CN104817288A - Cement grinding aid composition by taking glycerinum distillation residues as main raw material as well as preparation method and application thereof - Google Patents
Cement grinding aid composition by taking glycerinum distillation residues as main raw material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to cement grinding aid composition by taking glycerinum distillation residues as a main raw material as well as a preparation method and an application thereof. The preparation method of the cement grinding aid composition by taking the glycerinum distillation residue as the main raw material comprises the following steps: step a): carrying out solid-liquid separation to the glycerinum distillation residues, taking a liquid phase I, and adding an organic solvent to obtain a liquid phase II by carrying out the secondary solid-liquid separation to sodium chloride precipitate, removing the organic solvent to obtain a mixture A of which the main ingredient comprises glycerinum and polyglycerol; step b): adding the mixture A obtained in the steps a) into a reaction kettle, polymerizing the glycerinum in the presence of a metal catalyst and a copper and alkaline catalyst so as to obtain a mixture B, wherein the main ingredients of the mixture B comprise polyglycerol of which the degree of polymerization is 2.5-3.0 and glycerinum of which the degree of polymerization is 2-5%; step c): adding water into the mixture B obtained in the step b), adjusting the pH value of a solution to between 5 and 7, so as to obtain a solution C of which the sum of the mass percent concentrations of the glycerinum and the polyglycerol is 40-75%.
Description
Technical field
The present invention relates to a kind of cement grinding aid composition, particularly relating to a kind of take glycerol distilled residue as the cement grinding aid composition of main raw material, its preparation method and application.
Background technology
In chemosynthesis glycerol production process, can discharge glycerol distilled residue, its outward appearance is dark-brown or brownish black semi-solid state, wherein sodium chloride-containing 20%-50%, and glycerine 5%-20%, polyglycerol 5%-10%, surplus is water.Partial glycerol manufacturer adopts the way of air storage rainwater shower, and the indigenous method that natural separation goes out inorganic salt processes, serious environment pollution.The inorganic salt how less energy-consumption ground realizes wherein are separated with glycerine, polyglycerol, thus to realize industrial utilization be further very have realistic meaning.Document is had to show, first realize most of sodium-chlor with industrial centrifugal machine to be separated with glycerol distillation raffinate, ethanol is adopted to be solvent again, the sodium-chlor remained is precipitated out as far as possible, extract glycerine, polyglycerol wherein, after being separated solvent, product just can become mixed alcohol, and (main component has glycerine, polyglycerol, water).This mixed alcohol can use by making cement grinding aid to have document to show, has good cement and blast-furnace slag grinding-aid effect, but also partly can replace this kind of expensive material of trolamine.
But, this kind of mixed alcohol product in the market, wherein polyglycerol only accounts for 10%-20%, glycerine accounts for 20%-40%, all the other are the aqueous solution containing a small amount of sodium-chlor, and the grinding-aid effect of pure glycerin making cement grinding aid is poor, how the glycerine in glycerol distilled residue is also converted into polyglycerol, realizing highlyer utilizing more fully, is the technical problem underlying needing to solve.
Summary of the invention
Goal of the invention
An object of the present invention is to provide a kind of take glycerol distilled residue as the preparation method of the cement grinding aid composition of main raw material, is polyglycerol the transformation of glycerol in residue, improves product to the grinding aid of cement and reinforced effects.
The cement grinding aid composition of what another object of the present invention was to provide above-mentioned preparation method's gained with glycerol distilled residue is main raw material.
Another object of the present invention is to provide the application of above-mentioned composition as cement grinding aid.
Summary of the invention
In a first aspect of the present invention, providing a kind of take glycerol distilled residue as the preparation method of the cement grinding aid composition of main raw material, and it comprises the following steps:
Step is a): solid-liquid separation glycerol distilled residue, get liquid phase I and add organic solvent, after making Sodium chloride deposit wherein, solid-liquid separation obtains liquid phase II again, removing organic solvent wherein, obtain the mixture A that main component is glycerine and polyglycerol, the mass percent of wherein said glycerol distilled residue consists of sodium-chlor 20%-50%, glycerine 5%-20%, polyglycerol 5%-10%, surplus is water;
Step b): the mixture A of step a) gained is added in reactor, under metal catalyst and alkaline catalysts exist, in nitrogen atmosphere, make glycerine carry out polyreaction 2-5h at 200-240 DEG C, obtain the mixture B that the polymerization degree is 2.5-3.0, its main component is polyglycerol and mass percent is the glycerine of 2%-5%, described metal catalyst is copper, and described alkaline catalysts is salt of wormwood and/or sodium carbonate, and the quality of alkaline catalysts is the 1%-3% of mixture A quality;
Step c): to step b) add water in gained mixture B, and regulator solution pH value is between 5-7, the mass percent concentration sum obtaining glycerine and polyglycerol is the solution C of 40%-75%.
Step is a) prior art, through experiment, those skilled in the art can determine that the concrete grammar of solid-liquid separation is (as centrifugation, natural filtration or filtration under diminished pressure etc., the method of twice solid-liquid separation can be identical, also can be different), adopt the consumption of which kind of organic solvent and organic solvent, to remove the sodium-chlor in residue as far as possible, preferred described organic solvent is ethanol, and more preferably the mass ratio of described organic solvent and liquid phase I is (3-8): 1.Concrete operation can be: centrifugation glycerol distilled residue, isolate most of sodium-chlor, get liquid phase I, add organic solvent, stir, leave standstill, make Sodium chloride deposit, filter and obtain liquid phase II, distillation, removing organic solvent wherein, obtains the mixture A that main component is glycerine and polyglycerol.
Step b) described in alkaline catalysts be preferably sodium carbonate.This step directly carries out glycerol polymerization reaction by mixture A, has similar part with the polyreaction of high-purity glycerol, such as, as general knowledge, needs the water that removing polyreaction in time produces, to promote fully carrying out of polyreaction.But due to the purity restriction of glycerine in mixture A and the existence of some impurity, reaction conditions is not only more harsh, such as must carry out in nitrogen atmosphere, and applicant finds through lot of experiments, in adopting metal catalyst copper to react with glycerol polymerization, conventional alkaline catalysts coordinates, could in reaction conditions (temperature of the present invention, reaction times) under make glycerine major part be converted into the polyglycerol of the required polymerization degree, after step (c) and optional step (d), gained cement grinding aid composition shows good grinding aid and reinforced effects to cement.Due to reaction conditions restriction and consider energy consumption problem, the glycerine in mixture A does not have 100% to be converted into polyglycerol, and has remaining on a small quantity.Test proves that glycerine remaining on a small quantity does not affect the actual effect of grinding aid.Reaction product can take gas-chromatography and gaschromatographic mass spectrometry to be used in conjunction legal analysis polyglycerol; The polymerization degree can pass through refractive index, hydroxyl value (mgKOH/g) and the relation of the polymerization degree, determines the polymerization degree.Polyglycerol polymerization degree n=(56110 × 2-18 × Y)/(74 × Y-56110), Y are hydroxyl value; Polyglycerol refractive index (n.20/D) is Y=52480-34330 × (n.20/D) with the regression beeline equation of hydroxyl value (Y).The available A Pei refractometer of refractive index (n.20/D) detects and obtains.Without the need to carrying out separation and purification to reaction product during test refractive index, therefore the gained polymerization degree is the mean polymerisation degree of contained glycerine and polyglycerol in reaction product.Such monitoring polymerization degree, to control extent of reaction, has convenient and time-saving advantage.The preferred polymerization degree is 2.6 ~ 2.9.
Step c) in, according to prior art, the acidic substance being applicable to being used in concrete aspect can be chosen and carry out regulator solution pH value, preferably use oxalic acid regulator solution pH value.
Solution C can directly when cement grinding aid composition uses, and also can add alcamines material again, obtain the cement grinding aid composition of Compositional type after stirring, composite rear grinding aid reinforced effects is better.Therefore as improvement of the present invention, steps d can also be comprised): in step c) add alcamines cement grinding aid in gained solution C.The mass ratio of preferred described solution C and alcamines cement grinding aid is 1: (0.3-0.5).Described alcamines cement grinding aid is preferably trolamine (being called for short TEA) and/or tri-isopropanolamine (being called for short TIPA), is more preferably trolamine.
According to a second aspect of the present invention, providing what obtain according to above-mentioned preparation method take glycerol distilled residue as the cement grinding aid composition of main raw material, due to the glycerine major part in glycerol distilled residue is converted into polyglycerol, described cement grinding aid composition is good to the grinding aid of cement and reinforced effects, achieves that glycerol distilled residue is higher to be utilized more fully.
According to a third aspect of the present invention, provide the application of above-mentioned cement grinding aid composition, as cement grinding aid, to cement, there is good grinding aid and reinforced effects.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just as further illustrating the features and advantages of the invention instead of limitation of the present invention.
Below all embodiments relate to the producer of material and model as follows:
Dehydrated alcohol: Jinan Heng Run biochemical industry company limited, technical grade, content 99.5%;
Sodium carbonate: Weifang Hai Zhiyuan Chemical Co., Ltd., technical grade, content 99%;
Oxalic acid: Weifang Peng Chuan Chemical Co., Ltd., technical grade, content 96%;
Trolamine: Shanghai Fu Jia Chemical Co., Ltd., technical grade, content 85%;
Tri-isopropanolamine: Shanghai Fu Jia Chemical Co., Ltd., technical grade, content 85%;
Cement clinker: state, Yihe River Cement Group, 3 days intensity 34MPa, 28 days intensity 56MPa;
Gypsum: Xiao Chun gypsum company limited of Pizhou City, secondary natural dihydrate gypsum;
Slag: Linyi Steel Plant, industry byproduct;
Flyash: electricity generating corporation, Ltd of electricity charge county of state, second class powered coal ash;
Wingdale: Yongshun, Linyi City Luozhuang District building stones factory, CaO content 52%.
Embodiment 1
In certain factory's chemosynthesis glycerol production process, the glycerol distilled residue quality group of discharge becomes sodium-chlor 35%, glycerine 18%, polyglycerol 8%, and surplus is water.
Step is a): get glycerol distilled residue 1000g, centrifugation, remove most of sodium-chlor, get the liquid phase I500g after separation, add 1500g dehydrated alcohol, after abundant stirring, elimination inorganic salt, obtain liquid phase II, then remove ethanol with distiller air distillation, until mixture constant weight, obtain the mixture A that main component is glycerine and polyglycerol;
Step b): the mixture A getting 100g step a) gained adds in reactor, inserting a diameter in still is the copper wire of 2mm, in copper wire insertion reaction medium, add 1g sodium carbonate again as catalyzer, open nitrogen protection, 5h is reacted at being heated to 200 DEG C, the condenser connected by reactor in reaction process removes the water of generation in time, cooling obtains mixture B, wherein polyglycerol accounts for 80%, glycerine accounts for 5%, and by measuring the refractive index of mixture B, the mean polymerisation degree calculating polyglycerol is 2.8;
Step c): get 100g mixture B, add the water of 100g, be adjusted to pH=6 with oxalic acid, obtain 201g solution C, its concentration is 42.3%.
Steps d): in solution C, add trolamine, solution C and trolamine mass ratio are 1: 0.4, obtain cement grinding aid composition after stirring.
The present invention is that the cement grinding aid composition of main raw material is tested in the little mill of Ф 500mm × 500mm standard test with glycerol distilled residue by what obtain, and detailed process is as follows:
Mix according to following material proportion: the flyash that the slag that the gypsum that the grog that massfraction is 70%, massfraction are 4.0%, massfraction are 12%, massfraction are 8%, massfraction are the Wingdale of 6%, in the mixture obtained, add massfraction be the glycerol distilled residue that the present embodiment of mixture total mass 0.05% obtains is the cement grinding aid composition of main raw material, obtains the cement after processing after combined grinding 28min (minute).According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) " test strength of cement mortar; DBT-127 type Bo Shi ratio surface area instrument of breathing freely is adopted to detect the Blain specific surface of the slow setting grinding aid obtained; Detect consumptive use of water normal consistence, the time of coagulation of cement according to GB 1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection ", result is as shown in table 1.
In production practice, the setting of metal catalyst copper also can by realizing at the built-in coil pipe of reactor, and reactor inner coil pipe is the stainless steel tube of copper coating 2mm thickness.
Embodiment 2
In certain factory's chemosynthesis glycerol production process, the glycerol distilled residue quality group of eliminating becomes sodium-chlor 20%, glycerine 20%, polyglycerol 10%, and surplus is water.
Step is a): get glycerol distilled residue 1000g, centrifugation, remove most of sodium-chlor, get the liquid phase I500g after separation, add 2000g dehydrated alcohol, after abundant stirring, elimination inorganic salt, obtain liquid phase II, then remove ethanol with distiller air distillation, until mixture constant weight, obtain the mixture A that main component is glycerine and polyglycerol;
Step b): the mixture A getting 100g step a) gained adds in reactor, inserting a diameter in still is the copper wire of 2mm, copper wire insertion reaction medium, add 3g sodium carbonate again as catalyzer, open nitrogen protection, 2h is reacted at being heated to 240 DEG C, the condenser connected by reactor in reaction process removes the water of generation in time, cooling obtains mixture B, wherein polyglycerol accounts for 82%, glycerine accounts for 3%, and by measuring the refractive index of mixture B, the mean polymerisation degree calculating polyglycerol is 2.6; Step c): get 100g mixture B, add the water of 55g, be adjusted to pH=6.5 with oxalic acid, obtain 156g solution C, its concentration is 54.5%;
Steps d): in solution C, add trolamine, solution C and trolamine mass ratio are 1: 0.3, and obtaining after stirring take glycerin residue as the cement grinding aid composition of main raw material.
Mix according to following material proportion: the flyash that the slag that the gypsum that the grog that massfraction is 70%, massfraction are 4.0%, massfraction are 12%, massfraction are 8%, massfraction are the Wingdale of 6%, in the mixture obtained, add massfraction be the glycerol distilled residue that the present embodiment of mixture total mass 0.05% obtains is the cement grinding aid composition of main raw material, obtains the cement after processing after combined grinding 28min.According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) " test strength of cement mortar; DBT-127 type Bo Shi ratio surface area instrument of breathing freely is adopted to detect the Blain specific surface of the slow setting grinding aid obtained; Detect consumptive use of water normal consistence, the time of coagulation of cement according to GB 1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection ", result is as shown in table 1.
Embodiment 3
In certain factory's chemosynthesis glycerol production process, the glycerol distilled residue quality group of discharge becomes sodium-chlor 50%, glycerine 10%, polyglycerol 5%, and surplus is water.
Step is a): get glycerol distilled residue 1000g, centrifugation, remove most of sodium-chlor, get the liquid phase I400g after separation, add 3000g dehydrated alcohol, after abundant stirring, elimination inorganic salt, obtain liquid phase II, then remove ethanol with distiller air distillation, until mixture constant weight, obtain the mixture A that main component is glycerine and polyglycerol;
Step b): the mixture A getting 100g step a) gained adds in reactor, inserting a diameter in still is the copper wire of 2mm, in copper wire insertion reaction medium, add 2g sodium carbonate again as catalyzer, open nitrogen protection, 3h is reacted at being heated to 220 DEG C, the condenser connected by reactor in reaction process removes the water of generation in time, cooling obtains mixture B, wherein polyglycerol accounts for 71%, glycerine accounts for 4%, and by measuring the refractive index of mixture B, the mean polymerisation degree calculating polyglycerol is 2.9;
Step c): get 100g mixture B, add the water of 30g, be adjusted to pH=7 with oxalic acid, obtain solution 132.0g C, its concentration is 56.8%;
Steps d): in solution C, add trolamine, solution C and trolamine mass ratio are 1: 0.5, and obtaining after stirring take glycerol distilled residue as the cement grinding aid composition of main raw material.
Mix according to following material proportion: the flyash that the slag that the gypsum that the grog that massfraction is 70%, massfraction are 4.0%, massfraction are 12%, massfraction are 8%, massfraction are the Wingdale of 6%, in the mixture obtained, add massfraction be the glycerin residue that the present embodiment of mixture total mass 0.05% obtains is the cement grinding aid composition of main raw material, obtains the cement after processing after combined grinding 28min.According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) " test strength of cement mortar; DBT-127 type Bo Shi ratio surface area instrument of breathing freely is adopted to detect the Blain specific surface of the slow setting grinding aid obtained; Detect consumptive use of water normal consistence, the time of coagulation of cement according to GB 1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection ", result is as shown in table 1.
Embodiment 4
In certain factory's chemosynthesis glycerol production process, the glycerol distilled residue of discharge, its quality group becomes sodium-chlor 50%, glycerine 10%, polyglycerol 5%, and surplus is water.
Step is a): get glycerol distilled residue 1000g, centrifugation, remove most of sodium-chlor, get the liquid phase I400g after separation, add 3000g dehydrated alcohol, after abundant stirring, elimination inorganic salt, obtain liquid phase II, then remove ethanol with distiller air distillation, until mixture constant weight, obtain the mixture A that main component is glycerine and polyglycerol;
Step b): the mixture A getting 100g step a) gained adds in reactor, inserting a diameter in still is the copper wire of 2mm, in copper wire insertion reaction medium, add 2g sodium carbonate again as catalyzer, open nitrogen protection, 3h is reacted at being heated to 220 DEG C, the condenser connected by reactor in reaction process removes the water of generation in time, cooling obtains mixture B, wherein polyglycerol accounts for 71%, glycerine accounts for 4%, and by measuring the refractive index of mixture B, the mean polymerisation degree calculating polyglycerol is 2.9;
Step c): get 100g mixture B, add the water of 30g, be adjusted to pH=7 with oxalic acid, obtain 132g solution C, its concentration is 56.8%;
Steps d): in solution C, add tri-isopropanolamine, solution C and tri-isopropanolamine mass ratio are 1: 0.5, and obtaining after stirring take glycerol distilled residue as the cement grinding aid composition of main raw material.
Mix according to following material proportion: the flyash that the slag that the gypsum that the grog that massfraction is 70%, massfraction are 4.0%, massfraction are 12%, massfraction are 8%, massfraction are the Wingdale of 6%, in the mixture obtained, add massfraction be the glycerin residue that the present embodiment of mixture total mass 0.05% obtains is the cement grinding aid composition of main raw material, obtains the cement after processing after combined grinding 28min.According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) " test strength of cement mortar; DBT-127 type Bo Shi ratio surface area instrument of breathing freely is adopted to detect the Blain specific surface of the slow setting grinding aid obtained; Detect consumptive use of water normal consistence, the time of coagulation of cement according to GB 1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection ", result is as shown in table 1.
Comparative example 1
Test in the little mill of Ф 500mm × 500mm standard test, detailed process is as follows:
Mix according to following material proportion: the flyash that the slag that the gypsum that the grog that massfraction is 70%, massfraction are 4.0%, massfraction are 12%, massfraction are 8%, massfraction are the Wingdale of 6%, after combined grinding 28min, obtain the cement after processing.According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) " test strength of cement mortar; DBT-127 type Bo Shi ratio surface area instrument of breathing freely is adopted to detect the Blain specific surface of the slow setting grinding aid obtained; Detect consumptive use of water normal consistence, the time of coagulation of cement according to GB 1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection ", result is as shown in table 1.
Comparative example 2
Test in the little mill of Ф 500mm × 500mm standard test, detailed process is as follows:
Mix according to following material proportion: the flyash that the slag that the gypsum that the grog that massfraction is 70%, massfraction are 4.0%, massfraction are 12%, massfraction are 8%, massfraction are the Wingdale of 6%, in the mixture obtained, add the commercially available HY-IIIC type cement grinding aid that massfraction is mixture total mass 0.05%, after combined grinding 28min, obtain the cement after processing.According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) " test strength of cement mortar; DBT-127 type Bo Shi ratio surface area instrument of breathing freely is adopted to detect the Blain specific surface of the slow setting grinding aid obtained; Detect consumptive use of water normal consistence, the time of coagulation of cement according to GB 1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection ", result is as shown in table 1.
Embodiment 5
Mix according to following material proportion: the flyash that the slag that the gypsum that the grog that massfraction is 70%, massfraction are 4.0%, massfraction are 12%, massfraction are 8%, massfraction are the Wingdale of 6%, in the mixture obtained, add massfraction is the solution C that in the embodiment 1 of mixture total mass 0.05%, step C obtains, and obtains the cement after processing after combined grinding 28min.According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) " test strength of cement mortar; DBT-127 type Bo Shi ratio surface area instrument of breathing freely is adopted to detect the Blain specific surface of the slow setting grinding aid obtained; Detect consumptive use of water normal consistence, the time of coagulation of cement according to GB 1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection ", result is as shown in table 1.
Embodiment 6
Mix according to following material proportion: the flyash that the slag that the gypsum that the grog that massfraction is 70%, massfraction are 4.0%, massfraction are 12%, massfraction are 8%, massfraction are the Wingdale of 6%, in the mixture obtained, add massfraction is the solution C that in the embodiment 2 of mixture total mass 0.05%, step C obtains, and obtains the cement after processing after combined grinding 28min.According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) " test strength of cement mortar; DBT-127 type Bo Shi ratio surface area instrument of breathing freely is adopted to detect the Blain specific surface of the slow setting grinding aid obtained; Detect consumptive use of water normal consistence, the time of coagulation of cement according to GB 1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection ", result is as shown in table 1.
Embodiment 7
Mix according to following material proportion: the flyash that the slag that the gypsum that the grog that massfraction is 70%, massfraction are 4.0%, massfraction are 12%, massfraction are 8%, massfraction are the Wingdale of 6%, in the mixture obtained, add massfraction is the solution C that in the embodiment 3 of mixture total mass 0.05%, step C obtains, and obtains the cement after processing after combined grinding 28min.According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) " test strength of cement mortar; DBT-127 type Bo Shi ratio surface area instrument of breathing freely is adopted to detect the Blain specific surface of the slow setting grinding aid obtained; Detect consumptive use of water normal consistence, the time of coagulation of cement according to GB 1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection ", result is as shown in table 1.
By embodiment 1,2,3 and embodiment 5,6,7 data; Comparative example 1,2 and embodiment 5,6,7 data; Embodiment 3 and embodiment 4 data; Can find out:
(1) according to the present invention, glycerol distilled residue is processed, after making glycerol polymerization wherein, gained cement grinding aid composition has good grinding-aid effect, described cement grinding aid composition is used for cement grinding test, gained cement compares with comparative example 1 (blank), specific surface area increases, and fineness reduces; But the reinforced effects of cement is not obvious.
(2) according to the present invention, glycerol distilled residue is processed, make glycerol polymerization wherein, and composite with TEA after, it is more obvious when gained cement grinding aid composition is compared not composite with TEA to cement effect, described cement grinding aid composition is used for cement grinding test, cement early strength and later strength increase all to some extent, suitable with commercially available prod HY-IIIC type (comparative example 2) effect.
(3) according to the present invention, glycerol distilled residue is processed, make glycerol polymerization wherein, and composite with TIPA after, it is more obvious when gained cement grinding aid composition is compared not composite with TIPA to cement effect, TIPA is little to cement early strength contribution, and later strength has obvious increase.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
The little mill experimental result that table 1 embodiment of the present invention and comparative example obtain
Claims (9)
1. be a preparation method for the cement grinding aid composition of main raw material with glycerol distilled residue, it is characterized in that comprising the following steps:
Step is a): solid-liquid separation glycerol distilled residue, get liquid phase I and add organic solvent, after making Sodium chloride deposit wherein, solid-liquid separation obtains liquid phase II again, removing organic solvent wherein, obtain the mixture A that main component is glycerine and polyglycerol, the mass percent of wherein said glycerol distilled residue consists of sodium-chlor 20%-50%, glycerine 5%-20%, polyglycerol 5%-10%, surplus is water;
Step b): the mixture A of step a) gained is added in reactor, under metal catalyst and alkaline catalysts exist, in nitrogen atmosphere, make glycerine carry out polyreaction 2-5h at 200-240 DEG C, obtain the mixture B that the polymerization degree is 2.5-3.0, its main component is polyglycerol and mass percent is the glycerine of 2%-5%, described metal catalyst is copper, and described alkaline catalysts is salt of wormwood and/or sodium carbonate, and the quality of alkaline catalysts is the 1%-3% of mixture A quality;
Step c): to step b) add water in gained mixture B, and regulator solution pH value is between 5-7, the mass percent concentration sum obtaining glycerine and polyglycerol is the solution C of 40%-75%.
2. be the preparation method of the cement grinding aid composition of main raw material as claimed in claim 1 with glycerol distilled residue, it is characterized in that, also comprise steps d): in step c) adding alcamines cement grinding aid in gained solution C, the mass ratio of preferred described solution C and alcamines cement grinding aid is 1: (0.3-0.5).
3. be the preparation method of the cement grinding aid composition of main raw material as claimed in claim 2 with glycerol distilled residue, it is characterized in that, described alcamines cement grinding aid is trolamine and/or tri-isopropanolamine, preferred trolamine.
4. take glycerol distilled residue as the preparation method of the cement grinding aid composition of main raw material according to any one of claim 1-3, it is characterized in that, step a) described in organic solvent be ethanol.
5. take glycerol distilled residue as the preparation method of the cement grinding aid composition of main raw material according to any one of claim 1-4, it is characterized in that, step a) described in the mass ratio of organic solvent and liquid phase I be (3-8): 1.
6. take glycerol distilled residue as the preparation method of the cement grinding aid composition of main raw material according to any one of claim 1-3, it is characterized in that, step b) described in alkaline catalysts be sodium carbonate.
7. take glycerol distilled residue as the preparation method of the cement grinding aid composition of main raw material according to any one of claim 1-3, it is characterized in that, step c) in by oxalic acid regulator solution pH value.
8. the cement grinding aid composition of what preparation method according to any one of claim 1-7 obtained with glycerol distilled residue is main raw material.
9. according to claim 8 take glycerol distilled residue as the application of composition as cement grinding aid of main raw material.
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| CN105881791A (en) * | 2016-04-14 | 2016-08-24 | 福建师范大学泉港石化研究院 | Releasing agent prepared from glycerin distillation residues and preparation method thereof |
| CN105906228A (en) * | 2016-04-14 | 2016-08-31 | 福建师范大学泉港石化研究院 | Method for preparation of cement grinding aid additive from glycerin rectification residue |
| CN110282901A (en) * | 2019-07-02 | 2019-09-27 | 安徽海螺新材料科技有限公司 | A kind of cement grinding aid and preparation method thereof |
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| JP2013006736A (en) * | 2011-06-24 | 2013-01-10 | Kao Corp | Method for producing hydraulic powder |
| CN103011653A (en) * | 2012-12-13 | 2013-04-03 | 安徽珍珠水泥集团股份有限公司 | Preparation process of polyglycerol cement grinding aid |
| CN103524066A (en) * | 2013-10-21 | 2014-01-22 | 江苏聚威新材料有限公司 | Glycerin distillation residue treatment method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105881791A (en) * | 2016-04-14 | 2016-08-24 | 福建师范大学泉港石化研究院 | Releasing agent prepared from glycerin distillation residues and preparation method thereof |
| CN105906228A (en) * | 2016-04-14 | 2016-08-31 | 福建师范大学泉港石化研究院 | Method for preparation of cement grinding aid additive from glycerin rectification residue |
| CN110282901A (en) * | 2019-07-02 | 2019-09-27 | 安徽海螺新材料科技有限公司 | A kind of cement grinding aid and preparation method thereof |
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| CN104817288B (en) | 2016-08-24 |
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