CN114890694A

CN114890694A - Cement material based on aluminum ash recycling and preparation method thereof

Info

Publication number: CN114890694A
Application number: CN202210385658.3A
Authority: CN
Inventors: 王斌; 刘晓春; 刘玉林
Original assignee: Anhui Yongmaotai Environmental Protection Technology Co ltd
Current assignee: Anhui Yongmaotai Environmental Protection Technology Co ltd
Priority date: 2022-04-13
Filing date: 2022-04-13
Publication date: 2022-08-12

Abstract

The invention relates to the field of cement materials, aims to solve the problem that the existing aluminum ash cannot be reasonably utilized while polluting the environment, and particularly relates toThe cement material is added with the aluminum ash which is a waste generated in primary and secondary aluminum industries, the content of aluminum element can reach 30-55 wt%, the cement material is a renewable resource, compared with bauxite, the available aluminum component in the aluminum ash far exceeds that of high-grade bauxite, metal A l and Al N can be effectively utilized and converted into sulphoaluminate mineral, and the Ci O is a high-grade bauxite ₂ The method can provide partial silicon element required by dicalcium silicate minerals, so that the aluminum ash can replace partial bauxite to be used for producing the sulphoaluminate cement, the raw material cost can be greatly reduced, the waste recycling can be realized, the performance of the aluminum ash-based cement material can be greatly improved by adding the modifier, and the development of the aluminum ash-based cement material is promoted.

Description

Cement material based on aluminum ash recycling and preparation method thereof

Technical Field

The invention relates to the field of cement materials, in particular to a cement material based on aluminum ash recycling and a preparation method thereof.

Background

The aluminum ash is a waste produced in primary and secondary aluminum industries, the content of aluminum element can reach 30-55 wt%, and the aluminum ash is a renewable resource. Along with the rapid development of the aluminum industry in China, the yield of aluminum ash is more and more, although the emission of the aluminum ash is large, the aluminum ash is difficult to dispose, and an efficient utilization way is lacked, so that the aluminum ash is accumulated and treated at present, on one hand, the aluminum ash occupies land, pollutes soil, and granular dust also affects the atmosphere, and on the other hand, the waste of resources is caused.

In the traditional production of sulphoaluminate cement, bauxite, limestone and gypsum are used as main raw materials, and along with the rapid development of the aluminum production industry in China, the demand of the bauxite used as the raw material is larger and larger, so that the price of the bauxite is higher and higher. The high bauxite raw material price greatly increases the production cost of the traditional sulphoaluminate cement, and the searching of low-cost alternative raw materials becomes a necessary trend for the development of sulphoaluminate cement industry in the form. The available aluminum content in the aluminum ash far exceeds that of high-grade bauxite ore compared with bauxite, so that the aluminum ash can replace part of the bauxite to be used for producing the sulphoaluminate cement.

How to recycle and reasonably prepare the aluminum ash into the cement material and ensure that the cement material has good performance is the key of the invention, so that a cement material based on the recycling of the aluminum ash and a preparation method thereof are urgently needed to solve the problems.

Disclosure of Invention

In order to overcome the technical problems, the invention aims to provide a cement material based on aluminum ash recycling and a preparation method thereof: limestone, high alumina, dealkalized red mud and aluminum ash are added into a mixer to be uniformly mixed to obtain a mixture, the mixture is added into a ball mill to be ball-milled to form cement raw materials, the cement raw materials are placed into a calcining kiln to be calcined, the calcined raw materials are cooled to room temperature after being calcined to obtain cement clinker, the cement clinker and a modifier are added into the ball mill to be ball-milled to obtain the cement material based on the recycling of the aluminum ash, and the problem that the existing aluminum ash cannot be reasonably utilized while polluting the environment is solved.

The purpose of the invention can be realized by the following technical scheme:

the cement material based on the recycling of the aluminum ash comprises the following components in parts by weight:

50-80 parts of limestone, 35-55 parts of high bauxite, 22-48 parts of dealkalized red mud, 16-32 parts of aluminum ash and 3-18 parts of modifier;

the modifier is prepared by the following steps:

a1: adding maleic anhydride, glycidol and p-toluenesulfonic acid into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a reflux condenser, stirring and reacting for 1-2h under the conditions that the temperature is 70-75 ℃ and the stirring speed is 250-350r/min, introducing nitrogen for protection, stirring and dropwise adding phosphoric acid under the condition of cooling to 55-65 ℃, controlling the dropwise adding speed to be 1-2 drops/s, and continuing stirring and reacting for 3-4h after the dropwise adding is finished to obtain an intermediate 1;

the reaction principle is as follows:

reacting maleic anhydride with glycidol, hydrolyzing the maleic anhydride to form carboxyl, and then carrying out esterification reaction with hydroxyl on the glycidol so as to introduce epoxy groups, and then reacting the epoxy groups with phosphoric acid to obtain an intermediate 1 containing alkenyl, carboxyl and phosphoric acid groups;

a2: adding pentaerythritol, potassium hydroxide and deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, dropwise adding acrylonitrile while stirring under the conditions that the temperature is 20-25 ℃ and the stirring rate is 250-, obtaining an intermediate 2;

the reaction principle is as follows:

under alkaline conditions, pentaerythritol reacts with acrylonitrile, and hydroxyl on the pentaerythritol and alkenyl on the acrylonitrile undergo addition reaction to generate an intermediate 2 containing four cyano groups;

a3: adding the intermediate 2 into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, dropwise adding concentrated hydrochloric acid while stirring under the conditions that the temperature is 20-25 ℃ and the stirring rate is 250-350r/min, controlling the dropwise adding rate to be 1-2 drops/s, continuously stirring and reacting for 2-3h under the condition that the temperature is raised to 70-75 ℃ after the dropwise adding is finished, then continuously stirring and reacting for 6-7h under the condition that the temperature is lowered to 35-40 ℃, and rotationally evaporating and drying a reaction product after the reaction is finished to obtain an intermediate 3;

the reaction principle is as follows:

reacting the intermediate 2 with concentrated hydrochloric acid, and hydrolyzing the cyano group on the intermediate 2 by the concentrated hydrochloric acid to form carboxyl, thereby obtaining an intermediate 3 containing four carboxyl groups;

a4: adding ethanolamine, methyl acrylate and anhydrous methanol into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a reflux condenser tube, introducing nitrogen for protection, stirring and reacting for 30-50min under the conditions that the temperature is 20-25 ℃ and the stirring speed is 500r/min, then continuously stirring and reacting for 10-12h under the condition that the temperature is increased to 40-45 ℃, and evaporating the reaction product to dryness by rotation after the reaction is finished to obtain an intermediate 4;

the reaction principle is as follows:

performing Michael addition reaction on amino on ethanolamine and alkenyl on methyl acrylate by using ethanolamine and methyl acrylate to generate an intermediate 4 containing one hydroxyl and two ester groups;

a5: adding the intermediate 3, the intermediate 4, toluene, N-dimethylacetamide and p-toluenesulfonic acid into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a reflux condenser tube, introducing nitrogen for protection, heating to reflux under the condition that the stirring speed is 300 plus materials at 500r/min, stirring at constant temperature for reaction for 7-8h, and after the reaction is finished, rotationally evaporating a reaction product to remove toluene and N, N-dimethylacetamide to obtain an intermediate 5;

the reaction principle is as follows:

reacting the intermediate 3 with the intermediate 4, and carrying out esterification reaction on carboxyl on the intermediate 3 and hydroxyl on the intermediate 4 to form a star structure taking the intermediate 3 as a core so as to obtain an intermediate 5 with eight ester groups at the end;

a6: adding the intermediate 5, 2-bromoethanol and p-toluenesulfonic acid into a three-neck flask provided with a stirrer, a thermometer and a gas-guide tube, introducing nitrogen for protection, stirring and reacting for 7-8h under the conditions that the temperature is 110-;

the reaction principle is as follows:

reacting the intermediate 5 with 2-bromoethanol, and carrying out ester exchange reaction on an ester group on the end of the intermediate 5 and a hydroxyl group on the 2-bromoethanol, so as to introduce a bromine atom to the end of the intermediate 5, thereby obtaining an intermediate 6;

a7: adding the intermediate 1, the intermediate 6, cuprous bromide and deionized water into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a constant-pressure dropping funnel, introducing nitrogen for protection, stirring while simultaneously dropwise adding an acrylic acid solution and an ammonium persulfate solution under the conditions that the temperature is 65-75 ℃ and the stirring rate is 500r/min, controlling the dropwise adding rate to be 1-2 drops/s, continuously stirring for reacting for 2-3h after the dropwise adding is finished, cooling the reaction product to room temperature after the reaction is finished, and then adjusting the pH to be 6-8 by using a sodium hydroxide solution to obtain the cement modifier.

The reaction principle is as follows:

ammonium persulfate is used as an initiator, cuprous bromide is used as a catalyst, the intermediate 1, the intermediate 6 and acrylic acid react to form a macromolecular polymer through the polymerization reaction of the acrylic acid and the intermediate 1, then, a bromine atom on the intermediate 6 and the polymer generate a nucleophilic substitution reaction, and therefore, a plurality of polymer molecular chains are grafted to the intermediate 6, and the modifying agent with the star-shaped structure containing a large number of phosphate groups and carboxylic acid groups is obtained.

As a further scheme of the invention: the dosage ratio of the maleic anhydride, the glycidol and the p-toluenesulfonic acid in the step A1 is 0.12 mol: 0.1mol: 0.15-0.3 g.

As a further scheme of the invention: the dosage ratio of the pentaerythritol, the potassium hydroxide, the deionized water, the acrylonitrile, the chloroform and the distilled water in the step A2 is 10 g: 0.01 mol:1 mL: 25mL of: 40-50 mL: 40-50mL, wherein the molar concentration of the hydrochloric acid solution is 1mol/L, and the volume fraction of the ethanol solution is 90-95%.

As a further scheme of the invention: the ratio of the amount of intermediate 2 to concentrated hydrochloric acid in step a3 was 10 mmol: 15-20mL, and the mass fraction of the concentrated hydrochloric acid is 36-38%.

As a further scheme of the invention: the dosage ratio of the ethanolamine, the methyl acrylate and the anhydrous methanol in the step A4 is 10 mmol: 20 mmol: 40-50 mL.

As a further scheme of the invention: the amounts of intermediate 3, intermediate 4, toluene, N-dimethylacetamide and p-toluenesulfonic acid in step a5 were 10 mmol: 40mmol of: 20-40 mL: 40-50 mL: 0.6-1.8 g.

As a further scheme of the invention: the amount of the intermediate 5, 2-bromoethanol and p-toluenesulfonic acid in step a6 used was 10 mmol: 100 mmol: 1.5-3.5 g.

As a further scheme of the invention: the acrylic acid solution in the step A7 is a mixture of acrylic acid and deionized water according to a mass ratio of 1:1, the mass fraction of the ammonium persulfate solution is 10-15%, and the use ratio of the intermediate 1, the intermediate 6, cuprous bromide, deionized water, acrylic acid and ammonium persulfate is 0.1mol:0.22 mol: 0.5-1.0g 100-200 mL: 1mol:1.5-2.5 g.

As a further scheme of the invention: the preparation method of the cement material based on the recycling of the aluminum ash comprises the following steps:

the method comprises the following steps: weighing 50-80 parts of limestone, 35-55 parts of high-alumina bauxite, 22-48 parts of dealkalized red mud, 16-32 parts of aluminum ash and 3-18 parts of modifier for later use;

step two: adding limestone, high bauxite, dealkalized red mud and aluminum ash into a mixer, and uniformly mixing to obtain a mixture;

step three: adding the mixture into a ball mill for ball milling to form cement raw materials;

step four: placing the cement raw material into a calcining kiln, calcining at 1250-1450 ℃ for 20-40min, and cooling to room temperature after calcining to obtain cement clinker;

step five: adding the cement clinker and the modifier into a ball mill, and performing ball milling until the grinding fineness is 0.05-0.1mm to obtain the cement material based on the aluminum ash recycling.

The invention has the beneficial effects that:

the invention relates to a cement material based on aluminum ash recycling and a preparation method thereof.A limestone, bauxite, dealkalized red mud and aluminum ash are added into a mixer to be uniformly mixed to obtain a mixture, the mixture is added into a ball mill to be ball-milled to form cement raw meal, the cement raw meal is placed into a calcining kiln to be calcined, the calcining is completed and cooled to room temperature to obtain cement clinker, and the cement clinker and a modifier are added into the ball mill to be ball-milled to obtain the cement material based on aluminum ash recycling; the cement material is added with aluminum ash which is a waste produced in primary and secondary aluminum industries, the content of aluminum element can reach 30-55 wt%, the cement material is a renewable resource, compared with bauxite, the available aluminum component in the aluminum ash far exceeds that of high-grade bauxite, metal Al and AlN can be effectively utilized and converted into sulphoaluminate minerals, SiO is a SiO metal, and the like ₂ Can provide partial silicon element required by dicalcium silicate minerals, so that the aluminum ash can replace partial bauxite to be used for producing sulphoaluminate cement, not only can the raw material cost be greatly reduced, but also the waste can be recycled, and the aluminum can be greatly improved by adding the modifierThe performance of the cement material promotes the development of the aluminum cement material;

preparing a modifier in the process of preparing the cement material based on the recycling of the aluminum ash, utilizing maleic anhydride and glycidol to react so as to introduce an epoxy group, then reacting the epoxy group with phosphoric acid to obtain an intermediate 1 containing an alkenyl group, a carboxyl group and a phosphoric acid group, utilizing pentaerythritol to react with acrylonitrile to generate an intermediate 2 containing four cyano groups, utilizing the intermediate 2 to react with concentrated hydrochloric acid to obtain an intermediate 3 containing four carboxyl groups, utilizing ethanolamine and methyl acrylate to react so as to generate an intermediate 4 containing a hydroxyl group and two ester groups, and utilizing the intermediate 3 to react with the intermediate 4 to obtain an intermediate 5 containing eight ester groups at the end part; reacting the intermediate 5 with 2-bromoethanol to obtain an intermediate 6, reacting the intermediate 1, the intermediate 6 with acrylic acid, polymerizing the acrylic acid and the intermediate 1 to form a macromolecular polymer, and grafting a plurality of polymer molecular chains onto the intermediate 6 to obtain a star-structured modifier containing a large amount of phosphate groups and carboxylic acid groups; after the modifier is added into a cement material, carboxylate radicals and phosphate radicals on a molecular chain can be adsorbed on positive charges on the surfaces of cement particles, so that the surface of the cement particles is charged with negative charges to form an electric double layer structure, and when the cement particles are close to each other, the surfaces of the cement flocculation structure are charged with negative charges and mutually repel, so that the cement flocculation structure can not be aggregated together, and then water molecules wrapped in the cement flocculation structure can be released, thereby having the effects of reducing water and dispersing cement particles, increasing the fluidity of cement paste, leading concrete not to be isolated and bleeding, having good slump constant and slump constant retentivity and excellent mechanical property, the modifier can link a plurality of polymer molecular chains together, so that the mechanical property of the modifier is improved, a large amount of carboxylate radicals and phosphate radicals are increased, the effect of dispersing cement particles is further enhanced, and the property of cement is further improved.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1:

this embodiment is a method for preparing a modifier, including the following steps:

a1: adding 0.12mol of maleic anhydride, 0.1mol of glycidol and 0.15-0.3g of p-toluenesulfonic acid into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a reflux condenser, stirring and reacting for 1h at the temperature of 70 ℃ and the stirring speed of 250r/min, introducing nitrogen for protection, cooling to 55 ℃, stirring while dropwise adding phosphoric acid, controlling the dropwise adding speed to be 1 drop/s, and continuously stirring and reacting for 3h after the dropwise adding is finished to obtain an intermediate 1;

a2: adding 10g of pentaerythritol, 0.01mol of potassium hydroxide and 1mL of deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, dropwise adding 25mL of acrylonitrile under the conditions of the temperature of 20 ℃ and the stirring rate of 250r/min while stirring, controlling the dropwise adding rate to be 1 drop/s, continuously stirring and reacting for 10 hours after the dropwise adding is finished, then continuously stirring and reacting for 6 hours under the condition of heating to 35 ℃, cooling a reaction product to room temperature after the reaction is finished, then adding 40mL of chloroform and 40mL of distilled water, stirring for 10 minutes, then adjusting the pH to 7 by using a hydrochloric acid solution with the molar concentration of 1mol/L, standing and layering, drying an organic phase by using anhydrous sodium sulfate, then evaporating and concentrating, recrystallizing by using an ethanol solution with the volume fraction of 90%, carrying out vacuum suction filtration, placing a filter cake in a vacuum drying box to be constant in weight, obtaining an intermediate 2;

a3: adding 10mmol of the intermediate 2 into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, dropwise adding 15mL of concentrated hydrochloric acid with the mass fraction of 36% while stirring at the temperature of 20 ℃ and the stirring rate of 250r/min, controlling the dropwise adding rate to be 1 drop/s, continuously stirring and reacting for 2 hours under the condition of heating to 70 ℃ after dropwise adding is finished, then continuously stirring and reacting for 6 hours under the condition of cooling to 35 ℃, and rotationally evaporating a reaction product to dryness after the reaction is finished to obtain an intermediate 3;

a4: adding 10mmol of ethanolamine, 20mmol of methyl acrylate and 40mL of anhydrous methanol into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a reflux condenser tube, introducing nitrogen for protection, stirring and reacting for 30min under the conditions that the temperature is 20 ℃ and the stirring speed is 300r/min, then continuing stirring and reacting for 10h under the condition that the temperature is raised to 40 ℃, and evaporating the reaction product to dryness in a rotating manner after the reaction is finished to obtain an intermediate 4;

a5: adding 10mmol of the intermediate 3, 40mmol of the intermediate 4, 20mL of toluene, 40mLN, N-dimethylacetamide and 0.6g of p-toluenesulfonic acid into a three-neck flask provided with a stirrer, a thermometer, a gas guide tube and a reflux condenser tube, introducing nitrogen for protection, heating to reflux under the condition that the stirring speed is 300r/min, stirring at constant temperature for reaction for 7 hours, and performing rotary evaporation on a reaction product after the reaction is finished to remove toluene and N, N-dimethylacetamide to obtain an intermediate 5;

a6: adding 10mmol of intermediate 5, 100mmol of 2-bromoethanol and 1.5g of p-toluenesulfonic acid into a three-neck flask provided with a stirrer, a thermometer and an air guide tube, introducing nitrogen for protection, stirring and reacting for 7 hours at the temperature of 110 ℃ and at the stirring rate of 300r/min, and after the reaction is finished, carrying out rotary evaporation on a reaction product to remove redundant 2-bromoethanol to obtain an intermediate 6;

a7: adding 0.1mol of the intermediate 1, 0.22mol of the intermediate 6, 0.5g of cuprous bromide and 100mL of deionized water into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a constant-pressure dropping funnel, introducing nitrogen for protection, simultaneously dropwise adding an acrylic acid solution formed by mixing 1mol of acrylic acid and 72g of deionized water and an ammonium persulfate solution with the mass fraction of 10% and formed by dissolving 1.5g of ammonium persulfate in the deionized water under the conditions that the temperature is 65 ℃ and the stirring speed is 300r/min, controlling the dropwise adding speed to be 1 d/s, continuously stirring for reaction for 2h after the dropwise adding is finished, cooling a reaction product to room temperature after the reaction is finished, and then adjusting the pH to be 6 by using a sodium hydroxide solution to obtain the cement modifier.

Example 2:

the embodiment is a preparation method of a modifier, which comprises the following steps:

a1: adding 0.12mol of maleic anhydride, 0.1mol of glycidol and 0.21g of p-toluenesulfonic acid into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a reflux condenser, stirring and reacting for 1.5h under the conditions that the temperature is 72 ℃ and the stirring speed is 300r/min, then introducing nitrogen for protection, cooling to 60 ℃, stirring while dropwise adding phosphoric acid, controlling the dropwise adding speed to be 1 drop/s, and continuing stirring and reacting for 3.5h after the dropwise adding is finished to obtain an intermediate 1;

a2: adding 10g of pentaerythritol, 0.01mol of potassium hydroxide and 1mL of deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, dropwise adding 25mL of acrylonitrile under the conditions that the temperature is 22 ℃ and the stirring rate is 300r/min, controlling the dropping rate to be 1 drop/s, continuously stirring and reacting for 11h after the dropwise adding is finished, then continuously stirring and reacting for 6.5h under the condition that the temperature is raised to 38 ℃, cooling a reaction product to the room temperature after the reaction is finished, then adding 45mL of chloroform and 45mL of distilled water, stirring for 13min, then adjusting the pH to 7 by using a hydrochloric acid solution with the molar concentration of 1mol/L, standing, layering, drying an organic phase by using anhydrous sodium sulfate, then recrystallizing by using an ethanol solution with the volume fraction of 92% after evaporation and concentration, carrying out vacuum filtration, placing a filter cake in a vacuum drying oven to constant weight, obtaining an intermediate 2;

a3: adding 10mmol of the intermediate 2 into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, dropwise adding 18mL of concentrated hydrochloric acid with the mass fraction of 37% while stirring at the temperature of 22 ℃ and the stirring speed of 300r/min, controlling the dropwise adding speed to be 1 drop/s, continuously stirring and reacting for 2.5 hours under the condition of heating to 72 ℃ after dropwise adding, then continuously stirring and reacting for 6.5 hours under the condition of cooling to 38 ℃, and rotationally evaporating and drying a reaction product after the reaction is finished to obtain an intermediate 3;

a4: adding 10mmol of ethanolamine, 20mmol of methyl acrylate and 45mL of anhydrous methanol into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a reflux condenser tube, introducing nitrogen for protection, stirring and reacting for 40min under the conditions that the temperature is 22 ℃ and the stirring speed is 400r/min, then continuing stirring and reacting for 11h under the condition that the temperature is raised to 42 ℃, and evaporating the reaction product to dryness in a rotating manner after the reaction is finished to obtain an intermediate 4;

a5: adding 10mmol of the intermediate 3, 40mmol of the intermediate 4, 30mL of toluene, 45mLN, N-dimethylacetamide and 1.2g of p-toluenesulfonic acid into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a reflux condenser tube, introducing nitrogen for protection, heating to reflux under the condition of stirring speed of 400r/min, stirring at constant temperature for reaction for 7.5 hours, and after the reaction is finished, rotationally evaporating a reaction product to remove toluene and N, N-dimethylacetamide to obtain an intermediate 5;

a6: adding 10mmol of the intermediate 5, 100mmol of 2-bromoethanol and 2.5g of p-toluenesulfonic acid into a three-neck flask provided with a stirrer, a thermometer and a gas guide tube, introducing nitrogen for protection, stirring and reacting for 7.5 hours at the temperature of 120 ℃ and the stirring speed of 400r/min, and after the reaction is finished, performing rotary evaporation on a reaction product to remove redundant 2-bromoethanol to obtain an intermediate 6;

a7: adding 0.1mol of the intermediate 1, 0.22mol of the intermediate 6, 0.8g of cuprous bromide and 150mL of deionized water into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a constant-pressure dropping funnel, introducing nitrogen for protection, simultaneously dropwise adding an acrylic acid solution formed by mixing 1mol of acrylic acid and 72g of deionized water and an ammonium persulfate solution with the mass fraction of 12% and formed by dissolving 2.0g of ammonium persulfate in the deionized water under the conditions that the temperature is 70 ℃ and the stirring speed is 400r/min, controlling the dropwise adding speed to be 1 d/s, continuously stirring for reaction for 2.5h after the dropwise adding is finished, cooling a reaction product to room temperature after the reaction is finished, and then adjusting the pH to be 7 by using a sodium hydroxide solution to obtain the cement modifier.

Example 3:

a1: adding 0.12mol of maleic anhydride, 0.1mol of glycidol and 0.3g of p-toluenesulfonic acid into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a reflux condenser, stirring and reacting for 2h under the conditions that the temperature is 75 ℃ and the stirring speed is 350r/min, then introducing nitrogen for protection, adding phosphoric acid dropwise under the condition of cooling to 65 ℃ while stirring, controlling the dropping speed to be 2 drops/s, and continuing stirring and reacting for 4h after the dropping is finished to obtain an intermediate 1;

a2: adding 10g of pentaerythritol, 0.01mol of potassium hydroxide and 1mL of deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, dropwise adding 25mL of acrylonitrile under the conditions of 25 ℃ and 350r/min of stirring speed, controlling the dropwise adding speed to be 2 drops/s, continuously stirring and reacting for 12 hours after the dropwise adding is finished, then continuously stirring and reacting for 7 hours under the condition of heating to 40 ℃, cooling a reaction product to room temperature after the reaction is finished, then adding 50mL of chloroform and 50mL of distilled water, stirring for 15 minutes, then adjusting the pH to 7 by using a hydrochloric acid solution with the molar concentration of 1mol/L, standing and layering, drying an organic phase by using anhydrous sodium sulfate, then evaporating and concentrating, recrystallizing by using an ethanol solution with the volume fraction of 95%, carrying out vacuum suction filtration, placing a filter cake in a vacuum drying oven to constant weight, obtaining an intermediate 2;

a3: adding 10mmol of the intermediate 2 into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, dropwise adding 20mL of concentrated hydrochloric acid with the mass fraction of 38% while stirring at the temperature of 25 ℃ and the stirring speed of 350r/min, controlling the dropwise adding speed to be 2 drops/s, continuously stirring and reacting for 3 hours under the condition of heating to 75 ℃ after dropwise adding, then continuously stirring and reacting for 7 hours under the condition of cooling to 40 ℃, and rotationally evaporating and drying a reaction product after the reaction is finished to obtain an intermediate 3;

a4: adding 10mmol of ethanolamine, 20mmol of methyl acrylate and 50mL of anhydrous methanol into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a reflux condenser tube, introducing nitrogen for protection, stirring and reacting for 50min under the conditions that the temperature is 25 ℃ and the stirring speed is 500r/min, then continuing stirring and reacting for 12h under the condition that the temperature is raised to 45 ℃, and evaporating the reaction product to dryness in a rotating manner after the reaction is finished to obtain an intermediate 4;

a5: adding 10mmol of the intermediate 3, 40mmol of the intermediate 4, 40mL of toluene, 50mLN, N-dimethylacetamide and 1.8g of p-toluenesulfonic acid into a three-neck flask provided with a stirrer, a thermometer, a gas guide tube and a reflux condenser tube, introducing nitrogen for protection, heating to reflux under the condition of stirring speed of 500r/min, stirring at constant temperature for 8 hours, and after the reaction is finished, rotationally evaporating a reaction product to remove toluene and N, N-dimethylacetamide to obtain an intermediate 5;

a6: adding 10mmol of intermediate 5, 100mmol of 2-bromoethanol and 3.5g of p-toluenesulfonic acid into a three-neck flask provided with a stirrer, a thermometer and a gas guide tube, introducing nitrogen for protection, stirring and reacting for 8 hours at the temperature of 125 ℃ and the stirring speed of 500r/min, and after the reaction is finished, rotationally evaporating a reaction product to remove redundant 2-bromoethanol to obtain an intermediate 6;

a7: adding 0.1mol of the intermediate 1, 0.22mol of the intermediate 6, 1.0g of cuprous bromide and 200mL of deionized water into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a constant-pressure dropping funnel, introducing nitrogen for protection, simultaneously dropwise adding an acrylic acid solution formed by mixing 1mol of acrylic acid and 72g of deionized water and an ammonium persulfate solution with the mass fraction of 15% and formed by dissolving 2.5g of ammonium persulfate in the deionized water under the conditions that the temperature is 75 ℃ and the stirring speed is 500r/min, controlling the dropwise adding speed to be 2 drops/s, continuously stirring for reaction for 3 hours after the dropwise adding is finished, cooling a reaction product to room temperature after the reaction is finished, and then adjusting the pH to be 8 by using a sodium hydroxide solution to obtain the cement modifier.

Example 4:

the embodiment is a preparation method of a cement material based on aluminum ash recycling, which comprises the following steps:

the method comprises the following steps: weighing 50 parts of limestone, 35 parts of high bauxite, 22 parts of dealkalized red mud, 16 parts of aluminum ash and 3 parts of modifier from example 1 according to parts by weight for later use;

step four: placing the cement raw material into a calcining kiln, calcining at 1250 ℃ for 20min, cooling to room temperature after calcining is completed, and obtaining cement clinker;

step five: adding the cement clinker and the modifier into a ball mill, and performing ball milling until the grinding fineness is 0.1mm to obtain the cement material based on the aluminum ash recycling.

Example 5:

the method comprises the following steps: weighing 65 parts of limestone, 45 parts of high bauxite, 35 parts of dealkalized red mud, 24 parts of aluminum ash and 11 parts of modifier from example 2 according to parts by weight for later use;

step four: placing the cement raw material into a calcining kiln, calcining at 1350 ℃ for 30min, cooling to room temperature after calcining is completed, and obtaining cement clinker;

step five: adding the cement clinker and the modifier into a ball mill, and performing ball milling until the grinding fineness is 0.08mm to obtain the cement material based on the aluminum ash recycling.

Example 6:

the method comprises the following steps: weighing 80 parts of limestone, 55 parts of high alumina bauxite, 48 parts of dealkalized red mud, 32 parts of aluminum ash and 18 parts of modifier from example 3 according to parts by weight for later use;

step four: placing the cement raw material into a calcining kiln, calcining at 1450 ℃ for 40min, and cooling to room temperature after calcining to obtain cement clinker;

Comparative example 1:

comparative example 1 differs from example 6 in that no modifier is added.

Comparative example 2:

comparative example 2 differs from example 6 in that polynaphthalene formaldehyde sulfonic acid sodium salt is used instead of the modifier.

Comparative example 3:

comparative example 3 is the sulphoaluminate cement produced from aluminium ash of application No. 201410105340.0.

Comparative example 4:

comparative example 4 differs from comparative example 3 in that the modifier of example 3 was added.

The cement materials in examples 4-6 and comparative examples 1-4 are tested by referring to GB/T50080-2002 'common concrete mixture performance test method', the water reducing rates of examples 4-6 and comparative example 2 are calculated by using comparative example 1, the water reducing rate of comparative example 4 is calculated by using comparative example 3, the mechanical properties of the concrete are tested, and the test results are shown in the following table:

sample (I)	Water reduction rate%	7d compressive strength, MPa	28d compressive strength, MPa	Degree of collapse mm
					Example 4	44.7	36.7	59.1	215
Example 5	45.9	38.2	62.7	220
					Example 6	48.0	39.8	65.3	220
Comparative example 1	/	19.6	28.9	200
					Comparative example 2	32.1	31.7	42.8	210
Comparative example 3	/	18.1	27.4	200
					Comparative example 4	47.5	37.9	61.6	215

Referring to the data in the table, according to the comparison between the example and the comparative examples 1 to 2, it can be known that the addition of the modifier and the sodium polynaphthalenesulfonate can improve the mechanical properties of the cement material and reduce the water consumption, but the modifier has a better performance enhancing effect than the sodium polynaphthalenesulfonate, according to the comparison between the example and the comparative example 3, the cement material in the application has better performance than the cement material in the prior art, and according to the comparison between the comparative example 3 and the comparative example 4, the use of the modifier can modify the existing cement material, and has an obvious effect on improving the performance of the cement material.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.

Claims

1. The cement material based on the recycling of the aluminum ash is characterized by comprising the following components in parts by weight:

the modifier is prepared by the following steps:

a1: adding maleic anhydride, glycidol and p-toluenesulfonic acid into a three-neck flask, stirring for reaction, then dropwise adding phosphoric acid while stirring, and continuing stirring for reaction after dropwise adding is finished to obtain an intermediate 1;

a2: adding pentaerythritol, potassium hydroxide and deionized water into a three-neck flask, dropwise adding acrylonitrile while stirring, continuously stirring for reaction after the dropwise addition is finished, heating for continuous stirring for reaction, cooling a reaction product after the reaction is finished, adding chloroform and distilled water, then adjusting pH, standing, layering, drying an organic phase, recrystallizing, carrying out vacuum filtration, and drying a filter cake to constant weight to obtain an intermediate 2;

a3: adding the intermediate 2 into a three-neck flask, dropwise adding concentrated hydrochloric acid while stirring, heating after dropwise adding, continuously stirring for reaction, cooling, continuously stirring for reaction, and drying a reaction product after the reaction is finished to obtain an intermediate 3;

a4: adding ethanolamine, methyl acrylate and anhydrous methanol into a three-neck flask, stirring for reaction, heating, continuing stirring for reaction, and drying a reaction product after the reaction is finished to obtain an intermediate 4;

a5: adding the intermediate 3, the intermediate 4, toluene, N-dimethylacetamide and p-toluenesulfonic acid into a three-neck flask, heating to reflux, stirring at constant temperature for reaction, and performing rotary evaporation on a reaction product after the reaction is finished to obtain an intermediate 5;

a6: adding the intermediate 5, 2-bromoethanol and p-toluenesulfonic acid into a three-neck flask, stirring for reaction, and performing rotary evaporation on a reaction product after the reaction is finished to obtain an intermediate 6;

a7: adding the intermediate 1, the intermediate 6, cuprous bromide and deionized water into a three-neck flask, stirring while simultaneously dropwise adding an acrylic acid solution and an ammonium persulfate solution, continuing stirring for reaction after dropwise adding, cooling a reaction product after the reaction is finished, and then adjusting the pH value to obtain the cement modifier.

2. The cement material based on aluminum ash recycling according to claim 1, wherein the dosage ratio of maleic anhydride, glycidol and p-toluenesulfonic acid in the step A1 is 0.12 mol: 0.1mol: 0.15-0.3 g.

3. The aluminum ash recycling-based cement material as claimed in claim 1, wherein the amount ratio of pentaerythritol, potassium hydroxide, deionized water, acrylonitrile, chloroform and distilled water in step A2 is 10 g: 0.01 mol: 1mL of: 25mL of: 40-50 mL: 40-50mL, wherein the molar concentration of the hydrochloric acid solution is 1mol/L, and the volume fraction of the ethanol solution is 90-95%.

4. The cement material based on aluminum ash recycling according to claim 1, wherein the ratio of the amount of the intermediate 2 to the amount of the concentrated hydrochloric acid in the step A3 is 10 mmol: 15-20mL, and the mass fraction of the concentrated hydrochloric acid is 36-38%.

5. The cement material based on aluminum ash recycling according to claim 1, wherein the amount ratio of the ethanolamine, the methyl acrylate and the anhydrous methanol in the step A4 is 10 mmol: 20 mmol: 40-50 mL.

6. The aluminum ash recycling-based cement material as claimed in claim 1, wherein the amount of intermediate 3, intermediate 4, toluene, N-dimethylacetamide and p-toluenesulfonic acid used in step a5 is 10 mmol: 40mmol of: 20-40 mL: 40-50 mL: 0.6-1.8 g.

7. The cement material based on the recycling of aluminum ash as claimed in claim 1, wherein the amount of the intermediate 5, 2-bromoethanol and p-toluenesulfonic acid in the step A6 is 10 mmol: 100 mmol: 1.5-3.5 g.

8. The aluminum ash recycling-based cement material as claimed in claim 1, wherein the acrylic acid solution in the step A7 is a mixture of acrylic acid and deionized water in a mass ratio of 1:1, the mass fraction of the ammonium persulfate solution is 10-15%, and the use ratio of the intermediate 1, the intermediate 6, cuprous bromide, deionized water, acrylic acid and ammonium persulfate is 0.1mol:0.22 mol: 0.5-1.0g 100-200 mL: 1mol:1.5-2.5 g.

9. The method for preparing the cement material based on the recycling of the aluminum ash according to claim 1, characterized by comprising the following steps: