilaurate and dibutyl tin oxide, and the dosage of the catalyst is 1.5-3.5% of the total amount of the liquid material;
the polymerization inhibitor is one of benzenediol and phenothiazine, and the dosage of the polymerization inhibitor is 0.1-0.3% of the total amount of the liquid material.
Further, in S1, the molar ratio of the acrylate to the aliphatic polyamine is 1:1-1.5 (mol/mol).
Further, in S2, the following substances are used in parts by mass:
water: 60-65 parts
Intermediate product: 15-20 parts
Olefinsulfonic acid (salt): 2-4 parts
Acrylic acid: 15-18 parts
Chain transfer agent: 0.5-0.8 part
And (3) an initiator: 0.3-0.5 part
Reducing agent: 0.1-0.2 parts.
Further, in S2, the olefin sulfonic acid (salt) is one of sodium styrene sulfonate, sodium allyl sulfonate and 2-acrylamide-2-methylpropanesulfonic acid;
the chain transfer agent is one of thioglycollic acid, mercaptopropionic acid, mercaptoethanol, isopropanol and sodium hypophosphite;
the initiator is one of ammonium persulfate and hydrogen peroxide;
the reducing agent is one of vitamin C, ferrous sulfate and sodium thiosulfate.
Further, in S2, the copolymer has a molar mass of 1500-3500g/mol.
In the step S3, the usage amount of the fumed silica is 2-3% of the total amount of the gypsum retarder powder.
Compared with the prior art, the invention has the following advantages:
(1) The raw materials used in the invention are conventional chemical raw materials, the quality of the raw materials is stable and controllable, the process is simple, the whole process flow can be carried out in line, and the control difficulty is small, so that the quality of the formed gypsum retarder product is stable and controllable;
(2) The gypsum retarder prepared by the invention has the advantages that the effect of effectively prolonging the setting time with low doping amount is achieved through the design of the mixing ratio and the control of the molecular weight of the polymer, the application cost can be effectively reduced, the addition amount is 0.02-0.03% of the total weight of the gypsum, and the initial setting time of the gypsum can reach 100-250 minutes;
(3) The gypsum retarder produced by the method is mixed into gypsum, the time of retarding is increased and the mixing amount of the retarder shows a good linear relation, the setting time of the gypsum can be well adjusted, and the influence of the change of the environmental temperature on the retarding time is small, so that the applicability is wide.
Drawings
Fig. 1 is a schematic flow chart of the invention S3.
Reference numerals in the drawings: the device comprises a 1-heating device, a 2-isolating agent storage tank, a 3-gypsum retarder mother liquor storage tank, a 4-conveying pump, a 5-feed inlet, a 6-atomizer, a 7-spray drying device, an 8-blower, a 9-air outlet, a 10-cooling device and an 11-packaging machine.
Detailed Description
The following describes the embodiments of the present invention in detail, and the embodiments and specific operation procedures are given on the premise of the technical solution of the present invention, but the scope of protection of the present invention is not limited to the following embodiments.
Example 1
The preparation process of the gypsum retarder is characterized by comprising the following steps of:
s1, preparing an intermediate product of a gypsum retarder
Adding acrylic ester and aliphatic polyamine into a container, adding a proper amount of catalyst and polymerization inhibitor, carrying out amidation reaction at 100-110 ℃ for 4-6 hours, and forming an intermediate product;
s2, preparing mother solution of gypsum retarder
Taking an aqueous solution formed by the intermediate product prepared in the step S1, olefin sulfonic acid (salt) and water as a base material, adding a chain transfer agent, respectively dropwise adding an initiator, a reducing agent and an acrylic acid monomer, carrying out free radical copolymerization reaction at normal temperature, controlling the dropwise adding time to be 1-1.5h, continuing to react for 1.5-2h after the dropwise adding is finished to obtain a copolymer, adding an alkali substance to neutralize to pH 6-8, and obtaining a gypsum retarder mother solution;
s3, preparing gypsum retarder powder
And (3) carrying out spray drying on the gypsum retarder mother liquor prepared in the step (S2) to form gypsum retarder powder, namely conveying the gypsum retarder mother liquor from a gypsum retarder mother liquor tank 3 to a spray drying device 7 through a conveying pump 4, atomizing and spraying from an atomizer 6 at the top of the spray drying device 7, controlling the temperature of the feed inlet 5 of the spray drying device 7 to be 180-200 ℃ through a heating device 1, adding fumed silica to serve as a separating agent, conveying the separating agent from a separating agent storage tank 2 to the spray drying device 7, adjusting the introducing speed of the fumed silica, and supplying air to an air outlet 9 by a blower 8 to control the temperature of the air outlet 9 to be 85-95 ℃, and then cooling the material by a cooling device 10 and packaging the material in a packaging machine 11 to obtain the gypsum retarder powder.
In S1, acrylic ester is methyl acrylate; the aliphatic polyamine is N, N' -dimethyl-1, 3-propylene diamine; the catalyst is dibutyl tin dilaurate, and the dosage of the dibutyl tin dilaurate is 1.5-3.5% of the total amount of the liquid material;
the polymerization inhibitor is benzene diphenol, and the dosage of the polymerization inhibitor is 0.1-0.3% of the total amount of the liquid material.
In S1, the molar ratio of the acrylic ester to the aliphatic polyamine is 1:1.5 (mol/mol).
S2, adopting the following substances in parts by mass:
water: 60 parts of
Intermediate product: 15 parts of
Olefinsulfonic acid (salt): 2 parts of
Acrylic acid: 15 parts of
Chain transfer agent: 0.5 part
And (3) an initiator: 0.3 part
Reducing agent: 0.05 part.
In S2, the olefin sulfonic acid (salt) is sodium styrene sulfonate; the chain transfer agent is thioglycollic acid; the initiator is ammonium persulfate; the reducing agent is ferrous sulfate.
In S2, the molar mass of the copolymer is 1500-3500g/mol.
In S3, the usage amount of the fumed silica is 2-3% of the total amount of the gypsum retarder powder.
Example 2
The difference from example 1 is that:
in S1, acrylic ester is hydroxyethyl acrylate; the aliphatic polyamine is N, N-dimethyl ethylenediamine;
in S1, the molar ratio of the acrylic ester to the aliphatic polyamine is 1:1.0 (mol/mol).
Example 3
The difference from example 1 is that:
in S1, acrylic ester is methyl acrylate; the aliphatic polyamine is N, N-dimethyl ethylenediamine;
in S1, the molar ratio of the acrylic ester to the aliphatic polyamine is 1:1.2 (mol/mol).
Example 4
The difference from example 1 is that: s2, adopting the following substances in parts by mass:
water: 65 parts of
Intermediate product: 15 parts of
Olefinsulfonic acid (salt): 4 parts of
Acrylic acid: 18 parts of
Chain transfer agent: 0.5 part
And (3) an initiator: 0.3 part
Reducing agent: 0.1 part.
Example 5-example 11
Example 5-example 11 differs from example 1 in that the mass parts of the olefin sulfonic acid (salt), acrylic acid, intermediate products in S2 are different as shown in table 1 below:
TABLE 1
| Substance (B) | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 |
| Intermediate products | 20 | 15 | 20 | 15 | 20 | 20 | 15 |
| Olefin sulfonic acid (salt) | 4 | 4 | 4 | 2 | 2 | 2 | 2 |
| Acrylic acid | 18 | 15 | 15 | 18 | 18 | 15 | 15 |
To better compare the retarding effect and strength loss of the examples of the present invention with the commercial products, setting time, strength performance tests were performed according to GB/T17669 with the conventional citric acid and hydrolyzed protein retarders, and the results are shown in Table 2 below:
TABLE 2
As can be seen from examples 1-11, the gypsum retarder prepared by the invention has the addition amount of 0.02-0.03% of the total weight of gypsum, the initial setting time of the gypsum can reach 100-250 minutes, and compared with citric acid and hydrolyzed protein retarder, the setting time of the same addition amount is obviously increased, and the negative effect on the strength of the gypsum is small.
Claims (6)
1. The preparation process of the gypsum retarder is characterized by comprising the following steps of:
s1, preparing an intermediate product of a gypsum retarder
Adding acrylic ester and aliphatic polyamine into a container, adding a proper amount of catalyst and polymerization inhibitor, carrying out amidation reaction at 100-110 ℃ for 4-6 hours, and forming an intermediate product;
s2, preparing mother solution of gypsum retarder
Taking an aqueous solution formed by the intermediate product prepared in the step S1, olefin sulfonic acid (salt) and water as a base material, adding a chain transfer agent, respectively dropwise adding an initiator, a reducing agent and an acrylic acid monomer, carrying out free radical copolymerization reaction at normal temperature, controlling the dropwise adding time to be 1-1.5h, continuing to react for 1.5-2h after the dropwise adding is finished to obtain a copolymer, adding an alkali substance to neutralize to pH 6-8, and obtaining a gypsum retarder mother solution;
s3, preparing gypsum retarder powder
The gypsum retarder mother liquor prepared in the step S2 is subjected to spray drying to form gypsum retarder powder, specifically, the gypsum retarder mother liquor is conveyed into a spray drying tower, atomized and sprayed out from an atomizer at the top of the spray drying tower, the temperature of a feed inlet of the spray drying tower is controlled to be 180-200 ℃, fumed silica is added to serve as a separating agent, the introducing speed of the fumed silica is adjusted, the temperature of an air outlet is controlled to be 85-95 ℃, and the materials are packaged after being cooled to obtain the gypsum retarder powder;
in S1, the aliphatic polyamine is one of N, N' -dimethyl-1, 3-propylene diamine and N, N-dimethyl ethylenediamine;
s2, adopting the following substances in parts by mass:
water: 60-65 parts
Intermediate product: 15-20 parts
Olefinsulfonic acid (salt): 2-4 parts
Acrylic acid: 15-18 parts
Chain transfer agent: 0.5-0.8 part
And (3) an initiator: 0.3-0.5 part
Reducing agent: 0.1-0.2 parts.
2. The process for preparing a gypsum retarder according to claim 1, wherein, in S1,
the acrylic ester is one of methyl acrylate and hydroxyethyl acrylate;
the catalyst is one of dibutyl tin dilaurate and dibutyl tin oxide, and the dosage of the catalyst is 1.5-3.5% of the total amount of the liquid material;
the polymerization inhibitor is one of benzenediol and phenothiazine, and the dosage of the polymerization inhibitor is 0.1-0.3% of the total amount of the liquid material.
3. The process for preparing a gypsum retarder according to claim 1, wherein in S1, the molar ratio of the acrylic acid ester to the aliphatic polyamine is 1:1-1.5.
4. The process for preparing a gypsum retarder according to claim 1, wherein, in S2,
the olefin sulfonic acid (salt) is one of sodium styrene sulfonate, sodium allyl sulfonate and 2-acrylamide-2-methylpropanesulfonic acid;
the chain transfer agent is one of thioglycollic acid, mercaptopropionic acid, mercaptoethanol, isopropanol and sodium hypophosphite;
the initiator is one of ammonium persulfate and hydrogen peroxide;
the reducing agent is one of vitamin C, ferrous sulfate and sodium thiosulfate.
5. The process for preparing a gypsum retarder according to claim 1, wherein in S2, the copolymer has a molar mass of 1500-3500g/mol.
6. The process for preparing a gypsum retarder according to claim 1, wherein in S3, the fumed silica is used in an amount of 2-3% of the total amount of the gypsum retarder powder.
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